US20220234974A1 - Selective hydrogenation of alkynols to alkenols in the presence of a phosphorus compound - Google Patents

Selective hydrogenation of alkynols to alkenols in the presence of a phosphorus compound Download PDF

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US20220234974A1
US20220234974A1 US17/613,732 US202017613732A US2022234974A1 US 20220234974 A1 US20220234974 A1 US 20220234974A1 US 202017613732 A US202017613732 A US 202017613732A US 2022234974 A1 US2022234974 A1 US 2022234974A1
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Werner Bonrath
Jonathan Alan Medlock
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B01J35/0013—
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
    • C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/05—Alcohols containing rings other than six-membered aromatic rings
    • C07C33/14—Alcohols containing rings other than six-membered aromatic rings containing six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/05—Alcohols containing rings other than six-membered aromatic rings
    • C07C33/16—Alcohols containing rings other than six-membered aromatic rings containing rings with more than six ring members
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered

Definitions

  • the present invention relates to the hydrogenation of alkynols to alkenols.
  • Alkynes can be hydrogenated to alkenes by hydrogen in the presence of noble metal catalysts.
  • Palladium catalysts can be used for the hydrogenation of alkynols to alkenols.
  • Alkynols or the alkenols, respectively, are substances which are produced on an industrial scale and are of high importance, particularly for the field of vitamins and aroma chemicals.
  • a non-exhaustive list of such important alkynols and alkenols are 2-methylbut-3-yn-2-ol, 2-methylbut-3-en-2-ol, 3,7-dimethyloct-6-en-1-yn-3-ol, 3,7-dimethylocta-1,6-dien-3-ol, 3,7,11,15-tetramethylhexadec-1-yn-3-ol and 3,7,11,15-tetramethylhexadec-1-en-3-ol.
  • Another problem is that the selectivity at high conversion is not sufficiently high.
  • the target is to have transformed as much as possible of the starting material into the desired product.
  • there is a further drive to obtain as high conversion as possible because the alkynol, i.e. the starting material, and the alkenol, i.e. the product of the selective hydrogenation, are very difficult to separate.
  • running reactions at partial conversion followed by separation of the unreacted starting material and repeating the reaction is very difficult.
  • over-hydrogenation describes the effect that the hydrogenation of alkynol does not stop at the stage of alkenol but continues to yield significant amounts of alkanol, i.e. that the hydrogenation reaction does not selectively only hydrogenate the carbon-carbon triple bond to the carbon-carbon double bond, but that the carbon-carbon double bond is also hydrogenated to a carbon-carbon single bond in significant amounts.
  • the over-hydrogenated compound can be very difficult to be separated from the desired products.
  • Lindlar discloses in U.S. Pat. No. 2,681,938 a selective hydrogenation of alkynes to alkenes using a palladium catalyst which is modified by lead or bismuth.
  • alkynols leads to the formation of undesired side products, such as the formation of dimers or oligomers derived from the alkynol or the alkenol.
  • the problem to be solved by the present invention is to offer a process for the hydrogenation of alkynol selectively to an alkenol which yields high conversion, high selectivity and low over-hydrogenation.
  • the present invention relates to a process of hydrogenating an alkynol selectively to an alkenol by hydrogen using a hydrogenation catalyst which is palladium supported on a carrier; in the presence of an additive which is an organic phosphorus compound bearing either a phosphino or a phosphine oxide group; characterized in that in case the additive bears a phosphino group that the additive bears two or more phosphino groups.
  • a “C x-y alkyl” group is an alkyl group comprising x to y carbon atoms, i.e., for example, a C 1-3 -alkyl group is an alkyl group comprising 1 to 3 carbon atoms.
  • the alkyl group can be linear or branched. For example —CH(CH 3 )—CH 2 —CH 3 is considered as a C 4 -alkyl group.
  • Any wavy line in any formula of this document represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E-configuration.
  • an “alkynol” is a chemical compound which has at least one carbon-carbon triple bond and at least one hydroxyl group in its chemical formula.
  • an alkynol is a hydroxy functionalised alkyne.
  • an “alkenol” is a chemical compound which has at least one carbon-carbon double bond and at least one hydroxyl group in its chemical formula.
  • an alkenol is a hydroxy functionalised alkene.
  • hydrocarbyl group is a univalent group which formally is formed by removing a hydrogen atom from a hydrocarbon.
  • an alkynol is selectively hydrogenated to the respective alkenol.
  • the alkynol has at least one carbon-carbon triple bond and at least one hydroxyl group in its chemical formula whereas the respective alkenol has at least one carbon-carbon double bond and at least one hydroxyl group in its chemical formula.
  • the hydrogenation is selective, that is reducing the carbon-carbon triple bond to the respective carbon-carbon double bond.
  • the hydroxyl group as well as any other chemical groups which might be present in the alkynol are not modified by said hydrogenation reaction.
  • the hydrogenation is selective also in that sense that the carbon-carbon double bond of the alkenol is not, or at least not significantly, further hydrogenated to a carbon-carbon single bond (“over-hydrogenation”).
  • the alkynol is an alkynol which has a hydroxyl group attached to a carbon which is in alpha position to the carbon-carbon triple bond of the alkynol, i.e. the alkynol is preferably an alpha-alkynol.
  • the alkynol has preferably a following structural element
  • the alkynol is an alkynol in which the carbon-carbon triple bond is a terminal carbon-carbon triple bond.
  • alkynol is an alkynol of the formula (I)
  • the preferred substituent R 1 is a methyl group.
  • R 2 represents a saturated linear or branched or cyclic hydrocarbyl group with 1 to 46 C atoms which optionally comprises at least one chemical functional group, particularly at least one hydroxyl group.
  • R 1 and R 2 represent together an alkylene group forming a 5 to 7 membered ring.
  • the alkylene group may be linear or branched and optionally comprises at least one chemical functional group, and/or is olefinically unsaturated. It is preferred that alkylene group is not olefinically saturated.
  • the alkylene group is a pentylene group.
  • One of the preferred alkynols of this embodiment is 1-ethynylcyclohexan-1-ol.
  • R 2 is selected from the group consisting of formula (R2-I), (R2-II), (R2-III), (R2-IV), (R2-V), (R2-VI) and (R2-VII)
  • the alkynol is preferably an alkynol which is selected from the group consisting of 3-methyl-5-(2,6,6-trimethylcyclohex-1-en-1-yl)pent-1-yn-3-ol, (E)-3-methyl-1-(2,6,6-trimethylcyclohex-1-en-1-yl)pent-1-en-4-yn-3-ol, (Z)-3-methyl-1-(2,6,6-trimethylcyclohex-1-en-1-yl)pent-1-en-4-yn-3-ol, (E/Z)-3-methyl-1-(2,6,6-tri-m ethylcyclohex-1-en-1-yl)pent-1-en-4-yn-3-ol, 3-methyl-5-(2,6,6-trimethylcyclo-hex-2-en-1-yl)pent-1-yn-3-ol, (E)-3-methyl-1-(2,6,6-trimethylcyclohex-2-en-1-yl)pent-1
  • the process uses a hydrogenation catalyst which is palladium supported on a carrier.
  • Palladium is a noble metal.
  • Palladium is supported on a carrier, i.e. palladium is attached to/or deposited on a carrier.
  • the carrier is a solid material.
  • said carrier is carbon or an inorganic carrier.
  • Preferred inorganic carriers are oxides or carbonates.
  • Preferred oxides are oxides of silicon, aluminum or titanium or cerium. Particularly preferred are silicon dioxide, alumina and titanium dioxide and ceria.
  • Silicon dioxide can be used as pyrogenic silica or precipitated or ground silica as carrier.
  • silicon dioxide used as carrier is pyrogenic or precipitated silica.
  • Most preferred silicon dioxide is a silicon dioxide which is essential pure SiO 2 .
  • the silicon dioxide carrier consists of more than 95%, more preferably more than 98%, even more preferred more than 99%, by weight of SiO 2 .
  • Calcium carbonate is the preferred carbonate.
  • Preferred calcium carbonate is precipitated calcium carbonate.
  • carrier as used is a mixed oxide.
  • the supported palladium catalyst can be doped with other metals, for example lead.
  • a well-known catalyst of this type is the “Lindlar catalyst” which is palladium on calcium carbonate doped with lead.
  • Such Lindlar catalysts are for example commercially available from Sigma-Aldrich, Evonik, Johnson-Matthey or sacredstan Platinum.
  • More preferred hydrogenation catalysts are palladium on carbon, palladium on silica and palladium on alumina and palladium on carbonate; even more preferred is palladium on calcium carbonate, most preferred is palladium on calcium carbonate doped with lead.
  • the amount of palladium in the hydrogenation catalyst is preferably in the range of from 0.5 to 20 weight %, more preferably in the range of from 2 to 5 weight %, most preferably in the range of approximately 5 weight %, based on the total weight of the hydrogenation catalyst.
  • the hydrogenation catalyst is used in the form of a colloidal suspension.
  • Very suitable hydrogenation catalysts are catalysts as they are disclosed in WO 2009/096783 A1 or in Peter T. Witte et al., Top Catal (2012) 55:505-511 and commercialized by BASF under the trade name NanoSelectTM.
  • the hydrogenation catalyst does not comprise any contain organic any quaternary ammonium compounds.
  • the process is performed in the presence of an additive which is an organic phosphorus compound bearing either a phosphino or a phosphine oxide group.
  • said additive bearing a phosphine oxide group it is preferred that said additive has one or two, more preferred one, phosphine oxide group(s).
  • additive which is an organic phosphorus compound bearing a phosphine oxide is diphenylphosphine oxide.
  • the additive bearing a phosphino group that said additive has more 2 or more, preferably 2 to 4, more preferably 2 to 3, phosphino group(s).
  • the additive has more than one, preferably two, phosphino groups of the formula (III)
  • the alkyl group is preferably a C 1-6 -alkyl group.
  • the cycloalkyl group is preferably a C 5-8 -cycloalkyl group.
  • the additive is selected from the group consisting of 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)-propane, 1,4-bis(diphenylphosphino)butane, 1,3-bis(diphenylphosphino)-2-(diphenylphosphino)methyl-2-methylpropane, 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene and bis(2-diphenylphosphinoethyl)phenylphosphine, preferably selected from the group consisting of 1,2-bis(diphenylphosphino)ethane and 1,3-bis(diphenylphosphino)propane.
  • the additive can be added as such to the alkynol or as a pre-mixture or as a pre-solution to the alkynol before the beginning of the hydrogenation reaction or added during the hydrogenation process.
  • a pre-solution or a pre-mixture the additive is dissolved or dispersed in a small amount of an organic solvent or, preferably, of the alkynol.
  • the weight ratio of the additive to catalyst is in the range of 0.01:1-100:1, preferably of 0.1:1-10:1, and more preferably of 0.2:1-3:1.
  • the amount of hydrogenation catalyst (i.e. sum of palladium and carrier) is preferably in the range of from 0.0001 to 10% by weight %, more preferably in the range of from 0.001 to 1% by weight, most preferably in the range of from 0.01 to 0.1% by weight, based on the weight of the alkynol.
  • the amount of palladium is preferably 1 to 10% by weight, preferably 3 to 7% by weight, based on the weight of the hydrogenation catalyst.
  • the hydrogenation reaction is preferably carried out at a temperature in the range of from 10 to 150° C., more preferably at a temperature in the range of from 20 to 100° C., most preferably at a temperature in the range of from 40 to 90° C.
  • the hydrogenation reaction is preferably carried out at a hydrogen pressure in the range of from 1 to 25 bara (bar absolute) hydrogen, more preferably at a hydrogen pressure in the range of from 2 to 10 bara hydrogen, even more preferably at a hydrogen pressure in the range of from 2 to 6 bara hydrogen, further more preferably at a hydrogen pressure in the range of from 2.5 to 4 bara hydrogen most preferably at a hydrogen pressure in the range of from 2.5 to 3 bara hydrogen.
  • the hydrogenation reaction can be carried out without solvent or in the presence of an organic solvent.
  • the organic solvent is preferably selected from the group consisting of hydrocarbons, halogenated hydrocarbons, alcohols, ethers, esters, carbonates, amides, nitriles and ketones and mixtures thereof. More preferred are C 4-10 aliphatic hydrocarbons, C 6-10 aromatic hydrocarbons, C 6-10 aromatic hydrocarbons substituted with one or more C 1-4 linear alkyl groups or C 3-4 branched alkyl groups or halogens, C 1-4 linear alcohols or C 3-4 branched alcohols, acyclic and cyclic C 4-10 ethers, C 3-10 esters, C 3-10 ketones and mixtures thereof.
  • Especially preferred organic solvents are selected from the group consisting of hexane, heptane, toluene, methanol, ethanol, n-propanol, 2-propanol, n-butanol, tert.-butanol, tetrahydrofuran, 2-methyl-tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, ethylene carbonate, propylene carbonate, acetone, and mixtures thereof.
  • the most preferred solvent is heptane.
  • the hydrogenation is performed in the absence of any organic solvents.
  • the hydrogenation is performed in the absence of any organic quaternary ammonium compounds.
  • the hydrogenation is performed in the absence of any organic solvent and of any organic quaternary ammonium compound.
  • Said alkenol has the same chemical structure as the alkynol, with the exception that the carbon-carbon triple bond is in the alkenol a carbon-carbon double bond.
  • R 1 has the same meaning in formulae (I) and (II) and that R 2 has the same meaning in formulae (I) and (II).
  • the present invention relates to a composition
  • a composition comprising
  • composition is as also disclosed before very suitable to be hydrogenated by molecular hydrogen and yields in very high selectivity the alkenol of the formula (II)
  • the hydrogenation catalyst (80 mg, palladium-lead on calcium carbonate containing 5 weight % palladium) was placed in a 500 ml pressure reactor.
  • the respective additive in the amount as given in table 1 and a total of 270 g 2-methylbut-3-yn-2-ol were added to the reactor.
  • the vessel was sealed and purged with nitrogen 3 times (pressurise to 6 bara and release).
  • the reactor was heated to 70° C. and purged with hydrogen 3 times (pressurise to 4 bara and release).
  • the reactor was pressurised to 2.5 bara and the mixture was stirred.
  • the mixture was sampled multiple times near the end of the reaction to determine when the conversion had reached >99.9%. Samples were analysed by GC (area %) to determine the selectivity.
  • the hydrogenation catalyst (56 mg, palladium-lead on calcium carbonate, containing 5 weight % palladium) was placed in a 500m1 pressure reactor.
  • the respective additive in the amount as given in table 2 and a total of 250 g 3,7-dimethyloct-6-en-1-yn-3-ol were added to the reactor.
  • the vessel was sealed and purged with nitrogen 3 times (pressurise to 6 bara and release).
  • the reactor was heated to 55° C. and purged with hydrogen 3 times (pressurise to 4 bara and release).
  • the reactor was pressurised to 3 bara and the mixture was stirred.
  • the mixture was sampled multiple times near the end of the reaction to determine when the conversion had reached >99.9%. Samples were analysed by GC (area %) to determine the selectivity.
  • the hydrogenation catalyst (50 mg, palladium-lead on calcium carbonate, containing 5 weight % palladium) was placed in a 500m1 pressure reactor.
  • the respective additive in the amount as given in table 3 and a total of 260 g 3,7,11,15-tetramethylhexadec-1-yn-3-ol were added to the reactor.
  • the vessel was sealed and purged with nitrogen 3 times (pressurise to 6 bara and release).
  • the reactor was heated to 85° C. and purged with hydrogen 3 times (pressurise to 4 bara and release).
  • the reactor was pressurised to 3 bara and the mixture was stirred.
  • the mixture was sampled multiple times near the end of the reaction to determine when the conversion had reached >99.9%. Samples were analysed by GC (area %) to determine the selectivity.

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Abstract

The present invention relates to a process of hydrogenating an alkynol selectively to an alkenol by hydrogen using a hydrogenation catalyst which is palladium supported on a carrier in the presence of an additive which is an organic phosphorus compound bearing either a phosphine or a phosphine oxide group and with the proviso that if the additive bears a phosphino group that the additive bears two or more phosphino groups.

Description

    TECHNICAL FIELD
  • The present invention relates to the hydrogenation of alkynols to alkenols.
    • BACKGROUND OF THE INVENTION
  • Alkynes can be hydrogenated to alkenes by hydrogen in the presence of noble metal catalysts. Palladium catalysts can be used for the hydrogenation of alkynols to alkenols.
  • Alkynols or the alkenols, respectively, are substances which are produced on an industrial scale and are of high importance, particularly for the field of vitamins and aroma chemicals. A non-exhaustive list of such important alkynols and alkenols are 2-methylbut-3-yn-2-ol, 2-methylbut-3-en-2-ol, 3,7-dimethyloct-6-en-1-yn-3-ol, 3,7-dimethylocta-1,6-dien-3-ol, 3,7,11,15-tetramethylhexadec-1-yn-3-ol and 3,7,11,15-tetramethylhexadec-1-en-3-ol.
  • In the hydrogenation of alkynols there exist several problems. One problem is that next to the carbon-carbon triple bond also other chemical groups being eventually present might be hydrogenated. To a certain extent this problem can be solved by using protecting groups. This, however, requires additional steps of protection and deprotection which is not favourable in view of additional time, cost and waste formation.
  • Another problem is that the selectivity at high conversion is not sufficiently high. As in any chemical reaction, the target is to have transformed as much as possible of the starting material into the desired product. In the present case, there is a further drive to obtain as high conversion as possible, because the alkynol, i.e. the starting material, and the alkenol, i.e. the product of the selective hydrogenation, are very difficult to separate. Hence, running reactions at partial conversion followed by separation of the unreacted starting material and repeating the reaction is very difficult.
  • A particular problematic aspect in the selective hydrogenation of alkynols is the over-hydrogenation. Over-hydrogenation describes the effect that the hydrogenation of alkynol does not stop at the stage of alkenol but continues to yield significant amounts of alkanol, i.e. that the hydrogenation reaction does not selectively only hydrogenate the carbon-carbon triple bond to the carbon-carbon double bond, but that the carbon-carbon double bond is also hydrogenated to a carbon-carbon single bond in significant amounts. The over-hydrogenated compound can be very difficult to be separated from the desired products.
  • Lindlar discloses in U.S. Pat. No. 2,681,938 a selective hydrogenation of alkynes to alkenes using a palladium catalyst which is modified by lead or bismuth.
  • In U.S. Pat. No. 3,715,404 a selective hydrogenation is disclosed using a palladium catalyst which is partially deactivated by some specific organic sulphur compounds.
  • Furthermore, the hydrogenation of alkynols leads to the formation of undesired side products, such as the formation of dimers or oligomers derived from the alkynol or the alkenol.
    • SUMMARY OF THE INVENTION
  • Therefore, the problem to be solved by the present invention is to offer a process for the hydrogenation of alkynol selectively to an alkenol which yields high conversion, high selectivity and low over-hydrogenation.
  • Surprisingly, the process according to claim 1 has offered a solution to this problem. It has been found that particularly the use of additives having 2 or more phosphino groups are very advantageous in offering this combination of desired properties.
  • Further aspects of the invention are subject of further independent claims. Particularly preferred embodiments are subject of dependent claims.
    • DETAILED DESCRIPTION OF THE INVENTION
  • In a first aspect the present invention relates to a process of hydrogenating an alkynol selectively to an alkenol by hydrogen using a hydrogenation catalyst which is palladium supported on a carrier; in the presence of an additive which is an organic phosphorus compound bearing either a phosphino or a phosphine oxide group; characterized in that in case the additive bears a phosphino group that the additive bears two or more phosphino groups.
  • For sake of clarity, some terms as been used in the present document are defined as follows:
  • In the present document, a “Cx-yalkyl” group is an alkyl group comprising x to y carbon atoms, i.e., for example, a C1-3-alkyl group is an alkyl group comprising 1 to 3 carbon atoms. The alkyl group can be linear or branched. For example —CH(CH3)—CH2—CH3 is considered as a C4-alkyl group.
  • Any wavy line in any formula of this document represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E-configuration.
  • In case identical labels for symbols or groups are present in several formulae, in the present document, the definition of said group or symbol made in the context of one specific formula applies also to other formulae which comprises the same said label.
  • In the present document, an “alkynol” is a chemical compound which has at least one carbon-carbon triple bond and at least one hydroxyl group in its chemical formula. In other words, an alkynol is a hydroxy functionalised alkyne.
  • Analogously, an “alkenol” is a chemical compound which has at least one carbon-carbon double bond and at least one hydroxyl group in its chemical formula. In other words, an alkenol is a hydroxy functionalised alkene.
  • In the present document a “hydrocarbyl” group is a univalent group which formally is formed by removing a hydrogen atom from a hydrocarbon.
    • Alkynol
  • In this process an alkynol is selectively hydrogenated to the respective alkenol.
  • The alkynol has at least one carbon-carbon triple bond and at least one hydroxyl group in its chemical formula whereas the respective alkenol has at least one carbon-carbon double bond and at least one hydroxyl group in its chemical formula.
  • It is important for the present invention that the hydrogenation is selective, that is reducing the carbon-carbon triple bond to the respective carbon-carbon double bond. In other words, the hydroxyl group as well as any other chemical groups which might be present in the alkynol are not modified by said hydrogenation reaction. Particularly, the hydrogenation is selective also in that sense that the carbon-carbon double bond of the alkenol is not, or at least not significantly, further hydrogenated to a carbon-carbon single bond (“over-hydrogenation”).
  • It, furthermore, has been observed that—besides the reduced formation of over-hydrogenated products—also the formation of other side products, such as formation of dimers or oligomers derived from the starting material or products, are significantly reduced by the above process.
  • In one of the preferred embodiments, the alkynol is an alkynol which has a hydroxyl group attached to a carbon which is in alpha position to the carbon-carbon triple bond of the alkynol, i.e. the alkynol is preferably an alpha-alkynol.
  • The alkynol has preferably a following structural element
  • Figure US20220234974A1-20220728-C00001
  • in its structural formula, where * signifies the position(s) of further substituent(s).
  • In an even more preferred embodiment, the alkynol is an alkynol in which the carbon-carbon triple bond is a terminal carbon-carbon triple bond.
  • In a very preferred embodiment the alkynol has a following structural element
  • Figure US20220234974A1-20220728-C00002
  • in its structural formula where * signifies the position of further substituent(s).
  • In a very preferred embodiment the alkynol is an alkynol of the formula (I)
  • Figure US20220234974A1-20220728-C00003
  • wherein
  • either
      • R1 represents H or a methyl or ethyl group, preferably a methyl or ethyl group; and
      • R2 represents a saturated or unsaturated linear or branched or cyclic hydrocarbyl group with 1 to 46 C atoms which optionally comprises at least one chemical functional group, particularly at least one hydroxyl group;
  • or
      • R1 and R2 represent together an alkylene group forming a 5 to 7 membered ring;
      • with the proviso that R1 has the same meaning in formulae (I) and (II) and that R2 has the same meaning in formulae (I) and (II).
  • In formula (I) the preferred substituent R1 is a methyl group.
  • It is preferred that R2 represents a saturated linear or branched or cyclic hydrocarbyl group with 1 to 46 C atoms which optionally comprises at least one chemical functional group, particularly at least one hydroxyl group.
  • It is further preferred that in formula (I) the substituent R2 is a methyl group.
  • A very preferred alkynol of formula (I) is 2-methylbut-3-yn-2-ol (i.e. R1═R2=methyl).
  • In another embodiment, R1 and R2 represent together an alkylene group forming a 5 to 7 membered ring. The alkylene group may be linear or branched and optionally comprises at least one chemical functional group, and/or is olefinically unsaturated. It is preferred that alkylene group is not olefinically saturated.
  • Preferably the alkylene group is a pentylene group. One of the preferred alkynols of this embodiment is 1-ethynylcyclohexan-1-ol.
  • In another preferred embodiment the substituent is R2 is selected from the group consisting of formula (R2-I), (R2-II), (R2-III), (R2-IV), (R2-V), (R2-VI) and (R2-VII)
  • Figure US20220234974A1-20220728-C00004
      • wherein the dotted line represents the bond by which the substituent of formula (R2-I), (R2-II), (R2-III), (R2-IV), (R2-V), (R2-VI) or (R2-VII) is bound to the rest of the compound of formula (I) or formula (II);
      • and wherein any bond having dotted line (
        Figure US20220234974A1-20220728-P00001
        ) represents independently from each other either a single carbon-carbon bond or a double carbon-carbon bond, preferably a single carbon-carbon single bond;
      • and wherein any wavy line represents independently from each other a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z or in the E-configuration;
      • and wherein n represents 1, 2, 3, 4, 5 or 6, particularly 1 or 2 or 3, preferably 3 or 2, most preferably 2.
  • The alkynol is preferably an alkynol which is selected from the group consisting of 3-methyl-5-(2,6,6-trimethylcyclohex-1-en-1-yl)pent-1-yn-3-ol, (E)-3-methyl-1-(2,6,6-trimethylcyclohex-1-en-1-yl)pent-1-en-4-yn-3-ol, (Z)-3-methyl-1-(2,6,6-trimethylcyclohex-1-en-1-yl)pent-1-en-4-yn-3-ol, (E/Z)-3-methyl-1-(2,6,6-tri-m ethylcyclohex-1-en-1-yl)pent-1-en-4-yn-3-ol, 3-methyl-5-(2,6,6-trimethylcyclo-hex-2-en-1-yl)pent-1-yn-3-ol, (E)-3-methyl-1-(2,6,6-trimethylcyclohex-2-en-1-yl)pent-1-en-4-yn-3-ol, (Z)-3-methyl-1-(2,6,6-trimethylcyclohex-2-en-1-yl)pent-1-en-4-yn-3-ol, 3,7-dimethyloct-6-en-1-yn-3-ol, 3,7-dimethyloct-1-yn-3-ol, (E)-3,7-dimethylnon-6-en-1-yn-3-ol, (Z)-3,7-dimethylnon-6-en-1-yn-3-ol, (E/Z)-3,7-di-methylnon-6-en-1-yn-3-ol, 3,7-dimethylnon-1-yn-3-ol, 3,7,11-trimethyldodec-1-yn-3-ol, (E)-3,7,11-trimethyldodec-6-en-1-yn-3-ol, (Z)-3,7,11-trimethyldodec-6-en-1-yn-3-ol, (E/Z)-3,7,11-trimethyldodec-6-en-1-yn-3-ol, 3,7,11-trimethyldodec-10-en-1-yn-3-ol, (E)-3,7,11-trimethyldodeca-6,10-dien-1-yn-3-ol, (Z)-3,7,11-trimethyldo-deca-6,10-dien-1-yn-3-ol, (E/Z)-3,7,11-trimethyldodeca-6,10-dien-1-yn-3-ol, 3,7,11,15-tetramethylhexadec-1-yn-3-ol, (E)-3,7,11,15-tetramethylhexadec-6-en-1-yn-3-ol, (Z)-3,7,11,15-tetramethylhexadec-6-en-1-yn-3-ol, (E/Z)-3,7,11,15-tetra-methylhexadec-6-en-1-yn-3-ol, (E)-3,7,11,15-tetramethylhexadec-10-en-1-yn-3-ol, (Z)-3,7,11,15-tetramethylhexadec-10-en-1-yn-3-ol, (E/Z)-3,7,11,15-tetramethyl-hexadec-10-en-1-yn-3-ol, 3,7,11,15-tetramethylhexadec-14-en-1-yn-3-ol, (6E,10E)-3,7,11,15-tetramethylhexadeca-6,10-dien-1-yn-3-ol, (6E,10Z)-3,7,11,15-tetramethylhexadeca-6,10-dien-1-yn-3-ol, (6Z,10E)-3,7,11,15-tetramethylhexa-deca-6,10-dien-1-yn-3-ol, (6Z,10Z)-3,7,11,15-tetramethylhexadeca-6,10-dien-1-yn-3-ol, (E)-3,7,11,15-tetramethylhexadeca-10,14-dien-1-yn-3-ol, (Z)-3,7,11,15-tetramethylhexadeca-10,14-dien-1-yn-3-ol, (6E, 10E/Z)-3,7,11,15-tetramethylhexa-deca-6,10-dien-1-yn-3-ol, (6Z, 10E/Z)-3,7,11,15-tetramethylhexadeca-6,10-dien-1-yn-3-ol, (6E/Z,10E)-3,7,11,15-tetramethylhexadeca-6,10-dien-1-yn-3-ol, (6E/Z,10Z)-3,7,11,15-tetramethylhexadeca-6,10-dien-1-yn-3-ol, (6E/Z, 10E/Z)-3,7,11,15-tetramethylhexadeca-6,10-dien-1-yn-3-ol, (E)-3,7,11,15-tetramethyl-hexadeca-6,14-dien-1-yn-3-ol, (Z)-3,7,11,15-tetramethylhexadeca-6,14-dien-1-yn-3-ol, (E/Z)-3,7,11,15-tetramethylhexadeca-6,14-dien-1-yn-3-ol, (E)-3,7,11,15-tetra-methylhexadeca-10,14-dien-1-yn-3-ol, (Z)-3,7,11,15-tetramethylhexadeca-10,14-dien-1-yn-3-ol, (E/Z)-3,7,11,15-tetramethylhexadeca-10,14-dien-1-yn-3-ol, (6E,10E)-3,7,11,15-tetramethylhexadeca-6,10,14-trien-1-yn-3-ol, (6E,10Z)-3,7,11,15-tetramethylhexadeca-6,10,14-trien-1-yn-3-ol, (6Z,10E)-3,7,11,15-tetra-methylhexadeca-6,10,14-trien-1-yn-3-ol, (6Z,10Z)-3,7,11,15-tetramethylhexadeca-6,10,14-trien-1-yn-3-ol, (6E,10E/Z)-3,7,11,15-tetramethylhexadeca-6,10,14-trien-1-yn-3-ol, (6E/Z,10E)-3,7,11,15-tetramethylhexadeca-6,10,14-trien-1-yn-3-ol, (6Z,10E/Z)-3,7,11,15-tetramethylhexadeca-6,10,14-trien-1-yn-3-ol, (6E/Z,10Z)-3,7,11,15-tetramethylhexadeca-6,10,14-trien-1-yn-3-ol, and (6E/Z,10E/Z)-3,7,11,15-tetramethylhexadeca-6,10,14-trien-1-yn-3-ol.
    • Hydrogenation Catalyst
  • The process uses a hydrogenation catalyst which is palladium supported on a carrier.
  • Such hydrogenation catalysts are principally known to the person skilled in the art. Palladium is a noble metal. In the present invention Palladium is supported on a carrier, i.e. palladium is attached to/or deposited on a carrier. The carrier is a solid material.
  • Preferably said carrier is carbon or an inorganic carrier. Preferred inorganic carriers are oxides or carbonates. Preferred oxides are oxides of silicon, aluminum or titanium or cerium. Particularly preferred are silicon dioxide, alumina and titanium dioxide and ceria.
  • Silicon dioxide can be used as pyrogenic silica or precipitated or ground silica as carrier. Preferably silicon dioxide used as carrier is pyrogenic or precipitated silica. Most preferred silicon dioxide is a silicon dioxide which is essential pure SiO2. In other words, it is preferred that the silicon dioxide carrier consists of more than 95%, more preferably more than 98%, even more preferred more than 99%, by weight of SiO2.
  • Calcium carbonate is the preferred carbonate. Preferred calcium carbonate is precipitated calcium carbonate.
  • It is possible that carrier as used is a mixed oxide.
  • In addition, the supported palladium catalyst can be doped with other metals, for example lead. A well-known catalyst of this type is the “Lindlar catalyst” which is palladium on calcium carbonate doped with lead. Such Lindlar catalysts are for example commercially available from Sigma-Aldrich, Evonik, Johnson-Matthey or Hindustan Platinum.
  • More preferred hydrogenation catalysts are palladium on carbon, palladium on silica and palladium on alumina and palladium on carbonate; even more preferred is palladium on calcium carbonate, most preferred is palladium on calcium carbonate doped with lead.
  • The amount of palladium in the hydrogenation catalyst is preferably in the range of from 0.5 to 20 weight %, more preferably in the range of from 2 to 5 weight %, most preferably in the range of approximately 5 weight %, based on the total weight of the hydrogenation catalyst.
  • In one the embodiment, the hydrogenation catalyst is used in the form of a colloidal suspension.
  • Very suitable hydrogenation catalysts are catalysts as they are disclosed in WO 2009/096783 A1 or in Peter T. Witte et al., Top Catal (2012) 55:505-511 and commercialized by BASF under the trade name NanoSelect™.
  • In another preferred embodiment, the hydrogenation catalyst does not comprise any contain organic any quaternary ammonium compounds.
    • Additive
  • The process is performed in the presence of an additive which is an organic phosphorus compound bearing either a phosphino or a phosphine oxide group.
  • In case of the additive bearing a phosphine oxide group it is preferred that said additive has one or two, more preferred one, phosphine oxide group(s).
  • Particularly preferred as additive which is an organic phosphorus compound bearing a phosphine oxide is diphenylphosphine oxide.
  • In case of the additive bearing a phosphino group, that said additive has more 2 or more, preferably 2 to 4, more preferably 2 to 3, phosphino group(s).
  • In a preferred embodiment, the additive has more than one, preferably two, phosphino groups of the formula (III)
  • Figure US20220234974A1-20220728-C00005
      • wherein R is either an alkyl group or a cycloalkyl group or an aryl group, particularly a phenyl or a tolyl group and wherein the dotted line represents the bond by which the substituent of formula (III) is bound to the rest of the additive.
  • The alkyl group is preferably a C1-6-alkyl group. The cycloalkyl group is preferably a C5-8-cycloalkyl group.
  • In a preferred embodiment the additive is selected from the group consisting of 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)-propane, 1,4-bis(diphenylphosphino)butane, 1,3-bis(diphenylphosphino)-2-(diphenylphosphino)methyl-2-methylpropane, 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene and bis(2-diphenylphosphinoethyl)phenylphosphine, preferably selected from the group consisting of 1,2-bis(diphenylphosphino)ethane and 1,3-bis(diphenylphosphino)propane.
  • The additive can be added as such to the alkynol or as a pre-mixture or as a pre-solution to the alkynol before the beginning of the hydrogenation reaction or added during the hydrogenation process. In case of a pre-solution or a pre-mixture the additive is dissolved or dispersed in a small amount of an organic solvent or, preferably, of the alkynol.
  • It is preferred that the weight ratio of the additive to catalyst is in the range of 0.01:1-100:1, preferably of 0.1:1-10:1, and more preferably of 0.2:1-3:1.
  • The amount of hydrogenation catalyst (i.e. sum of palladium and carrier) is preferably in the range of from 0.0001 to 10% by weight %, more preferably in the range of from 0.001 to 1% by weight, most preferably in the range of from 0.01 to 0.1% by weight, based on the weight of the alkynol.
  • The amount of palladium is preferably 1 to 10% by weight, preferably 3 to 7% by weight, based on the weight of the hydrogenation catalyst.
  • The hydrogenation reaction is preferably carried out at a temperature in the range of from 10 to 150° C., more preferably at a temperature in the range of from 20 to 100° C., most preferably at a temperature in the range of from 40 to 90° C.
  • The hydrogenation reaction is preferably carried out at a hydrogen pressure in the range of from 1 to 25 bara (bar absolute) hydrogen, more preferably at a hydrogen pressure in the range of from 2 to 10 bara hydrogen, even more preferably at a hydrogen pressure in the range of from 2 to 6 bara hydrogen, further more preferably at a hydrogen pressure in the range of from 2.5 to 4 bara hydrogen most preferably at a hydrogen pressure in the range of from 2.5 to 3 bara hydrogen.
  • The hydrogenation reaction can be carried out without solvent or in the presence of an organic solvent. The organic solvent is preferably selected from the group consisting of hydrocarbons, halogenated hydrocarbons, alcohols, ethers, esters, carbonates, amides, nitriles and ketones and mixtures thereof. More preferred are C4-10 aliphatic hydrocarbons, C6-10 aromatic hydrocarbons, C6-10 aromatic hydrocarbons substituted with one or more C1-4 linear alkyl groups or C3-4 branched alkyl groups or halogens, C1-4 linear alcohols or C3-4 branched alcohols, acyclic and cyclic C4-10 ethers, C3-10 esters, C3-10 ketones and mixtures thereof. Especially preferred organic solvents are selected from the group consisting of hexane, heptane, toluene, methanol, ethanol, n-propanol, 2-propanol, n-butanol, tert.-butanol, tetrahydrofuran, 2-methyl-tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, ethylene carbonate, propylene carbonate, acetone, and mixtures thereof. The most preferred solvent is heptane.
  • Preferably, however, the hydrogenation is performed in the absence of any organic solvents.
  • In a preferred embodiment the hydrogenation is performed in the absence of any organic quaternary ammonium compounds.
  • In a very much preferred embodiment, the hydrogenation is performed in the absence of any organic solvent and of any organic quaternary ammonium compound.
  • The above described process yields selectively the respective alkenol. Said alkenol has the same chemical structure as the alkynol, with the exception that the carbon-carbon triple bond is in the alkenol a carbon-carbon double bond.
  • In other words, when in the preferred case the alkynol of formula (I)
  • Figure US20220234974A1-20220728-C00006
  • is hydrogenated, the alkenol formed by the selective hydrogenation is the alkenol of formula (II)
  • Figure US20220234974A1-20220728-C00007
  • with the proviso that R1 has the same meaning in formulae (I) and (II) and that R2 has the same meaning in formulae (I) and (II).
  • It has been found that the above process of hydrogenating an alkynol selectively to an alkenol that offers at the same time a very high selectivity and very low over-hydrogenation at a very high conversion.
  • In a further aspect, the present invention relates to a composition comprising
      • a compound of formula (I)
  • Figure US20220234974A1-20220728-C00008
      • wherein
        • either
          • R1 represents H or a methyl or ethyl group, preferably a methyl or ethyl group; and
          • R2 represents a saturated or unsaturated linear or branched or cyclic hydrocarbyl group with 1 to 46 C atoms which optionally comprises at least one chemical functional group, particularly at least one hydroxyl group;
        • or
          • R1 and R2 represent together an alkylene group forming a 5 to 7 membered ring;
      • a hydrogenation catalyst which is palladium supported on a carrier; and
      • at least one additive which is an organic phosphorus compound bearing either a phosphino or a phosphine oxide group, characterized in that in case the additive bears a phosphino group that the additive bears two or more phosphino groups.
  • The compound of formula (I), the hydrogenation catalyst as well as the additive have been disclosed and discussed in great detail above.
  • Said composition is as also disclosed before very suitable to be hydrogenated by molecular hydrogen and yields in very high selectivity the alkenol of the formula (II)
  • Figure US20220234974A1-20220728-C00009
    • Examples
  • The present invention is further illustrated by the following experiments. List of additives used for the examples:
  •
    PO1 diphenylphosphine oxide
    P1-1 tricyclohexyl phosphine
    P1-2 triphenylphosphine
    P1-3 tri-orthotolylphosphine
    P2-1 1,2-bis(diphenylphosphino)ethane
    P2-2 1,3-bis(diphenylphosphino)propane
    P2-3 1,4-bis(diphenylphosphino)butane
    P2-4 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene
    P3-1 bis(2-diphenylphosphinoethyl)phenylphosphine
    • Selective Hydrogenation Series 1 Hydrogenation of methylbut-3-yn-2-ol to methylbut-3-en-2-ol
  • The hydrogenation catalyst (80 mg, palladium-lead on calcium carbonate containing 5 weight % palladium) was placed in a 500 ml pressure reactor. The respective additive in the amount as given in table 1 and a total of 270 g 2-methylbut-3-yn-2-ol were added to the reactor. The vessel was sealed and purged with nitrogen 3 times (pressurise to 6 bara and release). The reactor was heated to 70° C. and purged with hydrogen 3 times (pressurise to 4 bara and release). The reactor was pressurised to 2.5 bara and the mixture was stirred. The mixture was sampled multiple times near the end of the reaction to determine when the conversion had reached >99.9%. Samples were analysed by GC (area %) to determine the selectivity.
  • TABLE 1
    Hydrogenation of methylbut-3-yn-2-ol.
    Conver- Selec- Over-
    Addi- Amount sion tivity2 Hyd*
    Example tive [mg] [%] [%]1 [%]1
    Ref. 1 None >99.9 94.9 1.7
    Ref. 2 P1-1 77 >99.9 95.7 1.2
    Ref. 3 P1-2 75 >99.9 96.7 0.9
    1 PO1 56 >99.9 95.5 0.9
    2 P2-1 55 >99.9 97.5 1.4
    2 P2-1 55 >99.9 97.5 1.4
    3 P2-2 57 >99.9 97.8 1.2
    4 P2-3 59 >99.9 97.8 1.2
    5 P3-1 65 >99.9 97.9 1.1
    1determined by GC in area %
    2selectivity: amount of alkenol in the final reaction mixture
    *Over-Hyd = over-hydrogenation: methylbutan-2-ol determined by GC in area %
    • Selective Hydrogenation Series 2 Hydrogenation of 3,7-dimethyloct-6-en-1-yn-3-ol to 3,7-dimethylocta-1,6-dien-3-ol
  • The hydrogenation catalyst (56 mg, palladium-lead on calcium carbonate, containing 5 weight % palladium) was placed in a 500m1 pressure reactor. The respective additive in the amount as given in table 2 and a total of 250 g 3,7-dimethyloct-6-en-1-yn-3-ol were added to the reactor. The vessel was sealed and purged with nitrogen 3 times (pressurise to 6 bara and release). The reactor was heated to 55° C. and purged with hydrogen 3 times (pressurise to 4 bara and release). The reactor was pressurised to 3 bara and the mixture was stirred. The mixture was sampled multiple times near the end of the reaction to determine when the conversion had reached >99.9%. Samples were analysed by GC (area %) to determine the selectivity.
  • TABLE 2
    Hydrogenation of 3,7-dimethyloct-6-en-1-yn-3-ol.
    Conver- Selec- Over-
    Addi- Amount sion tivity2 Hyd*
    Example tive [mg] [%] [%]1 [%]1
    Ref. 4 None >99.9 94.4 3.4
    Ref. 5 P1-1 86 >99.9 95.7 3.0
    6 P2-2 64 >99.9 95.6 3.1
    1determined by GC in area %
    2selectivity: amount of alkenol in the final reaction mixture
    *Over-Hyd = over-hydrogenation: 3,7-dimethyloct-6-en-3-ol and 3,7- dimethyloct-1-en-3-ol and 3,7-dimethyloctan-3-ol determined by GC in area %
    • Selective Hydrogenation Series 3 Hydrogenation of 3,7,11,15-tetramethylhexadec-1-yn-3-ol to 3,7,11,15-tetra-methylhexadec-1-en-3-ol
  • The hydrogenation catalyst (50 mg, palladium-lead on calcium carbonate, containing 5 weight % palladium) was placed in a 500m1 pressure reactor. The respective additive in the amount as given in table 3 and a total of 260 g 3,7,11,15-tetramethylhexadec-1-yn-3-ol were added to the reactor. The vessel was sealed and purged with nitrogen 3 times (pressurise to 6 bara and release). The reactor was heated to 85° C. and purged with hydrogen 3 times (pressurise to 4 bara and release). The reactor was pressurised to 3 bara and the mixture was stirred. The mixture was sampled multiple times near the end of the reaction to determine when the conversion had reached >99.9%. Samples were analysed by GC (area %) to determine the selectivity.
  • TABLE 3
    Hydrogenation of 3,7,11,15-tetramethylhexadec-
    1-yn-3-ol 3,7-dimethyloct-6-en-1-yn-3-ol.
    Conver- Selec- Over-
    Addi- Amount sion tivity2 Hyd*
    Example tive [mg] [%] [%]1 [%]1
    Ref. 6 None >99.9 88.5 8.0
    Ref. 7 P1-1 68 >99.9 90.5 6.1
    Ref. 8 P1-2 63 >99.9 92.3 4.3
    7 PO1 49 >99.9 92.5 3.8
    8 P2-1 48 >99.9 92.5 4.2
    9 P2-2 50 >99.9 92.3 4.4
    10 P2-3 52 >99.9 91.8 4.9
    11 P2-4 75 >99.9 90.6 5.9
    12 P3-1 65 >99.9 91.8 1.9
    1determined by GC in area %
    2selectivity: amount of alkenol in the final reaction mixture
    *Over-Hyd = over-hydrogenation: 3,7,11,15-tetramethylhexadecan-3-ol determined by GC in area %

Claims (15)

1. A process of hydrogenating an alkynol selectively to an alkenol by hydrogen using a hydrogenation catalyst which is palladium supported on a carrier;
in the presence of an additive which is an organic phosphorus compound bearing either a phosphino or a phosphine oxide group; wherein in case the additive bears a phosphino group that the additive bears two or more phosphino groups.
2. The process according to claim 1, wherein the alkynol is an alkynol which has a hydroxyl group attached to a carbon which is in alpha position to the carbon-carbon triple bond of the alkynol.
3. The process according to claim 1, wherein the carbon-carbon triple bond is a terminal carbon-carbon triple bond.
4. The process according to claim 1 wherein the alkynol is an alkynol of the formula (I)
Figure US20220234974A1-20220728-C00010
and the alkenol of the formula (II)
Figure US20220234974A1-20220728-C00011
wherein
either
R1 represents H or a methyl or ethyl group, preferably a methyl or ethyl group; and
R2 represents a saturated or unsaturated linear or branched or cyclic hydrocarbyl group with 1 to 46 C atoms which optionally comprises at least one chemical functional group, particularly at least one hydroxyl group;
or
R1 and R2 represent together an alkylene group forming a 5 to 7 membered ring;
with the proviso that R1 has the same meaning in formulae (I) and (II) and that R2 has the same meaning in formulae (I) and (II).
5. The process according to claim 1 wherein R1 is a methyl group.
6. The process according to claim 1 wherein R2 is a methyl group.
7. The process according to claim 1 wherein R2 is selected from the group consisting of formula (R2-I), (R2-II), (R2-III), (R2-IV), (R2-V), (R2-VI) and (R2-VII),
Figure US20220234974A1-20220728-C00012
wherein the dotted line represents the bond by which the substituent of formula (R2-I), (R2-II), (R2-III), (R2-IV), (R3-V), (R2-VI) or (R2-VII) is bound to the rest of the compound of formula (I) or formula (II);
and wherein any bond having dotted line (
Figure US20220234974A1-20220728-P00002
) represents independently from each other either a single carbon-carbon bond or a double carbon-carbon bond, preferably a single carbon-carbon bond;
and wherein any wavy line represents independently from each other a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z or in the E-configuration;
and wherein n represents 1, 2, 3, 4, 5 or 6, particularly 1 or 2 or 3, preferably 3 or 2, most preferably 2.
8. The process according to claim 1 wherein the additive has more than one phosphino groups of the formula (III)
Figure US20220234974A1-20220728-C00013
wherein R is either an alkyl group or a cycloalkyl group or an aryl group, particularly a phenyl or a tolyl group and wherein the dotted line represents the bond by which the substituent of formula (III) is bound to the rest of the additive.
9. The process according to claim 1 wherein the organic phosphorus compound is selected from the group consisting of 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)-propane, 1,4-bis(diphenylphosphino)butane, 1,3-bis(diphenylphosphino)-2-(diphenyl-phosphino)methyl-2-methylpropane, 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene and bis(2-diphenylphosphinoethyl)phenylphosphine; preferably selected from the group consisting of 1,2-bis(diphenylphosphino)ethane and 1,3-bis(diphenylphosphino)propane.
10. The process according to claim 1 wherein the hydrogenation is performed in the absence of any organic quaternary ammonium compounds.
11. The process according to claim 1 wherein the hydrogenation is performed in the absence of any organic solvents.
12. The process according to claim 1 wherein the carrier is carbon or an inorganic carrier, particularly an oxide or a carbonate, preferably silicon oxide, aluminum oxide or cerium oxide or titanium oxide or calcium carbonate.
13. The process according to claim 1 wherein the hydrogenation catalyst is in the form of a colloidal suspension.
14. The process according to claim 1 wherein the weight ratio of the additive to catalyst is in the range of 0.01:1-100:1, preferably of 0.1:1-10:1, and more preferably of 0.2:1-3:1.
15. Composition comprising
a compound of formula (I)
Figure US20220234974A1-20220728-C00014
wherein
either
R1 represents H or a methyl or ethyl group, preferably a methyl or ethyl group; and
R2 represents a saturated or unsaturated linear or branched or cyclic hydrocarbyl group with 1 to 46 C atoms which optionally comprises at least one chemical functional group, particularly at least one hydroxyl group;
or
R1 and R2 represent together an alkylene group forming a 5 to 7 membered ring;
a hydrogenation catalyst which is palladium supported on a carrier; and
at least one additive which is an organic phosphorus compound bearing either a phosphino or a phosphine oxide group;
wherein in case the additive bears a phosphino group that the additive bears two or more phosphino groups.
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