EP4630161A1 - Selective hydrogenation - Google Patents

Selective hydrogenation

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Publication number
EP4630161A1
EP4630161A1 EP23821273.2A EP23821273A EP4630161A1 EP 4630161 A1 EP4630161 A1 EP 4630161A1 EP 23821273 A EP23821273 A EP 23821273A EP 4630161 A1 EP4630161 A1 EP 4630161A1
Authority
EP
European Patent Office
Prior art keywords
formula
substituted
process according
alkyl
catalyst
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.)
Pending
Application number
EP23821273.2A
Other languages
German (de)
French (fr)
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 BV
Original Assignee
DSM IP Assets BV
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Filing date
Publication date
Application filed by DSM IP Assets BV filed Critical DSM IP Assets BV
Publication of EP4630161A1 publication Critical patent/EP4630161A1/en
Pending legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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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Abstract

The present invention relates to the use of a specific homogenous catalyst for the partial (selective) hydrogenation of a carbon-carbon triple bond, i.e. of alkynes to alkenes.

Description

Selective Hydrogenation
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. Thus, if a compound contains a double bond as well as a triple bond, only the triple bond is reduced to a double bond.
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.
It was found out that the 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+(L1)(L2)n]X (I), wherein
M is Rh or Ir, and
L1 is a bidentate phosphine ligand of formula (II) (R)2-P-A-P-(R1)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
R1 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
■■■(CH2)m--- 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
(II) when L2 is a monodentate ligand, then n is 2, and
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.
Therefore, 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+(L1)(L2)n]X (I), wherein
M is Rh or Ir, and
L1 is a bidentate phosphine ligand of formula (II)
(R)2-P-A-P-(R1)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
R1 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;
And wherein z is 0 or 1 , and
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.
Therefore, 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.
Therefore, 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.
Preferably, the present invention also relates to a process of selective hydrogenation of a compound of formula (III)
R5
R4C=C - C - R3 (Hl)
R2 wherein
R2 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
R3 is H or a linear or branched Ci-C4-alkyl, wherein the C chain can be substituted, and
R4 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
R5 is H or OH or a OCi-C4-alkyl; or a O(CO)Ci-C4-alkyl.
The product of the selective hydrogenation is the compound of formula (IV) wherein
R2, R3, R4 and R5 have the same meaning as defined in formula (III).
More preferably, the present invention also relates to a process of selective hydrogenation wherein a compound of formula (III)
R5
R4C=C - C - R3 (Hl)
R2 wherein
R2 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 R3 is a Ci-C2-alkyl, and
R4 is H or a linear or branched Ci-Ce-alkyl, wherein the C chain can be substituted, and
R5 is OH or a OCi-C2-alkyl is hydrogenated selectively to a compound of the formula (IV)
Even more preferably, the present invention also relates to a process of selective hydrogenation wherein of a compound of formula (III)
R5
R4C=C - C - R3 (H l)
R2 wherein
R2 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
R3 is a Ci-C2-alkyl, and
R4 is H, and R5 is OH or a O(CO)Ci-C2-alkyl is hydrogenated selectively to a compound of the formula (IV)
Most preferred compounds of formula (III) are the following of formula (Illa) to (Hid)
Therefore, 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)
R5
R4C=C - C - R3 (Hl)
R2 wherein
R2 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
R3 is H; linear or a branched Ci-C4-alkyl, wherein the C chain can be substituted, and
R4 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
R5 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)
Therefore, 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)
R5
R4C=C - C - R3 (H l)
R2 wherein
R2 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
R3 is a Ci-C2-alkyl, and
R4 is H; a cyclic, linear or branched Ci-Ce-alkyl, wherein the C chain can be substituted, and
R5 is OH or a O(CO)Ci-C2-alkyl, is hydrogenated selectively to a compound of the formula (IV)
Therefore, 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)
R5
R4C=C - C - R3 (H l)
R2 wherein
R2 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
R3 is a Ci-C2-alkyl, and
R4 is H, and
R5 is OH or a O(CO)Ci-C2-alkyl, is hydrogenated selectively to a compound of the formula (IV)
Therefore, 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
As stated above, the selective hydrogenation according to the present invention is carried out using a specific catalyst of formula (I).
Preferred catalysts of formula (I) are those, wherein M is Rh.
Therefore, 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)
5 is used. Therefore, 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.
Therefore, 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.
In case L2 is a monodentate ligand, then n = 2, i.e. that the catalyst of the formula (I) has two identical monodentate ligands.
Therefore, further preferred catalysts are those 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.
It is particularly preferred that carbonyl is not a monodentate ligand L2.
Therefore, 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.
Preferred catalysts are those wherein X is halide (such as Cl; I; Br, F'), BF4; PFe', tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ([BArF4]'),(Ph)4B', CIOT, TfO' or SbFe'. TfO' stands for triflate (=trifluoromethanesulfonate).
More preferred catalysts are those wherein X is BF4; PFe', tetrakis[3,5-bis(trifluorome- thyl)phenyl]borate ([BArF4]'),(Ph)4B', CIOT, TfO' or SbFe'.
Therefore, 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 ([BArF4]'), (Ph)4B' CIOT, TfO' and SbFe'.
Therefore, 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
BF4’, PFe', tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ([BArF4]'), (Ph)4B' CIOT, TfO' and SbF6'.
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.
Therefore, 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.
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. Preferred solvents are water, hexane, CH2CI2, toluene, ethyl acetate, THF (=tetrahydrofuran), 2-Me-THF (=2-methyl-tetrahydrofuran), cyclopentyl methyl ether (=CPME), methanol, ethanol and isopropanol, especially preferred solvents are methanol, water and hexane.
Therefore, 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.
Therefore, 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.
Therefore, 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.
Therefore, 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)).
Therefore, 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)).
Therefore, 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. Preferably, the hydrogenation process according to the present invention is carried out with (pure) H2 gas.
Therefore, 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. Therefore, 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.
The hydrogenation process can be carried out at ambient pressure as well as at elevated pressure. Preferably, the hydrogenation process according to the present invention is carried out at a pressure of 1 - 50 bar, more preferably at 1 - 30 bar. Usually, the reaction is carried out in an autoclave (or any other vessel, which can resist the pressure).
Therefore, 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.
Therefore, 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)
Therefore 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.
The following examples serve to illustrate the invention. The temperature is given in °C and all percentages are related to the weight. Examples
General catalyst synthesis (Example 1)
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.
All other used catalyst in the following examples have been produced in analogy to the process of example 1.
Hydrogenation Examples
Example 2: Hydrogenation reactions
440 mmol Dehydroisophytol (compound of formula (I I lb);=DI P), 650 ml methanol and 4,4 mmol of the [Rh(cyc-Japhos)(NBD)]BF4, which was produced as disclosed in example 1 , were put into an autoclave. The mixture was stirred and the H2 was added in form of H2 gas. The autoclave was thermostated to 25° C and hydrogen pressure released after the desired reaction time. Analysis of the reaction mixture resulted in Table 1 (No 1).
The following examples have been made in analogy to the process of example 2 (the tables
1-3 list the difference to the reaction conditions) dehydroisophytol; = 3,7,11 ,15-tetramethylhexadecan-3-ol.
phytol; = 3,7,11 ,15-tetramethylhexadecan-3-ol.
Tab e 3. *DIP=Dehydroisophytol; IP= isophytol; DilP=perhydrogenated dehydroisophytol;
= 3,7,11 ,15-tetramethylhexadecan-3-ol.

Claims

Claims
1. A process of selective hydrogenation comprising the step of selectively hydrogenating alkynes to alkenes in the presence of at least one catalyst of formula (I)
[M+(L1)(L2)n]X (I), wherein
M is Rh or Ir, and
L1 is a bidentate phosphine ligand of formula (II) (R)2-P-A-P-(R1)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
R1 is s substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, anisyl, tert-butyl or isopropyl,
A is a bridging moiety chosen from the group consisting of ■■■(CH2)m--- w erein m is an integer of value 1 - 6; and 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
(II) when L2 is a monodentate ligand, then n is 2, and
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.
2. The process according to claim 1 , wherein a starting material comprising a carboncarbon triple bond is hydrogenated selectively.
3. The process according to claim 1 or claim 2, wherein a compound of formula (III)
R5
R4C=C - C - R3 (Hl)
R2 wherein
R2 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
R3 is H; a linear or branched Ci-C4-alkyl, wherein the C chain can be substituted, and
R4 is H; s cyclic, linear or branched Ci-Ce-alkyl, wherein the C chain can be substituted; or a Cs- Ci2-cyclic aromatic moiety, which can be substituted, and
R5 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)
4. The process according to any of the preceding claims, wherein a compound of formula (III)
R5
R4C=C - C - R3 (Hl)
R2 wherein
R2 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
R3 is a Ci-C2-alkyl, and
R4 is H, and
R5 is OH or a O(CO)Ci-C2-alkyl, is hydrogenated selectively to a compound of the formula (IV)
5. The process according to any of the preceding claims, wherein a catalyst of formula (I), wherein M is Rh is used.
6. The process according to any of the preceding claims, 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)
7. The process according to any of the preceding claims, wherein a catalyst of formula (I), wherein L2 is a bidentate ligand chosen from the group consisting of cyclohexadiene, cycloheptadiene 1 ,5-cyclooctadiene (COD) and norbornadiene (NBD), and n is 1 is used.
8. The process according to any of the preceding claims 1 - 6, 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.
9. The process according to any of the preceding claims, 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(trifluoromethyl)phenyl]borate ([BArF4]'), (Ph)4B; CIOT, TfO’ and SbFe'.
10. The process according to any of the preceding claims, wherein the hydrogenation is carried out without any solvent.
11. The process according to any of the preceding claims 1 - 9, wherein the hydrogenation is carried out in at least one solvent.
12. The process according to any of the preceding claims, 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)).
13. The process according to any of the preceding claims, wherein the hydrogenation is carried out with (pure) H2 gas or with a gas, which comprises H2.
14. The process according to any of the preceding claims, wherein the hydrogenation is carried out at a pressure of 1 - 50 bar.
15. The process according to any of the preceding claims, wherein the hydrogenation is carried out carried at a temperature of -10 - 150 °C.
16. The process according to any of the preceding claims, characterized in that M = Rh in the catalyst of formula (I).
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GB1232015A (en) * 1967-07-27 1971-05-19
US6025295A (en) * 1996-12-23 2000-02-15 Seton Hall University Supported catalysts
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