WO2024121371A1 - Hydrogénation sélective - Google Patents

Hydrogénation sélective Download PDF

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Publication number
WO2024121371A1
WO2024121371A1 PCT/EP2023/084861 EP2023084861W WO2024121371A1 WO 2024121371 A1 WO2024121371 A1 WO 2024121371A1 EP 2023084861 W EP2023084861 W EP 2023084861W WO 2024121371 A1 WO2024121371 A1 WO 2024121371A1
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Prior art keywords
formula
substituted
process according
alkyl
catalyst
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PCT/EP2023/084861
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English (en)
Inventor
Werner Bonrath
Hans-Joachim Drexler
Detlef Heller
Nora JANNSEN
Jonathan Alan Medlock
Marc-André Mueller
Cornelia PRIBBENOW
Carmen SELLE
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Dsm Ip Assets B.V.
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Publication of WO2024121371A1 publication Critical patent/WO2024121371A1/fr

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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
    • B01J31/24—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
    • B01J31/2414—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 comprising aliphatic or saturated rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • 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
    • 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
    • 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
    • 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
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • 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
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
    • 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
    • B01J2531/822—Rhodium
    • 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
    • B01J2531/827—Iridium

Definitions

  • the present invention relates to the use of a specific homogenous catalyst for the partial (selective) hydrogenation of a carbon-carbon triple bond.
  • the catalyst is used for the selective hydrogenation, i.e. for the hydrogenation of alkynes to alkenes.
  • the catalyst is used for the selective hydrogenation, i.e. for the hydrogenation of alkynes to alkenes.
  • Homogeneous catalysis refers to reactions where the catalyst is in the same phase as the reactants, principally in solution.
  • the aim of the present work was to improve the selectivity of selective hydrogenation reactions catalyzed by such catalysts.
  • transition metal catalyst with a specific bidentate phosphine ligand system shows a good efficiency of the hydrogenation while using mild reaction conditions.
  • the catalyst used in the selective hydrogenation according to the present invention has the following formula (I)
  • M is Rh or Ir
  • L1 is a bidentate phosphine ligand of formula (II) (R) 2 -P-A-P-(R 1 ) 2 (II), wherein
  • R is a substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, anisyl, tert-butyl or isopropyl, and
  • R 1 is a substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, anisyl, tert-butyl or isopropyl, and
  • A is a bridging moiety chosen from the group consisting of
  • w erein m is an integer of value 1 - 6; wherein z is 0 or 1 , and
  • L2 is a bidentate ligand or a monodentate ligand, with the proviso that when L2 is a bidentate ligand, then n is 1 and L2 is not a bidentate ligand of formula
  • X is an anion; and wherein any dotted line in formulae represents the bond by which the substituent is bound to the rest of the molecule.
  • the catalyst of the present invention is used in selective catalytic hydrogenation of starting material, especially of starting material comprising a carbon-carbon triple bond, more especially of alkynol compounds, especially preferred a-alkynol compounds.
  • the present invention relates in a first aspect, to a process of selective hydrogenation (H) comprising the step of selectively hydrogenating alkynes to alkenes in the presence of at least one catalyst of formula (I)
  • M is Rh or Ir
  • L1 is a bidentate phosphine ligand of formula (II)
  • R is a substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, anisyl, tert-butyl or isopropyl, and
  • R 1 is a substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, anisyl, tert-butyl or isopropyl, and
  • A is a bridging moiety chosen from the group consisting of integer of value 1 - 6;
  • L2 is bidentate ligand or a monodentate ligand, with the proviso that when L2 is a bidentate ligand, then n is 1 and L2 is not a bidentate ligand of formula (II) when L2 is a monodentate ligand, then n is 2, and
  • X is an anion
  • the catalyst of the formula (I) is a homogenous catalyst.
  • the present invention also relates to a process of selective hydrogenation (H1), which is the process of selective hydrogenation (H), wherein starting material comprising a carbon-carbon triple bond are hydrogenated selectively.
  • the present invention also relates to a process of selective hydrogenation (H2), which is the process of selective hydrogenation (H) or (H1), wherein alkynol compounds are hydrogenated selectively. Therefore, the present invention also relates to a process of selective hydrogenation (H2’), which is the process of selective hydrogenation (H) or (H 1), wherein a-alkynol compounds are hydrogenated selectively.
  • the present invention also relates to a process of selective hydrogenation of a compound of formula (III)
  • R 4 C C - C - R 3 ( Hl )
  • R 2 is a linear or branched Ci-Css-alkyl; or a linear or branched C2-C35-alkenyl moiety, wherein the C chain can be substituted, and
  • R 3 is H or a linear or branched Ci-C4-alkyl, wherein the C chain can be substituted, and
  • R 4 is H or a cyclic, linear or branched Ci-Ce-alkyl, wherein the C chain can be substituted; or a Cs- C12- cyclic aromatic moiety, which can be substituted, and
  • R 5 is H or OH or a OCi-C4-alkyl; or a O(CO)Ci-C4-alkyl.
  • R 2 , R 3 , R 4 and R 5 have the same meaning as defined in formula (III).
  • the present invention also relates to a process of selective hydrogenation wherein a compound of formula (III)
  • R 4 C C - C - R 3 ( Hl )
  • R 2 is a linear or branched Ci-Cso-alkyl; or a linear or branched C2-Cso-alkenyl moiety, wherein the C chain can be substituted, and R 3 is a Ci-C2-alkyl, and
  • R 4 is H or a linear or branched Ci-Ce-alkyl, wherein the C chain can be substituted, and
  • R 5 is OH or a OCi-C2-alkyl is hydrogenated selectively to a compound of the formula (IV)
  • the present invention also relates to a process of selective hydrogenation wherein of a compound of formula (III)
  • R 4 C C - C - R 3 ( H l )
  • R 2 is a linear or branched Ci-C2o-alkyl; or a linear or branched C2-C2o-alkenyl moiety, wherein the C chain can be substituted, and
  • R 3 is a Ci-C2-alkyl
  • R 4 is H, and R 5 is OH or a O(CO)Ci-C 2 -alkyl is hydrogenated selectively to a compound of the formula (IV)
  • the present invention also relates to a process of selective hydrogenation (H3), which is the process of selective hydrogenation (H), (H1) or (H2), wherein a compound of formula (III)
  • R 4 C C - C - R 3 ( Hl )
  • R 2 is a linear or branched Ci-Css-alkyl; or a linear or branched C2-C35-alkenyl moiety, wherein the C chain can be substituted, and
  • R 3 is H; linear or a branched Ci-C4-alkyl, wherein the C chain can be substituted, and
  • R 4 is H; cyclic, a linear or branched Ci-Ce-alkyl, wherein the C chain can be substituted; or a C5- Ci2-cyclic aromatic moiety, which can be substituted, and
  • R 5 is H or OH or a OCi-C4-alkyl or a O(CO)Ci-C4-alkyl, is hydrogenated selectively to a compound of the formula (IV)
  • the present invention also relates to a process of selective hydrogenation (H3’), which is the process of selective hydrogenation (H), (H1), (H2) or (H2’), wherein a compound of formula (III)
  • R 4 C C - C - R 3 ( H l )
  • R 2 is a linear or branched Ci-Cso-alkyl; or a linear or branched C2-Cso-alkenyl moiety, wherein the C chain can be substituted, and
  • R 3 is a Ci-C2-alkyl
  • R 4 is H; a cyclic, linear or branched Ci-Ce-alkyl, wherein the C chain can be substituted, and
  • R 5 is OH or a O(CO)Ci-C 2 -alkyl, is hydrogenated selectively to a compound of the formula (IV)
  • the present invention also relates to a process of selective hydrogenation (H3”), which is the process of selective hydrogenation (H), (H1), (H2) or (H2’), wherein a compound of formula (III)
  • R 4 C C - C - R 3 ( H l )
  • R 2 is a linear or branched Ci-C2o-alkyl; or a linear or branched C2-C2o-alkenyl moiety, wherein the C chain can be substituted, and
  • R 3 is a Ci-C2-alkyl
  • R 4 is H
  • R 5 is OH or a O(CO)Ci-C 2 -alkyl, is hydrogenated selectively to a compound of the formula (IV)
  • the present invention also relates to a process of selective hydrogenation (H3’”), which is the process of selective hydrogenation (H), (H1), (H2) or (H2’), wherein a com- pound of formula (Illa), (I lib), (I He) or (Hid) is hydrogenated selectively to a compound of the formula (IVa), (I b), (IVc) or (IVd), respectively
  • Preferred catalysts of formula (I) are those, wherein M is Rh.
  • the present invention also relates to a process of selective hydrogenation (H4), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”) or (H3’”), wherein a catalyst of formula (I), wherein M is Rh is used.
  • Preferred catalysts of formula (I) are those, wherein L1 is a bidentate phosphine ligand chosen from the group consisting of the following ligands of formulae (Ila) to (lip) More preferred catalysts of formula (I) are those, whereinLI is a bidentate phosphine ligand chosen from the group consisting of the following ligands of formulae Therefore, the present invention also relates to a process of selective hydrogenation (H5), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”) or (H4), wherein a catalyst of formula (I), wherein L1 is a bidentate phosphine ligand chosen from the group consisting of the ligands of formula (Ila) to (lip)
  • the present invention also relates to a process of selective hydrogenation (H5’), which is the hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”) or (H4), wherein a catalyst of formula (I), wherein
  • L1 is a bidentate phosphine ligand chosen from the group consisting of the ligands is used.
  • Preferred catalysts are those wherein L2 is bidentate ligand chosen from the group consisting of cyclohexadiene, cycloheptadiene 1 ,5-cyclooctadiene (COD), norbornadiene (NBD), and n is 1.
  • the present invention also relates to a process of selective hydrogenation (H6), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5) or (H5’), wherein a catalyst of formula (I), wherein L2 is bidentate ligand chosen from the group consisting of cyclohexadiene, cycloheptadiene, 1 ,5-cyclooctadiene (COD) and norbornadiene (NBD) and n is 1 is used.
  • H6 selective hydrogenation
  • n 2 i.e. that the catalyst of the formula (I) has two identical monodentate ligands.
  • L2 is a monodentate ligand chosen from the group consisting of ReOH, wherein Re is a linear or branched Ci - Cs-alkyl moiety; cyclooctene, cycloheptene, cyclohexene, norbornene and ethene and n is 2.
  • carbonyl is not a monodentate ligand L2.
  • the present invention also relates to a process of selective hydrogenation (H7), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5) or (H5’), wherein a catalyst of formula (I), wherein L2 is a monodentate ligand chosen from the group consisting of ReOH, wherein Re is a linear or branched Ci - Cs-alkyl moiety; cyclooctene, cycloheptene, cyclohexene, norbornene and ethene and n is 2 is used.
  • a catalyst of formula (I) wherein L2 is a monodentate ligand chosen from the group consisting of ReOH, wherein Re is a linear or branched Ci - Cs-alkyl moiety; cyclooctene, cycloheptene, cyclohexene, nor
  • Preferred catalysts are those wherein X is halide (such as Cl; I; Br, F'), BF4; PFe', tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ([BAr F 4]'),(Ph)4B', CIOT, TfO' or SbFe'.
  • More preferred catalysts are those wherein X is BF4; PFe', tetrakis[3,5-bis(trifluorome- thyl)phenyl]borate ([BAr F 4]'),(Ph)4B', CIOT, TfO' or SbFe'.
  • the present invention also relates to a process of selective hydrogenation (H8), which is the selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6) or (H7), wherein a catalyst of formula (I), wherein X is chosen from the group consisting of halide (such as Cl; I; Br, F'), BF4; PFe', tetrakis[3,5-bis(trifluorome- thyl)phenyl]borate ([BAr F 4]'), (Ph)4B' CIOT, TfO' and SbFe'.
  • halide such as Cl; I; Br, F'
  • BF4 BF4
  • PFe' tetrakis[3,5-bis(trifluorome- thyl)phenyl]borate
  • the present invention also relates to a process of selective hydrogenation (H8’), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6) or (H7), wherein a catalyst of formula (I), wherein X is chosen from the group consisting of
  • the catalysts, which are used in the hydrogenation according to the present invention are made as disclosed in the prior art.
  • the hydrogenation according to the present invention can be carried without any solvent.
  • the present invention also relates to a process of selective hydrogenation (H9), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6), (H7), (H8) or (H8’), wherein the hydrogenation is carried out without any solvent.
  • H9 selective hydrogenation
  • the hydrogenation according to the present invention can be carried out in the presence of at least one inert solvent.
  • the hydrogenation can be carried out in a solvent (or mixture of solvents).
  • Suitable solvents are alkanes, esters, carbonates, lactones, ethers, amides, hydrocarbons, halogenated hydrocarbons, water and alcohols.
  • the present invention also relates to a process of selective hydrogenation (H10), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6), (H7), (H8) or (H8’), wherein the hydrogenation is carried out in at least one solvent.
  • H10 selective hydrogenation
  • the present invention also relates to a process of selective hydrogenation (H10’), which is the process of selective hydrogenation (H10), wherein the solvent is chosen from the group consisting of alkanes, esters, carbonates, lactones, ethers, amides, hydrocarbons, halogenated hydrocarbons, water and alcohols.
  • H10 selective hydrogenation
  • the solvent is chosen from the group consisting of alkanes, esters, carbonates, lactones, ethers, amides, hydrocarbons, halogenated hydrocarbons, water and alcohols.
  • the present invention also relates to a process of selective hydrogenation (H10”), which is the process of selective hydrogenation (H10), wherein the solvent is chosen from the group consisting of water, hexane, CH2CI2, toluene, ethyl acetate, THF, 2-Me-THF, cyclopentyl methyl ether, methanol, ethanol and isopropanol.
  • H10 selective hydrogenation
  • the present invention also relates to a process of selective hydrogenation (H10’”), which is the process of selective hydrogenation (H10), wherein the solvent is chosen from the group consisting of methanol, water and hexane.
  • the catalyst of formula (I) according to the present invention is usually used in an amount of 0.001 - 1 mol-% (preferably 0.001 - 0.5 mol-%) (based on the number of moles of the compounds of formula (III)).
  • the present invention also relates to a process of selective hydrogenation (H11), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6), (H7), (H8), (H8’), (H9), (H10), (H10’), (H10”) or (H10’”), wherein the at least one catalyst of formula (I) is used in an amount of 0.001 - 1 mol-% (based on the number of moles of the compounds of formula (III)).
  • the present invention also relates to a process of selective hydrogenation (H1 T), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6), (H7), (H8), (H8’), (H9), (H10), (H10’), (H10”) or (H10’”), wherein the at least one catalyst of formula (I) is used in an amount of 0.001 - 0.5 mol-% (based on the number of moles of the compounds of formula (III)).
  • the hydrogenation process can be carried out with (pure) H2 gas or with a gas, which comprises H2.
  • the hydrogenation process according to the present invention is carried out with (pure) H2 gas.
  • the present invention also relates to a process of selective hydrogenation (H12), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6), (H7), (H8), (H8’), (H9), (H10), (H10’), (H10”), (H10’”), (H11) or (H1 T), wherein the hydrogenation is carried out with (pure) H2 gas or with a gas, which comprises H2.
  • the present invention also relates to a process of selective hydrogenation (H12’), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6), (H7), (H8), (H8’), (H9), (H10), (H10’), (H10”), (H10’”), (H11) or (H1 T), wherein the hydrogenation is carried out with H2 gas.
  • H12 selective hydrogenation
  • the hydrogenation process can be carried out at ambient pressure as well as at elevated pressure.
  • the hydrogenation process according to the present invention is carried out at a pressure of 1 - 50 bar, more preferably at 1 - 30 bar.
  • the reaction is carried out in an autoclave (or any other vessel, which can resist the pressure).
  • the present invention also relates to a process of selective hydrogenation (H13), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6), (H7), (H8), (H8’), (H9), (H10), (H10’), (H10”), (H10’”), (H11), (H1 T), (H12) or (H12’), wherein the hydrogenation is carried out at ambient pressure.
  • H13 is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6), (H7), (H8), (H8’), (H9), (H10), (H10’), (H10”), (H10’”), (H11), (H
  • the present invention also relates to a process of selective hydrogenation (H13’), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6), (H7), (H8), (H8’), (H9), (H10), (H10’), (H10”), (H10’”), (H11), (H1 T), (H12) or (H12’), wherein the hydrogenation is carried out at a pressure of 1 - 50 bar, preferably at 1 - 30 bar.
  • the hydrogenation is usually carried out at a temperature of -10 - 150 °C. (preferably 10 - 100 °C)
  • the present invention also relates to a process of selective hydrogenation (H14), which is the process of selective hydrogenation (H), (H1), (H2), (H2’), (H3), (H3’), (H3”), (H3’”), (H4), (H5), (H5’), (H6), (H7), (H8), (H8’), (H9), (H10), (H10’), (H10”), (H10’”), (H11), (H1 T), (H12), (H12’), (H13) or (H 13’), wherein the hydrogenation is carried out at a temperature of -10 - 150 °C.
  • Rh(COD)acac (1 mmol) was dissolved in THF (3 mL) and the reaction mixture was cooled to -78°C.
  • the ligand (1.0 eq) dissolved in THF (7 mL) was added dropwise over a period of 30 min followed by the addition of HBF4 (125 pl (50 % in H2O)). Then the catalyst was participated with diethyl ether (40 mL), filtered off, washed with diethyl ether and dried afterwards.
  • dehydroisophytol 3,7,11 ,15-tetramethylhexadecan-3-ol.
  • phytol 3,7,11 ,15-tetramethylhexadecan-3-ol.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne l'utilisation d'un catalyseur homogène spécifique pour l'hydrogénation partielle (sélective) d'une triple liaison carbone-carbone, c'est-à-dire, d'alcynes en alcènes.
PCT/EP2023/084861 2022-12-09 2023-12-08 Hydrogénation sélective WO2024121371A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1232015A (fr) * 1967-07-27 1971-05-19
US6005148A (en) * 1996-12-23 1999-12-21 Seton Hall University Supported catalysts
US20040116713A1 (en) * 2001-01-10 2004-06-17 Matthias Beller Novel n-phenyl-pyrrol bisphosphane compounds and the metal complexes of the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1232015A (fr) * 1967-07-27 1971-05-19
US6005148A (en) * 1996-12-23 1999-12-21 Seton Hall University Supported catalysts
US20040116713A1 (en) * 2001-01-10 2004-06-17 Matthias Beller Novel n-phenyl-pyrrol bisphosphane compounds and the metal complexes of the same

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