WO2024099888A1 - Procédé amélioré de conversion d'aminonitriles modifiés en amino-alcools correspondants - Google Patents

Procédé amélioré de conversion d'aminonitriles modifiés en amino-alcools correspondants Download PDF

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WO2024099888A1
WO2024099888A1 PCT/EP2023/080631 EP2023080631W WO2024099888A1 WO 2024099888 A1 WO2024099888 A1 WO 2024099888A1 EP 2023080631 W EP2023080631 W EP 2023080631W WO 2024099888 A1 WO2024099888 A1 WO 2024099888A1
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compound
formula
transition metal
metal catalyst
homogeneous transition
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Carolin Limburg
Martin Ernst
Kirsten Dahmen
Thomas Schaub
Sebastian Haupt
Thomas Schmidt
Anika RITTER
Rocco Paciello
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • 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
    • B01J31/20—Carbonyls
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/10—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • C07C231/24—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • 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
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/0247—Tripodal ligands, e.g. comprising the tris(pyrazolyl)borate skeleton, "tpz", neutral analogues thereof by CH/BH exchange or anionic analogues of the latter by exchange of one of the pyrazolyl groups for an anionic complexing group such as carboxylate or -R-Cp
    • 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
    • B01J2531/821—Ruthenium

Definitions

  • the present invention relates to a process for converting an N-formyl-protected aminonitrile compound to the corresponding N-formyl-protected amino alcohol or amino alcohol compound or mixtures thereof by reductive hydrolysis in the presence of water, hydrogen and a homogeneous transition metal catalyst, which is a coordination complex composed of one or more Ru coordination centers and at least one tri-dentate ligand having 3 phosphine functions but no other heteroatoms, and which is brought into contact with a chloride source.
  • the homogeneous transition metal catalyst exhibits a particular good stability, activity, selectivity and long lifetime.
  • the present invention also relates to a homogeneous transition metal catalyst which is a coordination complex composed of one or more Ru coordination centers, at least one chloride ligand and at least one 1 , 1 , 1 -T ri s(b is (3 , 5- dimethylphenyl)phosphinomethyl)ethane ligand, a tri-dentate ligand having 3 phosphine functions but no other heteroatoms.
  • the nitration step of this synthesis route is not very selective, and it is associated with safety issues as some nitroalkanes are shock-sensitive and can explode when not treated properly.
  • WO 2020/094454 A recently suggested a synthesis route which is based on the reductive nitrile hydrolysis of the corresponding nitrile compound.
  • Central step of this approach is the reductive hydrolysis of the nitrile group of the starting compound.
  • the nitrile is hydrogenated in the presence of a homogeneous transition metal catalyst and water to form the corresponding alcohol and ammonia as a byproduct.
  • an N-formyl-protected aminonitrile is employed as starting compound and such N-formyl-aminonitrile is converted either (i) directly in a one-step process to the desired amino alcohol or (ii) in a two-step process with the formation of the corresponding N-formyl-amino alcohol as intermediate which is deprotected to the desired amino alcohol in a separate second step, as shown below.
  • the reductive hydrolysis of the nitrile group for the formation of the corresponding alcohol group in the one-step process or the first step of the two-step process is carried out in the presence of hydrogen, water and preferably with a ruthenium (Ru) based complex as homogeneous transition metal catalyst.
  • the deprotection of the N-formyl protected amino group can be carried out under the same conditions and with the same catalyst (one-step-process or second step of the two-step process) or under different conditions with a different catalyst (separate second step of the two- step process), e.g., by means of a hydrolysis or hydrogenation using a hydrolysis or hydrogenation catalyst.
  • ruthenium (Ru) based complex as homogeneous catalyst characterized by an extended catalyst lifetime.
  • the present invention accordingly relates to the provision of a process for manufacturing an amino alcohol compound of the formula I
  • step a) applying hydrogen to the reaction mixture which comprises the compound of the formula III, a homogeneous transition metal catalyst and water, to convert the compound of the formula III at least partially to the compound of the formula I or the formula II or a mixture thereof, b) separating the mixture obtained in step a) into a first fraction comprising compound of the formula I or compound of the formula II or a mixture thereof potentially together with unreacted compound of the formula III and a second fraction comprising the homogeneous transition metal catalyst, potentially together with compound of the formula II and/or unreacted compound of the formula III, c) collecting the first fraction of step
  • the cleavage of the N- formyl group is significantly slower than the reductive hydrolysis of the nitrile function. This is essential because otherwise a significant portion of unprotected nitrile would be formed which would decompose in a reverse Strecker reaction.
  • the yield of the final amino alcohol compound of the formula I is usually significantly smaller than the yield of the intermediate N-formyl-protected amino alcohol compound of the formula II, particularly if the reaction time is comparably short.
  • the process of the invention for manufacturing an amino alcohol compound of the formula I or an N-formyl-protected amino alcohol compound of the formula II, or a mixture thereof by converting an N-formyl-protected aminonitrile compound of the formula III is incorporated in a process for manufacturing an amino alcohol compound of the formula I, characterized in that
  • step a) results in the formation of a mixture comprising the product compound of the formula I, potentially together with unreacted compound of the formula III and/or intermediate N-formyl-protected amino alcohol compound of the formula II,
  • step b) the mixture resulting from step a) is separated from the homogeneous transition metal catalyst within step b),
  • step c) the fraction resulting from step b) including the product compound of the formula I is collected and optionally purified from potentially formed intermediate compound of the formula II and/or potentially present unreacted starting compound of the formula III by the means of a fractionated distillation within step c), and
  • step c1 the potentially formed intermediate compound of the formula II and/or the potentially unreacted starting compound of the formula III separated from the product compound of the formula I by step c) are recycled partially or fully into the reductive hydrolysis of step a).
  • the present invention also relates to a process for manufacturing an amino alcohol compound of the formula I wherein R1 and R2 are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, comprising the steps of a) applying hydrogen to the reaction mixture which comprises an N-formyl-protected aminonitrile compound of the formula III a homogeneous transition metal catalyst and water, to convert the compound of the formula III at least partially to the compound of the formula I, b) separating the mixture obtained in step a) into a first fraction comprising the compound of the formula I, potentially together with unreacted compound of the formula III and/or intermediate N-formyl-protected amino alcohol compound of the formula II and a second fraction comprising the homogeneous transition metal catalyst, potentially together with unreacted compound of the formula III and/or intermediate compound of the formula II, c) collecting the first fraction of step b) and optionally purifying the product compound of the formula I from potentially present intermediate compound of the formula II and/or potentially present un
  • the process of the invention for manufacturing an amino alcohol compound of the formula I or an N-formyl-protected amino alcohol compound of the formula II, or a mixture thereof by converting an N-formyl-protected aminonitrile compound of the formula III is incorporated in a process for manufacturing an amino alcohol compound of the formula I, characterized in that
  • step a) results in the formation of a mixture comprising the intermediate N-formyl-protected amino alcohol compound of the formula II, potentially together with unreacted compound of the formula III and/or the product compound of the formula I,
  • step b) the mixture resulting from step a) is separated from the homogeneous transition metal catalyst within step b),
  • step c) the fraction resulting from step b) including the intermediate compound of the formula II is collected and optionally purified from potentially present unreacted starting compound of the formula III by the means of a fractionated distillation within step c),
  • step c1) the potentially present unreacted starting compound of the formula III separated from the intermediate compound of the formula II by step c) is recycled partially or fully into the reductive hydrolysis of step a) and
  • step c2) the intermediate N-formyl-protected amino alcohol compound of the formula II in the fraction resulting from step b) and collected in step c) is converted into the product compound of the formula I by hydrolysis or hydrogenation of the N-formyl group, optionally followed by a purification by distillation of the resulting product compound of the formula I.
  • the present invention also relates to a process for manufacturing an amino alcohol compound of the formula I
  • step a) applying hydrogen to the reaction mixture which comprises an N-formyl-protected aminonitrile compound of the formula III a homogeneous transition metal catalyst and water, to convert the compound of the formula III at least partially to the intermediate N-formyl-protected amino alcohol compound of the formula II b) separating the mixture obtained in step a) into a first fraction comprising the intermediate compound of the formula II, potentially together with unreacted starting compound of the formula III and/or product compound of the formula I, and a second fraction comprising the homogeneous transition metal catalyst, potentially together with intermediate compound of the formula II and/or unreacted starting compound of the formula III, c) collecting the first fraction of step b) and optionally purifying the intermediate compound of the formula II from potentially present unreacted starting compound of the formula III by the means of a fractionated distillation, c1 ) optionally recycling
  • step c) the purification of step c) and recycling of step c1) is mandatory.
  • step c2) In a particular embodiment of the process for manufacturing an amino alcohol compound of the formula I according to the invention employing a separate converting step c2), the purification of step c2) is mandatory.
  • the recycling of the homogeneous transition metal catalyst of step d) is mandatory.
  • at least 50% b.w. of the homogeneous transition metal catalyst (based on the amount of the transition metal) separated as second fraction of step b) is recycled into the into the reaction mixture of step a).
  • the recycling the homogeneous transition metal catalyst of step d) is mandatory and carried out as a catalyst preformation in the presence of water and a chloride source at a temperature in the range from 160 to 250 °C, preferably in the range from 180 to 220 °C and under a hydrogen pressure, preferably of at least 40 bara, more preferably of at least 80 bara for a time period (average residence time in the case of a continuous process) of preferably at least 6 h, more preferably of at least 10 h.
  • the chloride source is employed in an amount of at least 2-fold of the ruthenium content, more preferably in the range from 2- to 3-fold of the ruthenium content based on the molar ratio of chloride per ruthenium.
  • the content of water in the mixture of step d) is preferably in the range from 1 to 50% b.w., more preferably in the range from 1 to 30% b.w., and most preferably in the range from 1 to 20% b.w., based on the total mixture.
  • Such a preformation step allows for a particular effective recycling of the homogeneous transition metal catalyst by replacing inactivating ligands, which are formed during the process, with chloride ions.
  • alkyl refers to a linear or branched, saturated hydrocarbon group, without any hetero atom, e.g., an ethyl residue.
  • aryl refers to a hydrocarbon radical without any hetero atom, but optionally substituted with one or more alkyl radicals, e.g., a phenyl residue or a tolyl residue.
  • arylalkyl refers to aryl-comprising residues whose aryl radical is linked via an alkyl chain of at least one carbon atom to the remainder of the molecule, e.g., a benzyl residue.
  • heteroatom refers to any atom other than carbon atom or hydrogen atom.
  • room temperature refers to a temperature of 23 °C.
  • step c2) The conversion of the intermediate N-formyl-protected amino alcohol compound of the formula II into the product compound of the formula I by hydrolysis or hydrogenation of the N-formyl group in step c2) is carried out in the presence of a suitable hydrolysis or hydrogenation catalyst known in the art.
  • the conversion of step c2) can be carried out by hydrolysis of the amide group of the intermediate N-formyl-protected amino alcohol compound of the formula II, preferably by acidic hydrolysis using a strong acid such as hydrochloric acid or sulfuric acid as hydrolysis catalyst, which cleaves the nitrogen-carbon bond of this group into an amine group (or its corresponding ammonium group) and a carboxylic acid group, releasing the formyl residue in form of formic acid.
  • step c2 can be carried out by hydrogenation of the amide group of the intermediate N-formyl-protected amino alcohol compound of the formula II, preferably by application of increased hydrogen pressure in the presence of a suitable hydrogenation catalyst, which cleaves the nitrogen-carbon bond of this group into an amine group and an alcohol group, releasing the formyl residue in form of methanol.
  • a suitable hydrogenation catalyst which cleaves the nitrogen-carbon bond of this group into an amine group and an alcohol group, releasing the formyl residue in form of methanol.
  • Such hydrogenative cleavage of amides is generally known to the skilled person (e.g., Balaraman et al., J. Am. Chem. Soc.
  • Such hydrolysis as well as such hydrogenation is usually performed at increased temperature, preferably in the range from 50 to 250 °C.
  • the reaction time for such hydrolysis as well as such hydrogenation is in the range from 1 to 20 h.
  • the process for converting an N-formyl-protected aminonitrile compound of the formula III and the processes for manufacturing an amino alcohol compound of the formula I according to the invention can be performed continuously, semi-continuously (semi-batch) or discontinuously (batch). Preference is given to continuous processes.
  • the process for converting an N-formyl-protected aminonitrile compound of the formula III and the processes for manufacturing an amino alcohol compound of the formula I according to the invention are caried out with a compound of the formula III in which both residues R1 and R2 are methyl groups.
  • the compound of the formula III is N-(1-cyano-1 ,2-dimethyl- propyl)formamide and the process results in the formation of 2-amino-2-methyl-1 -propanol as compound of the formula I and/or N-1 (1-hydroxy-2-methylpropan-2-yl)formamide as compound of the formula II.
  • N-formyl-protected aminonitrile compounds of the formula III are accessible e.g., by the reaction of the corresponding cyanohydrin with formamide in acetic acid as described in WO 2020/094454 A.
  • the homogeneous transition metal catalyst is partially transformed into inactive or less active species during the reductive hydrolysis of step a), and that such inactivation can be reverted by contacting the homogeneous transition metal catalyst of the invention with chloride sources. Without the regeneration of the homogeneous transition metal catalyst by adding a chloride source, the activity and selectivity of that homogeneous transition metal catalyst decreases over the time, which is particularly problematic in processes where the homogeneous transition metal catalyst is to be recycled. Without being bound by theory, it is assumed that small amounts of CO and/or CN _ , which are formed during the process, partially replace the original ligands of the Ru complex resulting in a less active and less selective catalyst.
  • reactivation is a prerequisite for an efficient reuse of the homogeneous transition metal catalyst within a separate performance of the process or in the course of a recycling step d) of the process.
  • the regenerated homogeneous transition metal catalyst can be reused in the reductive hydrolysis reaction (step a)), either immediately after its regeneration or after a storage period.
  • the chloride salts which can be used as chloride source for the contacting of the homogeneous transition metal catalyst are preferably selected from LiCI, NaCI, KCI, NH4CI, NR4CI, CaCh, MgCh, AlC , FeC and anion-exchange resins in a Cl-form.
  • a more preferred chloride source is selected from the group consisting of HCI, LiCI, NaCI, KCI, NH4CI and NR4CI.
  • a particularly preferred chloride source is selected from the group consisting of HCI and NH4CI. It is possible to use a single compound as chloride source or mixtures of two or more different chloride source compounds.
  • hydrochloric acid (HCI) is used as chloride source, it may be employed in gaseous form or in form or a solution, preferably in form of an aqueous solution.
  • the residues R of the NR4CI salt are organyl residues with 1 to 10 carbon atoms. The four residues of this salt can be different or the same.
  • each organyl residue R of the NR4CI salt is an alkyl group.
  • each organyl residue R of the NR4CI salt has 1 to 4 carbon atoms.
  • Particularly preferred residues R of the NR4CI salt are methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl or any combination thereof.
  • the contacting of the homogeneous transition metal catalyst with the chloride source can be carried out (i) during the reductive hydrolysis reaction of step a), (ii) during the separation method of step b), or (iii) during the recycling of step d), or any combination thereof.
  • the contacting of the homogeneous transition metal catalyst with the chloride source is carried out in a way that the chloride source is employed in an amount so that the molar ratio of chloride to ruthenium during step a) is at least 2, more preferably at least 3, particularly in the range from 2 to 100, more particularly in the range from 3 to 10.
  • the appropriate amount of chloride source can be added directly to the reaction mixture of step a) so that the preferred molar ratio of chloride to ruthenium is adjusted.
  • the chloride source can be added in the appropriate amount to the compound mixture of step c) or d) and this is indirectly transferred into the reaction mixture of step a).
  • the contacting of homogeneous transition metal catalyst with the chloride source can be carried out during step b) or step d) in a way that the homogeneous transition metal catalyst takes up chloride from the chloride source so that after this contacting the catalyst comprises in average at least 1 , more preferably at least 2 chloride ion ligands.
  • the excess of chloride source can be removed from the catalyst after the contacting and binding of chloride ion ligands to the catalyst.
  • This can be realised for example by the use of a chloride ion exchange resin which is passed by the compound mixture during step d) before the recycling into step a). If the contacting is carried out during the recycling of step d), this contacting preferably lasts at least 0.25 h, more preferably at least 1 h, and is preferably at a temperature in the range from 130 to 220 °C.
  • the homogeneous transition metal catalyst is a coordination complex composed of ligands and one or more ruthenium (Ru) coordination centers. Furthermore, the homogeneous transition metal catalyst comprises at least one ligand being a tri- dentate ligand having 3 phosphine functions but no other heteroatoms.
  • this mandatory ligand of the homogeneous transition metal catalyst of the invention is a tri-dentate phosphine compound of the formula IV or , with A being an alkanetriyl functional group having 1 to 20 carbon atoms, each Q being independently of each other an alkanediyl functional group having 1 to 10 carbon atoms, and each R3 being independently of each other an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 6 to 20 carbon atoms.
  • the A residue is an alkanetriyl functional group having 4 to 14 carbon atoms.
  • the Q residues are alkanediyl functional groups having 1 to 4 carbon atoms, and preferably both Q residues of the tri-dentate phosphine compound of the formula V are identical.
  • the R3 residues are aryl group having 6 to 12 carbon atoms, and preferably all R3 residues of the tri- dentate dentate phosphine compound of the formula IV or the formula V are identical.
  • the at least one mandatory tri-dentate phosphine ligand of the homogeneous transition metal catalyst is selected from the group consisting of 1 ,1 ,1 - tris(diphenylphosphinomethyl)ethane (triphos), 1 ,1 ,1-tris(bis(3,5- dimethylphenyl)phosphinomethyl)ethane (triphos-xyl), 1 ,1 ,1 -tris(bis(o- tolyl)phosphinomethyl)ethan (triphos-tol), and bis(2-diphenylphosphinoethyl)phenylphosphine (dppepp).
  • the mandatory ligand of the homogeneous transition metal catalyst is either 1 ,1 ,1-tris(diphenylphosphinomethyl)ethane (triphos) or tris(bis(3,5- dimethylphenyl)phosphinomethyl)ethane (triphos-xyl).
  • the homogeneous transition metal catalyst comprises at least on tris(bis(3 ,5- dimethylphenyl)phosphinomethyl)ethane (triphos-xyl) ligand.
  • the homogeneous transition metal catalyst comprises one or more further ligands, preferably selected from the group consisting of triphenylphosphine (TPP), bis(diphenylphosphino)ethane (dppe), 4,5- bis(diphenylphosphino)-9,9-dimethylxanthene (xanthphos), Cl’, H’, CN’, acetylacetonate, methallyl, 1 ,5-cyclooctadien, and CO.
  • TPP triphenylphosphine
  • dppe bis(diphenylphosphino)ethane
  • xanthphos 4,5- bis(diphenylphosphino)-9,9-dimethylxanthene
  • Cl acetylacetonate
  • methallyl 1 ,5-cyclooctadien
  • CO acetylacetonate
  • Particularly preferred further ligands are Cl’ and H’.
  • Particularly preferred transition metal catalyst comprises not more than one CO ligand, more preferably no CO ligand amongst the further ligands.
  • Particularly preferred transition metal catalyst comprises not more than one CN’ ligand, more preferably no CN’ ligand amongst the further ligands.
  • More particularly preferred transition metal catalyst comprises not more than one CO or CN’ ligand, more preferably no CO and no CN’ ligand amongst the further ligands.
  • Particularly preferred homogeneous transition metal catalyst for the processes of the invention are selected from the group consisting of [Ru2(triphos)2(p-C )]CI, [Ru(triphos)(CO)(H)2], [Ru(triphos)(methallyl)],[Ru2(triphos-xyl)2(p-Cl3)]CI, [Ru(triphos-xyl)(CO)(H)2], and [Ru(triphos- xyl)(methallyl)].
  • the homogeneous transition metal catalyst of the invention can be prepared by contacting a precursor which contains the ruthenium in the form of an ion, e.g., a ruthenium salt, preferably a ruthenium chloride salt, or a different complex of ruthenium where the original ligands are replaced at least partially by the ligands according to the invention by the means of a ligand replacement reaction.
  • a precursor which contains the ruthenium in the form of an ion e.g., a ruthenium salt, preferably a ruthenium chloride salt, or a different complex of ruthenium where the original ligands are replaced at least partially by the ligands according to the invention by the means of a ligand replacement reaction.
  • Typical commercially available ruthenium containing precursor suitable for the preparation (including in situ formation) of the homogeneous transition metal catalyst of the invention are
  • ruthenium salts such as ruthenium(lll) chloride, ruthenium(lll) chloride trihydrate, ruthenium(lll)chloride hydrate, ruthenium(lll) acetylacetonate ([Ru(acetylacetonate)3]), ruthenium(lll) bromide, ruthenium(lll) iodide, or ammonium hexachlororuthenate(IV) and
  • ruthenium complexes such as bis(2,4-dimethylpentadienyl)ruthenium(ll), bis(2- methylallyl)(1 ,5-cyclooctadiene)ruthenium(ll), chloro(1 ,5- cyclooctadiene)(pentamethylcyclopentadienyl) ruthenium(ll) ([Ru(pentamethylcyclopentadienyl)(COD)CI]), chloro(pentamethylcyclopentadienyl) ruthenium(ll) (tetramer), dicarbonylcyclopentadienylruthenium(ll) (dimer) ([Ru(cyclopentadienyl)(CO)2]2), dichloro(benzene)ruthenium(ll) (polymer) ([Ru(benzene)Cl2]n), di-p-chlorobis[(p-cymene)chlororuthenium(ll)
  • the preparation of the homogeneous transition metal catalyst of the invention can be carried out by a separate process or in situ within the processes of the invention, preferably within step a) thereof, e.g., by adding the Ru containing precursor RuC x 3 H2O and the ligand 1 ,1 ,1- tris(diphenylphosphinomethyl)ethane to the reaction mixture of step a).
  • the employed homogeneous transition metal catalyst is the complex being formed in situ within the reaction mixture by adding to the reaction mixture of the process (i) a ruthenium containing precursor, (ii) at least one tri-dentate ligand having 3 phosphine functions but no other heteroatoms and (iii) one or more further ligands (unless they are not already part of the precursor).
  • these components for the in situ formation of the homogeneous transition metal catalyst are added to the reaction mixture of step a).
  • these components may alternatively be added to the compound mixture of step b) or d).
  • the reductive hydrolysis in step a) is preferably carried out at a temperature in the range from 20 to 200 °C, more preferably from 50 to 180 °C, and particularly from 100 to 170 °C.
  • the hydrogen pressure employed within this step a) is preferably in the range from 0.1 to 400 bar, more preferably from 5 to 200 bar, particularly from 5 to 80 bar.
  • the reductive hydrolysis of step a) can be carried out in all reactors known to a skilled person for this type of reaction.
  • the reductive hydrolysis can be performed in one single reactor or in a set of two or more consecutive reactors.
  • the amount of homogeneous transition metal catalyst used based on the amount of the N-formyl-protected aminonitrile compound of the formula III can be varied in a wide range.
  • the homogeneous transition metal catalyst is employed in a sub- stoichiometric amount relative to the N-formyl-protected aminonitrile compound of the formula III.
  • the amount of the homogeneous transition metal catalyst is in the range from 0.05 to 100 ppm b.w., preferably from 3 to 30 ppm b.w., particularly from 5 to 25 ppm b.w., calculated as ruthenium and based on the amount of the compound of the formula III. In a batch process where the compound of the formula III decreases over the time, this concentration refers to the starting conditions of the reductive hydrolysis.
  • the reductive hydrolysis of step a) is carried out in the presence of water.
  • the content of water in the reaction mixture of step a) is in the range from 1 to 50% b.w., more preferably in the range from 1 to 30% b.w., and most preferably in the range from 1 to 20% b.w., based on the total reaction mixture.
  • the reductive hydrolysis of step a) is carried out in the presence of a solvent.
  • solvent comprises any compound in the reaction mixture of step a) other than the N-formyl-protected aminonitrile compound of the formula III, the amino alcohol compound of the formula I, the intermediate N-formyl-protected amino alcohol compound of the formula II, the homogeneous transition metal catalyst including its components, and the water.
  • Preferred solvents are aliphatic (linear, branched or cyclic) compounds which comprises one or more alcohol, ether and/or amide functions.
  • Such aliphatic solvents with one or more alcohol, ether and/or amide functions may also comprise additional functional groups, such as amino groups (primary, secondary or tertiary), keto groups, carboxylic acid groups, ester groups and halogenic substituents.
  • additional functional groups such as amino groups (primary, secondary or tertiary), keto groups, carboxylic acid groups, ester groups and halogenic substituents.
  • Typical aliphatic solvents with one or more alcohol, ether and/or amide functions are
  • cycloaliphatic ethers such as dioxane, tetrahydrofuran, morpholin or derivatives thereof (e.g., 2-methyl-tetrahydrofuran or dimorpholinyldiethyl ether),
  • linear aliphatic ethers and polyethers such as dialkyl ethers, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether and other glymes (oligomeric or polymeric ether compounds based on propylene glycol or ethylene glycol, e.g., tetraethylene glycol dimethyl ether (TEGdme), tetraethylene glycol monomethyl ether (TEGmme), tetraethylene glycol monobuthyl ether (TEGmbe)),
  • di- or polyhydric alcohols such as ethylene glycol, butanediol, hexanediol, cyclohexandiol,
  • aliphatic amides including intramolecular amides (lactams)
  • lactams such as N- methylpropanamide or 1-(2-hydroxyethyl)-2-pyrrolidone.
  • Preferred aliphatic solvents with one or more alcohol and/or ether functions are the compounds selected from the group consisting of dioxane, tetrahydrofuran and derivatives thereof, morpholine and derivatives thereof, glymes and 1-(2-hydroxyethyl)-2-pyrrolidone.
  • Particularly preferred solvents with one or more alcohol and/or ether functions are the compounds selected from the group consisting of dioxane, 2,2’-dimorpholinyldiethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether and 1-(2- hydroxyethyl)-2-pyrrolidone.
  • the use of solvents with a comparably high boiling point e.g., a boiling point which is higher than the amine alcohol compound of the formula I, which is produced by the processes of the invention.
  • a comparably high boiling point e.g., a boiling point which is higher than the amine alcohol compound of the formula I, which is produced by the processes of the invention.
  • Using such a high boiling solvent reduces the loss of solvent during the processes which is a relevant advantage in particular for a continuous process.
  • the content of solvent in the reaction mixture of step a) is in the range from 0 to 99% b.w., more preferably in the range from 50 to 95% b.w., and most preferably in the range from 60 to 80% b.w., based on the total reaction mixture.
  • the molar ratio of water to solvent is preferably in the range from 50:1 to 1 :50, more preferably in the range from 5:1 to 1 :30, most preferably in the range from 3:1 to 1 :10.
  • the processes of the invention are carried out without solvent or essentially without solvent, which means a content of solvent which is not more than 5% b.w., more preferably not more than 2% b.w. based on the total reaction mixture of step a).
  • the content of the N-formyl-protected aminonitrile compound of the formula III (the starting compound of this reaction) can be varied in a wide range.
  • the content of this starting is in the range from 1 to 50% b.w., preferably from 5 to 20% b.w. based on the total amount of the reaction mixture.
  • this concentration refers to the starting conditions of the reductive hydrolysis.
  • a continuous process is preferably operated with a feed of the starting compound of the formula III which is chosen that way that the content of the compound of the formula III within the reaction mixture of the reactor (step a)) in the preferred range is maintained during the process.
  • the separation of step b) is carried out by the means of distillation.
  • a distillation can be a mere evaporation or a distillation with more than one theoretical trays, preferably it is an evaporation.
  • Such distillation of step b) is carried out usually at a head temperature in the range from 100 to 300°C, preferably in the range from 150 to 250°C, particularly preferably in the range from 180 to 220°C, and at a reduced pressure usually of up to 150 mbara, preferably of up to 100 mbara, particularly preferably of up to 60 mbara.
  • a distillation e.g., an evaporation as separation method for step b
  • the homogeneous transition metal catalyst ends up in the bottom fraction.
  • a homogeneous transition metal catalyst which is a coordination complex composed of ligands and one or more ruthenium (Ru) coordination centers, wherein the ligands comprise at least one chloride ligand, preferably at least two chloride ligands per Ru coordination center, and at least one tri-dentate ligand having 3 phosphine functions but no other heteroatoms, being 1 ,1 ,1-Tris(bis(3,5-dimethylphenyl)phosphinomethyl)ethane (triphos- xyl).
  • Ru ruthenium
  • Such a homogeneous transition metal catalyst is particularly stable and able to withstand the conditions of step a) and b) of the process for converting an N-formyl-protected aminonitrile compound of the formula III according to the invention without being inactivated. Accordingly, such a homogeneous transition metal catalyst is suitable to be employed within the processes of the invention.
  • Fig. 1 Scheme of a continuously operated lab plant consisting of a reactor cascade with three autoclaves (c1 , c2 and c3), a vacuum evaporation column (k1), a catalyst recycling vessel (B1) and a product vessel (B2).
  • the reactors are charged with the components of the reaction mixture (streams a and b) using pumps (P1 and P2) and pressurized with hydrogen (stream c).
  • the recycled catalyst is pumped (P3) from the catalyst recycling vessel back to the reactors (stream e).
  • Product (stream d) is collected in the product vessel.
  • Fig. 2 Graph showing the composition of the product stream d over the operation time for the continuous reductive hydrolysis of N-(1-cyano-1 ,2-dimethyl-propyl)formamide (Compound A) to N-1 (1-hydroxy-2-methylpropan-2-yl)formamide (Compound B) and 2-amino-2-methyl-1 -propanol (Compound C) as described in Example 4-1 without addition of a chloride source.
  • the dashed line and the solid line without dots show the tetraethylene glycol dimethyl ether (TEGdme) and the water content, respectively, as weight percentage measured by gas chromatography (left scale applicable).
  • the solid line with square dots, the dotted line with circular dots and the dashed line with rhombic dots show the Compound A, Compound B and Compound C content, respectively, as weight percentage measured by gas chromatography (right scale applicable). After an operation time of about 22 h the content of the product Compounds B and C decreases significantly.
  • Fig. 3 Graph showing the composition of the product stream d over the operation time for the continuous reductive hydrolysis of N-(1-cyano-1 ,2-dimethyl-propyl)formamide (Compound A) to N-1 (1-hydroxy-2-methylpropan-2-yl)formamide (Compound B) and 2-amino-2-methyl-1 -propanol (Compound C) as described in Example 4-2 with addition of a chloride source (NH4CI).
  • the dashed line and the solid line without dots show the tetraethylene glycol dimethyl ether (TEGdme) and the water content, respectively, as weight percentage measured by gas chromatography (left scale applicable).
  • the solid line with square dots, the dotted line with circular dots and the dashed line with rhombic dots show the Compound A, Compound B and Compound C content, respectively, as weight percentage measured by gas chromatography (right scale applicable). Even after an operation time of more than 50 h the content of the product Compounds B and C remains on a unchanged high level. The content of product compound C is particularly high.
  • N-(1-cyano-1 ,2-dimethyl-propyl)formamide was synthesized from acetone cyanohydrin and formamide as described in the EP 433883 A and DE 1950280 A.
  • GC analyses were performed using an Agilent 7890 B device equipped with an RTX-35 Amin column (30m, 0.25 mm, 0.5pm).
  • Carrier gas Helium
  • Any conversion rate presented in these examples was calculated as the relative loss of the starting compound based on the measurement of the respective weight calibrated GC-areas. Any yield presented in these examples was calculated as proportion of the respective target compound related to the converted part of the starting compound based on the measurement of the respective weight calibrated GC-areas.
  • Catalyst 1 In a 250 ml four neck round-bottom flask 157 mg of Catalyst 1 were treated with a solution of 64,9 mg trifluoromethanesulfonic acid (HOTf) and 12 ml methanol. After stirring the reaction mixture for 4 h at room temperature all volatiles were evaporated to give a yellow precipitate, which was dried under vacuum. The yellow solid was washed twice with 10 ml n-pentane and dried again under vacuum to yield 67 mg (35.8 %) of Catalyst 2. The identity of Catalyst 2 was proven by 31 P NMR (200 MHz, CD 2 CI 2 ), 13 C-NMR (125 MHz, CD 2 CI 2 ) and 1 H NMR (500MHz, CD2CI2).
  • Catalyst 3 A yield of 4.37 g (93.9%) of Catalyst 3 was obtained as a pale-yellow solid.
  • the identity of Catalyst 3 was proven by 31 P NMR (200 MHz, CD 2 CI 2 ), 13 C-NMR (125 MHz, CD 2 CI 2 ) and 1 H NMR (500MHz, CD 2 CI 2 ).
  • Example 1-1 the ruthenium catalyst was formed in situ.
  • the autoclave was charged simultaneously with RuC *3H 2 O and triphos in an equimolar ratio.
  • the reaction mixture was analyzed by 31 P NMR after the preformation step to prove the in situ formation of [Ru 2 (triphos) 2 (p-C )]CI (Catalyst 3-in-situ).
  • RuC *3H 2 O was used as starting material.
  • Example 2-1 Similar to Example 1-1 , a 100 ml autoclave was purged with hydrogen and charged with 32.3 mg RuC *3H2O, 115.8 mg triphos, 5g water and 17 g 1 ,4-dioxane (Catalyst 3-in-situ). The autoclave was pressurized with 35 bar hydrogen and heated to 130 °C. The catalyst solution was stirred for 1 h at the same conditions as a preformation of the catalyst. The autoclave was depressurized to 10 bar and 2 g of Compound A dissolved in 8 g 1 ,4-dioxane were added. The reaction mixture was heated to 130 °C, pressurized to 40 bar hydrogen and stirred for 10 min at the same conditions. The reaction mixture was analyzed via GC (Example 2-1).
  • Example 2-1 the reaction mixture of Example 2-1 was evaporated in vacuum at 190 °C for 20 h (until dryness).
  • the resulting ruthenium containing residue was dissolved in 17 g 1 ,4- dioxane and transferred into the hydrogen-purged 100 ml autoclave. 5 g water was added, and the autoclave was pressurized with 40 bar hydrogen and heated to 130°C. After the reaction temperature of 130 °C was reached, the autoclave was depressurized to 10 bar and 2 g of Compound A dissolved in 8 g 1 ,4-dioxane were added to analyze the efficiency of such recycled catalyst.
  • the reaction mixture was heated to 130 °C, pressurized to 40 bar hydrogen and stirred for 10 min at the same conditions.
  • the reaction mixture was analyzed via GC (Example 2-2). This catalyst recycling via evaporation of the reaction products was repeated five times.
  • the reaction mixtures after each catalyst recycle were analyzed via GC (Example 2-3 to 2-6) and 31 P NMR which proved the formation of [Ru(triphos)(CO)(H)2], [Ru(triphos)(CO)2] and [Ru(triphos)(H)(CO)2] + .
  • the analyses of the conversion rates and the yields for the Examples 2-1 to 2-6 as measured by GC were summarized in Table 2.
  • a 100 ml autoclave was purged with hydrogen and charged with 96.6 mg Catalyst 1 , 20 mg NH4CI dissolved in 5g water and 17 g 1 ,4-dioxane.
  • the autoclave was pressurized with 35 bar hydrogen and heated to 130 °C.
  • the catalyst solution was stirred for 1 h at the same conditions as a preformation of the catalyst.
  • the autoclave was depressurized to 10 bar and 1 g of Compound A dissolved in 8 g 1 ,4-dioxane were added.
  • the reaction mixture was heated to 130 °C, pressurized to 40 bar hydrogen and stirred for 1 h at the same conditions.
  • the reaction mixture was analyzed via GC (Example 3-1) and 31 P NMR which proved the formation of Catalyst 3.
  • Example 3-1 In a subsequent step, the reaction mixture of Example 3-1 was evaporated in vacuum at 190 °C for 20 h (until dryness). The resulting ruthenium containing residue was dissolved in 17 g 1 ,4- dioxane and transferred into the hydrogen-purged 100 ml autoclave. 20 mg NH4CI dissolved in 5g water were added, and the autoclave was pressurized with 35 bar hydrogen and heated to 130°C. After the reaction temperature of 130°C was reached, the autoclave was depressurized to 10 bar and 1 g of Compound A dissolved in 8 g 1 ,4-dioxane were added.
  • Example 3-2 The conversion rates and the yields analyses of the Examples 3-1 and 3-2 as measured by GC were summarized in Table 3.
  • TEGdme was added via P1 with 1 ml/min and water was added via P2 with 0.5 ml/min and the catalyst recycling pump P3 was started with 1.7 ml/min. Meanwhile the reactor cascade C1 to C3 was heated to 130 °C, the evaporator K1 was heated to 155 °C and a vacuum of 100 mbara was applied at K1 to evaporate the excess of TEGdme and water.
  • the reactor feed via pump P1 was changed from pure TEGdme to a solution of 20 wt% of Compound A in TEGdme (stream a), which was added with 1 ml/min.
  • the Compound A was converted to a mixture of Compound B and Compound C at 40 bar hydrogen and 130 °C.
  • a constant flow of 0.5 ml/min water (stream b) and 9 l/h hydrogen (stream c) was applied, and the reaction pressure was controlled by the depressurization valve into the evaporator K1 .
  • the reaction mixture was fed into the evaporator and a mixture of TEGdme, water, Compound B and Compound C was evaporated (stream d) at 180 to 200 °C, 50 mbara and collected in vessel B2.
  • the catalyst containing evaporation sump (stream e) was recycled into the reactor C1 with 1 .7 ml/min using the catalyst recycling pump P3.
  • the hydrogen-purged lab plant was charged with a solution of 0.46 mg triphos, 0.17 g of Catalyst s and 0.05 g NH4CI in 263 g TEGdme and 59.3 g water using the pump P1 with 5 ml/min until the catalyst recycle vessel B1 is filled with a minimal liquid level. Meanwhile the lab plant was pressurized to 40 bar with 9 l/h hydrogen. After the addition of the Ru-catalyst solution is completed, TEGdme was added via P1 with 1 ml/min and a solution of 1 .74 g NH4CI in 2 I water was added via P2 with 0.5 ml/min and the catalyst recycling pump P3 is started with 1.7 ml/min.
  • the reactor cascade C1 - C3 was heated to 130 °C, the evaporator K1 was heated to 155°C and a vacuum of 100 mbara was applied at K1 to evaporate the excess of TEGdme and water.
  • the reactor feed via pump P1 was changed from pure TEGdme to a solution of 20 wt% of Compound A in TEGdme (stream a), which was added with 1 ml/min.
  • the Compound A was converted to a mixture of Compound B and Compound C at 40 bar hydrogen and 130°C.
  • a constant flow of 0.5 ml/min water (stream b) and 9 l/h hydrogen (stream c) was applied, and the reaction pressure was controlled by the depressurization valve into the evaporator K1 .
  • reaction mixture was fed into the evaporator and a mixture of TEGdme, water, Compound B and Compound C was evaporated (stream d) at 180 to 200 °C, 50 mbara and collected in vessel B2.
  • the catalyst containing evaporation sump (stream e) was recycled into the reactor C1 with 1 .7 ml/min using the catalyst recycling pump P3.
  • composition of the product stream d was analyzed via GC which is depicted in Figure 3. No catalyst deactivation was observed within the tested operation time of 53 h.
  • RuC *3H2O 388 ppm b.w.
  • P-containing ligand 5 g water and 17 g TEGdme.
  • the autoclave was pressurized with 35 bar hydrogen, heated to 130 °C and stirred for 1 h at the same conditions.
  • the autoclave was depressurized to 10 bar and 2 g of Compound A dissolved in 8 g TEGdme were added.
  • the reaction mixture was heated to 130 °C, pressurized to 40 bar hydrogen and stirred for 4 h at the same conditions.
  • RuC *3H2O 388 ppm b.w.
  • triphos ligand Ru:P ratio of 1 :4.5 on molar basis
  • 5 g water and 17 g solvent As catalyst preformation, the autoclave was pressurized with 35 bar hydrogen, heated to 130 °C and stirred for 1 h at the same conditions. The autoclave was depressurized to 10 bar and 2 g of Compound A dissolved in 8 g of the solvent were added. The reaction mixture was heated to 130 °C, pressurized to 40 bar hydrogen and stirred for 4 h at the same conditions.

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Abstract

La présente invention concerne un procédé de conversion d'un composé aminonitrile N-formyle protégé en composé amino-alcool N-formyle ou amino-alcool correspondant ou des mélanges de ceux-ci par hydrolyse réductrice en présence d'eau, d'hydrogène et d'un catalyseur de métal de transition homogène, qui est un complexe de coordination composé d'un ou de plusieurs centres de coordination de Ru et d'au moins un ligand tridenté ayant 3 fonctions phosphine mais pas d'autres hétéroatomes, et qui est mis en contact avec une source de chlorure. Dans un tel procédé, le catalyseur de métal de transition homogène présente une bonne stabilité, une bonne activité, une bonne sélectivité et une longue durée de vie. Par conséquent, la présente invention concerne également un catalyseur de métal de transition homogène qui est un complexe de coordination composé d'un ou de plusieurs centres de coordination de Ru, d'au moins un ligand de chlorure et d'au moins un ligand de 1,1,1-Tris(bis(3,5-diméthylphényl)phosphinométhyl)éthane, d'un ligand tridenté ayant 3 fonctions phosphine mais pas d'autres hétéroatomes.
PCT/EP2023/080631 2022-11-11 2023-11-03 Procédé amélioré de conversion d'aminonitriles modifiés en amino-alcools correspondants WO2024099888A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1950280A1 (de) 1969-10-06 1971-04-15 Basf Ag Verfahren zur Herstellung von alpha-N-Formylaminosaeureverbindungen
EP0433883A1 (fr) 1989-12-22 1991-06-26 BASF Aktiengesellschaft Procédé pour la préparation d'alpha-formylaminonitriles
US20140073817A1 (en) 2012-09-10 2014-03-13 Basf Se Method for preparing menthone from isopulegol
WO2020094454A1 (fr) 2018-11-09 2020-05-14 Basf Se Procédé de production d'amino-alcools substitués

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1950280A1 (de) 1969-10-06 1971-04-15 Basf Ag Verfahren zur Herstellung von alpha-N-Formylaminosaeureverbindungen
EP0433883A1 (fr) 1989-12-22 1991-06-26 BASF Aktiengesellschaft Procédé pour la préparation d'alpha-formylaminonitriles
US20140073817A1 (en) 2012-09-10 2014-03-13 Basf Se Method for preparing menthone from isopulegol
WO2020094454A1 (fr) 2018-11-09 2020-05-14 Basf Se Procédé de production d'amino-alcools substitués

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BALARAMAN ET AL., J. AM. CHEM. SOC., vol. 132, 2010, pages 16756 - 16758
CALLEJA ET AL., CHEM. EUR. J., vol. 25, no. 40, 2019, pages 9498 - 9503
JIANG ET AL., INORGANICA CHIMICA ACTA, vol. 290, 1999, pages 64 - 79
NAKAGAWA ET AL., DALTON TRANSACTIONS, vol. 45, 2016, pages 6856 - 6865
P. CALLEJA, ET AL.: "Ruthenium-catalysed deaminative hydrogenation of amino nitriles: direct access to 1,2-amino alcohols", CHEMISTRY - A EUROPEAN JOURNAL, vol. 25, no. 40, 8 March 2019 (2019-03-08), Wiley-VCH Verlag, Weinheim DE, pages 9498 - 9503, XP071849531, ISSN: 0947-6539, DOI: 10.1002/chem.201900531 *

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