WO2014094169A1 - Hydrogenation catalyst - Google Patents

Hydrogenation catalyst Download PDF

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Publication number
WO2014094169A1
WO2014094169A1 PCT/CA2013/050995 CA2013050995W WO2014094169A1 WO 2014094169 A1 WO2014094169 A1 WO 2014094169A1 CA 2013050995 W CA2013050995 W CA 2013050995W WO 2014094169 A1 WO2014094169 A1 WO 2014094169A1
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Prior art keywords
catalyst
hydrogenation
linker
nanoparticles
iron
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PCT/CA2013/050995
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French (fr)
Inventor
Audrey Moores
Chao-Jun Li
Reuben HUDSON
Yasuhiro Uozumi
Takao OSAKO
Yoichi Yamada
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The Royal Institution For The Advancement Of Learning/Mcgill University
Riken
National Institutes Of Natural Sciences
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Publication of WO2014094169A1 publication Critical patent/WO2014094169A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • B01J31/1683—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins the linkage being to a soluble polymer, e.g. PEG or dendrimer, i.e. molecular weight enlarged complexes
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/20—Preparation of ethers by reactions not forming ether-oxygen bonds by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers

Definitions

  • the invention relates generally to a catalyst for selective hydrogenation of chemical compounds.
  • the present invention describes a novel synthesis of a polymer supported Fe°
  • NPs nano-particles
  • NPs nano-particles
  • the present invention describes the embedding of the catalytically active Fe NPs into an amphiphilic polymer resin.
  • Two beneficial effects on catalysis are observed from this functionalization. Firstly, the polymer increased the longevity or lifespan of the nanoparticles, which revealed catalytic activity in ethanol and water: ethanol mixtures, up to 9: 1.
  • the Fe NPs polymer resin enabled use of the formed catalyst in a flow system.
  • the chemical industry has widely accepted the use of flow systems to alleviate waste, work-up effort and scale-up problems, given the ease by which the pressurizing of flow systems can be performed.
  • a catalyst comprising an amphiphilic polymer resin with embedded iron (Fe°) nanoparticles for hydrogenation of chemical compounds.
  • the catalyst of the present invention increase longevity of the zero (0) oxidation state of the iron (Fe°) nanoparticles in protic solvents.
  • the process of the present invention enabled hydrogenation of chemical compounds using iron nanoparticles catalyst in a flow system using protic solvents.
  • a hydrogenation catalyst comprising an amphiphilic polymer resin with a resin support; a linker attached to the support, wherein the linker comprises a functionalized group (FG) selected from COOH, NH 2 a halide or combinations thereof, and an embedded iron Fe° nanoparticles.
  • FG functionalized group
  • the catalyst herein described wherein the resin support is composed of polystyrene beads.
  • the catalyst herein described wherein the spacer is polyethylene glycol.
  • the catalyst herein described wherein the functional group is NH 2 .
  • the catalyst herein described wherein the embedded Fe° nanoparticles are loaded at a concentration of from 1 to 15 mg Fe / g catalyst.
  • the catalyst herein described wherein the concentration is 12 mg Fe / g catalyst.
  • the process for hydrogenation herein described wherein the protic solvent is ethanol, water or a mixture thereof.
  • Fig.1 represents a schematic view of flow hydrogenation with polymer supported iron (Fe°) nano-particles according to one embodiment of the present invention
  • Fig.2 represents a Catalyst prepared by thermal decomposition of Fe(CO) 5 according to one embodiment of the present invention
  • Fig.3 represents Catalyst prepared by black tea reduction of FeS0 4 according to one embodiment of the present invention
  • Fig 4 A to F are TEM (transmission electron micrograph) images of various embodiments of the present invention: A) and B) FeNP@PS-PEG-NH 2 (thermal decomposition); C) FeNP@PS-PEG-NH 2 (tea reduction); D) FeNP@PS-PEG-Br (thermal decomposition); E) FeNP@PS-PEG-COOH (thermal decomposition); F) FeNP@PS-NH 2 (thermal decomposition);
  • Fig. 5 is a high resolution TEM image depicting lattice fringes of FeNP@PS-PEG-
  • Fig. 6 is a five gram scale up of cinnamyl acetate demonstrating the ease of scale-up that the flow system provides, and also the robust nature of the catalyst in prolonged reactions according to one embodiment of the present invention.
  • catalyst, use and process of the present invention comprise those wherein the following embodiments are present, either independently or in combination.
  • a catalyst for hydrogenation of chemical compounds comprising an amphiphilic polymer resin supporting iron nanoparticles according to an embodiment of the invention is described herein with reference to hydrogenation of functional groups present on a chemical compound.
  • a catalyst comprising an amphiphilic polymer resin that supports iron nanoparticles for hydrogenation of alkenes, alkynes, aromatic aldehyde and aromatic imine functionalities on a chemical compound.
  • amphiphilic polymer is defined herein as a polymer having at least one lipophilic portion and at least one hydrophilic portion.
  • lipophilic is defined herein as a material that has an affinity for and the ability to dissolve lipids. It is believed that Fe is found and protected in a lipophilic area of the amphiphilic polymer resin.
  • embedded is herein defined with regard to the iron NP as at least partially within the polymer resin.
  • an hydrogenation catalyst comprising an amphiphilic polymer resin with a resin support, a linker attached to the support, wherein the linker comprises a functionalized group selected from NH 2 ; COOH; halogen such as Br, CI, and I; SH; OH; OS0 3 H; OP(OH) 2 and combinations thereof, and an embedded iron Fe° nanoparticles.
  • the amphiphilic polymer resin is composed of polystyrene beads having functional groups that coordinate iron.
  • the functional groups that coordinate iron are attached to the polystyrene beads by a linker.
  • the linker coordinates iron.
  • the linker is polyethylene glycol derivative.
  • the functional groups that coordinate iron are NH 2 or C0 2 H.
  • the functional group that coordinates iron is NH 2 .
  • the functional group that coordinates iron is C0 2 H.
  • the iron nanoparticles are loaded between 1.03 and 11.72 mg of iron nanoparticles for 1 g of polymer resin.
  • a process for hydrogenation of chemical compounds using a catalyst comprising an amphiphilic polymer resin that supported iron nanoparticles.
  • a process comprising an amphiphilic polymer resin that supported iron nanoparticles for hydrogenation of alkenes, alkynes, aromatic aldehyde and aromatic imine functionalities on a chemical compound.
  • the process is carried out in a protic solvent.
  • the protic solvent is alcohol based solvent, water or a mixture thereof.
  • the protic solvent is ethanol, water or a mixture thereof.
  • the protic solvent is ethanol.
  • the process is carried out under pressure between 10 to
  • the process is carried out under pressure between 20 to 50 bar. In a further embodiment, the process is carried out under pressure between 30 to 50 bar. In a further embodiment, the process is carried out under pressure between 35 to 45 bar.
  • the process is carried out at a temperature between 60 to 100°C.
  • the process is carried out in a flow system.
  • the catalyst of the present invention is used in a flow system.
  • the flow system is used with a flow rate between 0.5 ml/min to 2 ml/min.
  • the flow system is used with a flow rate between 0.75 ml/min to 1.25 ml/min.
  • amphiphilic polymer resin as a support for Fe NPs is illustrated in Figure 1.
  • the linker spacers include: ethylene glycol, diethylene glycols; triethylene glycol; propylene glycol; 1 ,3-propanediol; 1 ,4-butanediol (examples of which include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol and 2-butoxyethanol) and combinations thereof.
  • the preferred spacer is a PEG with a molecular weight of between 1000 and 5000 Da, where in a preferred embodiment the molecular weight of the PEG is 3000 Da.
  • Fe NPs were synthesized in situ, in the presence of the resin, either by thermal decomposition of Fe(CO) 5 ( Figure 2) or through the greener black tea reduction of FeS0 4 ( Figure 3).
  • the lines are separated by 2.45 A, which is in good agreement with the interatomic spacing calculated to be 2.49 A, from either base-centered cubic (bcc) or face-centered cubic (fee) iron. These are very different from spacing measured for iron oxides.
  • Figure 5 demonstrates the Fe(0) nature of the nanoparticles. Fewer particles were visible when using the tea reduction method, most of them having again a size of ⁇ 5nm ( Figure 4 C).
  • Amines are found to be the best Fe NPs stabilizers, where they used notably in the original synthesis of fFe NPs by thermal decomposition, and are were better ligands than either -Br or -COOH functionalized polymers. Removal of the PEG spacer while keeping the amine functionality (entry 5) had a drastic effect on loading with a 10 fold drop in Fe content, perhaps because the extra oxygen atoms help to coordinate iron, helping seed the formation of nanoparticles.
  • reaction conditions 100 ° C, 40 bar, 1 mL/min through 300 mg catalsyst, 0.05M Styrene in EtOH
  • Reaction Conditions 0.05M substrate in EtOH, 100"C, 40 bar H 2 , 1 mL/min, 300 mg FeNP@PS-PEG-NH 2 5 Reaction Conditions: 0.05M substrate in EtOH, 100 C, 60 bar H 2 , 1 mL/min 300 mg FeNP@PS-PEG-NH 2
  • Reaction conditions 0 bar H 2 , 100 ° C, 0.5 ml/min, 0.05 M substrate in EtOH, (residence time 116 seconds)
  • TentagelTM S COOH, TentagelTM S Br and TentagelTM S NH 2 were purchased from RAPP polymere. Aminomethylated polystyrene was purchased from Nova biochem. High purity water was obtained by the use of a Milli-Q- MilliporeTM with 0.22 ⁇ filter, Q-guard1 and ultrapure organex cartridge.
  • Linker-terminated polystyrene/(polyethylene glycol) beads (TentagelTM produced by RAPP Polymere or aminomethylated poly-styrene from Nova, 1 gram) and 1 -octadecene (60 mL, 90% Aldrich) were combined with a magnetic stir bar in a 200 mL round bottom shlenk flask. The mixture was degassed with N 2 at 120 ° C for 30 minutes. The temperature was then raised to 180 ° C, at which point Fe(CO) 5 (2.1 mL, 99.99%, Aldrich) was quickly injected. The reaction was stirred for 30 minutes at 180 ° C under a blanket of N 2 , then allowed to cool to room temperature. The resultant polymer-supported iron nanoparticles (FeNP@PS-(PEG)-FG) were then washed 3 times with hexanes (50 mL, 99% Aldrich) and dried under vacuum.
  • TeNP@PS-(PEG)-FG were then
  • EXAMPLE 2 Synthesis of FeNP@PS-(PEG)-NH 2 by black tea reduction: [0074] The extract of black tea (20 g) was brewed with boiling water (1 L) and steeped until it reached room temperature At room temperature, this extract was added to a solution of amine-terminated polystyrene/polyethylene glycol beads (1 gram), FeS0 4 (3.767 g) and water (2 L) with a magnetic stir bar in a 4L glass jug. After stirring for 24 hours, the polymer was filtered and collected.
  • Leica EMFCS microtome The resultant slices were loaded onto carbon/formvar grids and subjected to TEM analysis on a JEM-2010F (HR7) operated at 120 kV.
  • the interatomic spacing was measured on Figure 3 using the measuring toll of the GI MP software over 14 lines.
  • a cartridge was packed with 300 mg of PS-LK supported iron nanoparticles and connected to an H-CubeTM flow hydrogenation system.
  • a solution of various substrates (0.05 M) in ethanol, water, or a mixture of the two was passed through the flow system at different rates, temperatures and hydrogen pressures.
  • the resultant solution was characterized by GC-MS and quantified by GC-FID.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Described herein is a catalyst for hydrogenation of chemical compounds comprising an amphiphilic polymer resin with embedded iron nanoparticles and its use. Also described herein is a process for the manufacture of a chemical compound comprising hydrogenation of alkenes, alkynes, aromatic aldehydes and aromatic imines functionalities in the presence of a catalyst defined and a process for hydrogenation of chemical compounds using the catalyst comprising an amphiphilic polymer resin with embedded iron nanoparticles.

Description

HYDROGENATION CATALYST
FIELD OF INVENTION
[0001 ] The invention relates generally to a catalyst for selective hydrogenation of chemical compounds.
BACKGROUND OF THE INVENTION
[0002] Hydrogenation, known to chemists for decades, remains to this day among the most studied reactions. Its industrial applications span from petrochemical conversion to pharmaceuticals synthesis and there is a plethora of catalysts active for this transformation. However, hydrogenation reactions heavily rely on the chemistry of group 9 and 10 metals. These elements are very expensive and their price is highly volatile on the stock market. Additionally, regulations on their presence at ppm levels in drugs is highly regulated by organizations such as the FDA, because of their inherent toxicity. In response to both the economic and environmental concerns, research efforts have been made to improve recovery and limit leaching, or to seek group 9 and 10 metal-free solutions.
SUM MARY
[0003] The present invention describes a novel synthesis of a polymer supported Fe°
NPs (nano-particles) catalyst, which displays excellent reactivity for the selective hydrogenation of alkenes, alkynes, aromatic imines and aldehydes in a flow system. Further demonstrating the industrial applicability of the present catalyst, it is robust to water exposure, surpassing hydrogenation reaction yields for aqueous mixtures of known iron nanoparticle systems. This work represents for the first time the merger of three green chemistry themes: flow hydrogenation with H2; water and ethanol as benign solvents, and the use of biologically benign heterogeneous iron as a catalyst. The present invention also reduces the aforesaid difficulties and disadvantages.
[0004] The present invention describes the embedding of the catalytically active Fe NPs into an amphiphilic polymer resin. Two beneficial effects on catalysis are observed from this functionalization. Firstly, the polymer increased the longevity or lifespan of the nanoparticles, which revealed catalytic activity in ethanol and water: ethanol mixtures, up to 9: 1. Secondly, the Fe NPs polymer resin enabled use of the formed catalyst in a flow system. The chemical industry has widely accepted the use of flow systems to alleviate waste, work-up effort and scale-up problems, given the ease by which the pressurizing of flow systems can be performed.
[0005] We herein report for the first time the application to alkene and alkyne hydrogenation of three green chemistry themes— flow chemistry, water as a benign solvent, and the use of cheap, non-toxic and biologically-essential heterogeneous iron. [0006] From one aspect, there is provided a catalyst comprising an amphiphilic polymer resin with embedded iron (Fe°) nanoparticles for hydrogenation of chemical compounds.
[0007] Advantageously, the catalyst of the present invention increase longevity of the zero (0) oxidation state of the iron (Fe°) nanoparticles in protic solvents.
[0008] In a further aspect, there is provided the use of a catalyst of the present invention for hydrogenation of chemical compounds.
[0009] In a further aspect, there is provided a process for the manufacture of a chemical compound comprising hydrogenation step in the presence of a catalyst of the present invention.
[0010] Alternatively, there is provided a process for hydrogenation of a chemical compound using a catalyst comprising an amphiphilic polymer resin that embedded iron (Fe°) nanoparticles.
[001 1 ] Advantageously, the process of the present invention enabled hydrogenation of chemical compounds using iron nanoparticles catalyst in a flow system using protic solvents. In one aspect of the present invention there is provided a hydrogenation catalyst comprising an amphiphilic polymer resin with a resin support; a linker attached to the support, wherein the linker comprises a functionalized group (FG) selected from COOH, NH2 a halide or combinations thereof, and an embedded iron Fe° nanoparticles..
[0012] In accordance with a further aspect of the present invention, there is provided the catalyst herein described, wherein the iron is embedded in a lipophilic portion of the amphiphilic polymer.
[0013] In accordance with a yet further aspect of the present invention, there is provided the catalyst herein described, wherein the resin support is composed of polystyrene beads..
[0014] In accordance with a still further aspect of the present invention, there is provided the catalyst herein described, wherein the functional groups are attached to the polystyrene beads with a linker.
[0015] [0014] In accordance with a still further aspect of the present invention, there is provided the catalyst herein described, wherein the linker includes a spacer.
[0016] In accordance with another aspect of the present invention, there is provided the catalyst herein described, wherein the linker is polyethylene glycol derivative.
[0017] In accordance with a further aspect of the present invention, there is provided the catalyst herein described, wherein the spacer is polyethylene glycol. [0018] In accordance with a further aspect of the present invention, there is provided the catalyst herein described, wherein the functional group is NH2.
[0019] In accordance with a further aspect of the present invention, there is provided the catalyst herein described, wherein the embedded Fe° nanoparticles are loaded at a concentration of from 1 to 15 mg Fe / g catalyst.
[0020] In accordance with a further aspect of the present invention, there is provided the catalyst herein described, wherein the concentration is 12 mg Fe / g catalyst.
[0021 ] In accordance with a further aspect of the present invention, there is provided the catalyst herein described, for hydrogenation of alkenes, alkynes, aromatic aldehydes and aromatic imines.
[0022] In another aspect of the present invention there is provided a process for the manufacture of a chemical compound comprising hydrogenation of alkenes, alkynes, aromatic aldehydes and aromatic imines functionalities in the presence of a catalyst defined herein
[0023] In a further aspect of the present invention there is provided a process for hydrogenation of chemical compounds using a catalyst comprising an amphiphilic polymer resin with embedded iron nanoparticles.
[0024] In accordance with another aspect of the present invention, there is provided the process for hydrogenation herein described, wherein the hydrogenation is carried out in a protic solvent.
[0025] In accordance with a further aspect of the present invention, there is provided the process for hydrogenation herein described, wherein the protic solvent is ethanol, water or a mixture thereof.
[0026] In accordance with a yet further aspect of the present invention, there is provided the process for hydrogenation herein described, wherein the hydrogenation is carried out under pressure between 10 to 60 bar.
[0027] In accordance with a still further aspect of the present invention, there is provided the process for hydrogenation herein described, wherein the hydrogenation is carried out in at a temperature between 60 to 100°C.
[0028] In accordance with a further aspect of the present invention, there is provided the process for hydrogenation herein described, wherein the catalyst is used in a flow system. [0029] In accordance with another aspect of the present invention, there is provided the process for hydrogenation herein described, wherein the flow system is used with a flow rate between 0.5 ml/min to 2 ml/min.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Further aspects and advantages of the present invention will become better understood with reference to the description in association with the following drawings in which:
[0031 ] Fig.1 represents a schematic view of flow hydrogenation with polymer supported iron (Fe°) nano-particles according to one embodiment of the present invention;
[0032] Fig.2 represents a Catalyst prepared by thermal decomposition of Fe(CO)5 according to one embodiment of the present invention;
[0033] Fig.3 represents Catalyst prepared by black tea reduction of FeS04 according to one embodiment of the present invention;
[0034] Fig 4 A to F are TEM (transmission electron micrograph) images of various embodiments of the present invention: A) and B) FeNP@PS-PEG-NH2 (thermal decomposition); C) FeNP@PS-PEG-NH2 (tea reduction); D) FeNP@PS-PEG-Br (thermal decomposition); E) FeNP@PS-PEG-COOH (thermal decomposition); F) FeNP@PS-NH2 (thermal decomposition);
[0035] Fig. 5 is a high resolution TEM image depicting lattice fringes of FeNP@PS-PEG-
NH2 according to one embodiment of the present invention; and
[0036] Fig. 6 is a five gram scale up of cinnamyl acetate demonstrating the ease of scale-up that the flow system provides, and also the robust nature of the catalyst in prolonged reactions according to one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0037] This invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. Also, the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of "including", "comprising", or "having", "containing", "involving" and variations thereof herein, is meant to encompass the items listed thereafter as well as, optionally, additional items. In the following description, the same numerical references refer to similar elements. In the drawings, like reference characters designate like or similar parts.
[0038] In one embodiment, catalyst, use and process of the present invention comprise those wherein the following embodiments are present, either independently or in combination.
[0039] In one embodiment, there is provided a catalyst for hydrogenation of chemical compounds comprising an amphiphilic polymer resin supporting iron nanoparticles according to an embodiment of the invention is described herein with reference to hydrogenation of functional groups present on a chemical compound. In a further embodiment, there is provided a catalyst comprising an amphiphilic polymer resin that supports iron nanoparticles for hydrogenation of alkenes, alkynes, aromatic aldehyde and aromatic imine functionalities on a chemical compound.
[0040] The term "amphiphilic polymer" is defined herein as a polymer having at least one lipophilic portion and at least one hydrophilic portion.
[0041 ] The term "lipophilic" is defined herein as a material that has an affinity for and the ability to dissolve lipids. It is believed that Fe is found and protected in a lipophilic area of the amphiphilic polymer resin.
[0042] The term "embedded" is herein defined with regard to the iron NP as at least partially within the polymer resin.
[0043] In a further embodiment, there is provided an hydrogenation catalyst comprising an amphiphilic polymer resin with a resin support, a linker attached to the support, wherein the linker comprises a functionalized group selected from NH2; COOH; halogen such as Br, CI, and I; SH; OH; OS03H; OP(OH)2 and combinations thereof, and an embedded iron Fe° nanoparticles.
[0044] In a further embodiment, the amphiphilic polymer resin is composed of polystyrene beads having functional groups that coordinate iron. In another embodiment, the functional groups that coordinate iron are attached to the polystyrene beads by a linker. In a further embodiment, the linker coordinates iron. The present inventors have discovered that the embedded iron0 catalyst of the present invention is surprisingly stable even after numerous hydrogenation reactions cycles. This stability is most likely due to the combination of elements of the catalyst but particularly the coordination of the iron0 with a functional group, and where in a preferred embodiment the functional group is with an amine.
[0045] In a further embodiment, the linker is polyethylene glycol derivative.
[0046] In a further embodiment, the functional groups that coordinate iron are NH2 or C02H.
[0047] In a further embodiment, the functional group that coordinates iron is NH2.
[0048] In a further embodiment, the functional group that coordinates iron is C02H.
[0049] In a further embodiment, the iron nanoparticles are loaded between 1.03 and 11.72 mg of iron nanoparticles for 1 g of polymer resin.
[0050] In another embodiment, there is provided a process for hydrogenation of chemical compounds using a catalyst comprising an amphiphilic polymer resin that supported iron nanoparticles. In a further embodiment, there is provided a process comprising an amphiphilic polymer resin that supported iron nanoparticles for hydrogenation of alkenes, alkynes, aromatic aldehyde and aromatic imine functionalities on a chemical compound.
[0051 ] In a further embodiment, the process is carried out in a protic solvent. In a further embodiment, the protic solvent is alcohol based solvent, water or a mixture thereof. In a further embodiment, the protic solvent is ethanol, water or a mixture thereof. In a further embodiment, the protic solvent is ethanol.
[0052] In a further embodiment, the process is carried out under pressure between 10 to
60 bar. In a further embodiment, the process is carried out under pressure between 20 to 50 bar. In a further embodiment, the process is carried out under pressure between 30 to 50 bar. In a further embodiment, the process is carried out under pressure between 35 to 45 bar.
[0053] In a further embodiment, the process is carried out at a temperature between 60 to 100°C.
[0054] In a further embodiment, the process is carried out in a flow system. In an altenate embodiment, the catalyst of the present invention is used in a flow system. In a further embodiment, the flow system is used with a flow rate between 0.5 ml/min to 2 ml/min. In a further embodiment, the flow system is used with a flow rate between 0.75 ml/min to 1.25 ml/min.
[0055] The amphiphilic polymer resin as a support for Fe NPs is illustrated in Figure 1.
The resin is composed of a support resin such as polystyrene (PS) beads (average size 90 micron), functionalized with a variety of linkers (LK). These linkers are terminated with a functional group (FG = NH2; COOH; halogen such as: Br, CI, I: SH; OH; OS03H; OP(OH)2 and combinationals thereof) and may optionally contain a polyethylene glycol (PEG) spacer. It is the linker with the support that affords the amphiphilic polymer resin its duality of hydrophobicity and hydrophilicity. These polymer resins were purchased and used as is. Alternate support resins include polyalkylene polymers, halogenated polymers, polyesters, , polyamides, cellulose derived polymers sulfonated polymers and combinations thereof.
[0056] The linker spacers include: ethylene glycol, diethylene glycols; triethylene glycol; propylene glycol; 1 ,3-propanediol; 1 ,4-butanediol (examples of which include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol and 2-butoxyethanol) and combinations thereof. The preferred spacer is a PEG with a molecular weight of between 1000 and 5000 Da, where in a preferred embodiment the molecular weight of the PEG is 3000 Da.
[0057] The Fe NPs were synthesized in situ, in the presence of the resin, either by thermal decomposition of Fe(CO)5 (Figure 2) or through the greener black tea reduction of FeS04 (Figure 3).
[0058] The second synthesis (greener black tea reduction) was only performed with PS-
PEG-NH2 polymer resin. The resulting materials were characterized by transmission electron microscopy (TEM) of slices of the materials obtained through microtomy. This method allowed visualizing the Fe NPs inside the matrix (Figure 4). Once again, PS-(PEG)-NH2 afforded good results. Well dispersed and monodispersed approximate 5 nm Fe NPs were observed in the case of thermal decomposition (Figure 4, A and B). At high resolution, regular lines evince the crystal lattice of FeNP@PS-PEG-NH2 (Figure 5).
[0059] The lines are separated by 2.45 A, which is in good agreement with the interatomic spacing calculated to be 2.49 A, from either base-centered cubic (bcc) or face-centered cubic (fee) iron. These are very different from spacing measured for iron oxides.
[0060] Figure 5 demonstrates the Fe(0) nature of the nanoparticles. Fewer particles were visible when using the tea reduction method, most of them having again a size of ~5nm (Figure 4 C).
[0061 ] With both PS-(PEG)-Br and PS-(PEG)-COOH, the thermal decomposition produced larger particles between 15 and 20 nm for Br and 5 and 20 nm for COOH. PS-NH2 afforded localized clusters of particles between 5 and 10 nm. Large sections of the matrix did not contain Fe NPs. In no sample tested was there any iron oxide layer at the surface of the particles, as we had observed in past work for iron. This demonstrates a very high stability of this system toward oxidation. [0062] In addition to TEM, the materials were characterized by ICP-MS (Table 1 ). The highest loading was obtained with FeNP@PS-PEG-NH2 with 11.72 mg Fe/g catalyst(entry 1 ), confirming the observation made by TEM. Interestingly, thermal decomposition was a more efficient method than tea reduction as the latter produced material with about 5 times less iron content (entry 2). I n fact, the reaction conditions of thermal decomposition, which occurs at 180°C, are more favorable to iron diffusion, than those of tea reduction (room temperature). A change in the terminal group, from NH2 to COOH (entry 3) or Br (entry 4) affected loading, although all PEGylated systems could successfully immobilize Fe NPs. Amines are found to be the best Fe NPs stabilizers, where they used notably in the original synthesis of fFe NPs by thermal decomposition, and are were better ligands than either -Br or -COOH functionalized polymers. Removal of the PEG spacer while keeping the amine functionality (entry 5) had a drastic effect on loading with a 10 fold drop in Fe content, perhaps because the extra oxygen atoms help to coordinate iron, helping seed the formation of nanoparticles.
[0063] These polymer supported-Fe NPs were then used in both flow and batch reactors for hydrogenation of styrene in ethanol (Table 1 ). Though all polymer systems provided quantitative yields in flow, only the FeNP@PS-PEG-NH2 generated by thermal decomposition provided a moderate yield in batch conditions (entry 1 ).
Table 1 - Iron loading and styrene hydrogenation yield of polymer-immobilized Fe NPs
Entry Composition Fe Flow Batch
Loading3 Yield (%)c
(%)b
1 FeNP(∑ ¾PS-PEG-NH2 d 1 1.72 100 44%
2 FeNP(∑ ¾PS-PEG-NH2 e 2.55 100 13%
3 FeNP(∑ ¾PS-PEG-COOHd 5.01 100 24%
4 FeNP(∑ ¾PS-PEG-Brd 4.05 100 8%
5 FeNP(∑ ¾PS-NH2 d 1.03 100 19%
a mg Fe/g catalyst measured by ICP
b reaction conditions: 100°C, 40 bar, 1 mL/min through 300 mg catalsyst, 0.05M Styrene in EtOH
c reaction conditions: 100°C, 40 bar, 0.005M Styrene in EtOH (17 ml_), 6 hours
d Fe nanoparticles generated by thermal decomposition of Fe(CO)5
e Fe nanoparticles generated by reduction of black tea-extract reduction of FeS04
[0064] Selective hydrogenation of styrene's olefinic double bond served as a model reaction for the optimization of reaction conditions (Table 2). A pressure of 40 bar H2, temperature of 100°C and flow rate of 2 mL/min constituted the benchmark conditions, achieving a 92% conversion of styrene to ethyl benzene (entry 1 ). Increasing the pressure to 60 bar pushed the yield to 95% (entry 2). Decreasing the flow rate to 1 mL/min afforded a quantitative yield, by improving residence time on the catalyst (entry 4). From there, decreasing the pressure to 10 bar dropped the yield to 54% (entry 6). Decreasing the temperature (entries 7 and 8) slightly decreased the yield. Interestingly, the reaction still proceeded with a 95% yield in a 50:50 mixture of water and ethanol (entry 10), and an 88% yield in a 10:90 mixture of ethanol and water (entry 1 1 ).
[0065] This result contrasts with what is observed when using iron/iron oxide core-shell where the 50:50 mixture did affect drastically catalysis. It is believed that increased stability of the Fe NPs in an almost pure water environment is caused by the embedding of the particles inside lipophilic pockets of the polymers, preventing water oxidation of their surface of the iron NPs.
[0066] These optimized conditions of the one embodiment of the present invention also afforded quantitative yields for FeNP@PS-PEG-COOH, FeNP@PS-PEG-Br, FeNP@PS-NH2 (Table 1 ), all generated by thermal decomposition of Fe(CO)5 as well as FeNP@PS-PEG-NH2 generated by black tea extract reduction of FeS04. At least for the nanoparticles generated by thermal decomposition of Fe(CO)5, we assume all reduction to happen by iron because 1 ) the purity of the reagent was 99.999% and 2) ICP-MS of the digested sample detected no nickel, a common contaminant of iron known to be active for hydrogenation. We also assume the mechanism to be heterogeneous because ICP-MS analysis of the product solution indicated only 0.007 ppm soluble iron.
Table 2 - Screening of hydrogenation conditions3
Entry Pressure Temp (°C) Flow Yield (%)
(bar) (ml/min)
1 40 100 2 92
2 60 100 2 95
3 20 100 2 85
4 40 100 1 100
5 40 100 0.5 94
6 10 100 1 54
7 40 80 1 95
8 40 60 1 94
9b 40 100 1 100
10c 40 100 1 95
1 1d 40 100 1 88
12e 40 100 λ 0
a Reaction Conditions: Styrene (0.05 M) in EtOH was passed through 250 mg of FeNP@PS-PEG-NH2 resin (generated by thermal decomposition of Fe(CO)s).
bA mixture of EtOH and H2O (1 :99 v:v) was used as the solvent.
°A mixture of EtOH and H2O (50:50 v:v) was used as the solvent.
d A mixture of EtOH and H2O (10:90 v:v) was used as the solvent.
e No catalyst was used
[0067] The functional group tolerance and selectivity are herein described (Table 3). The catalyst system is very active for aromatic alkene hydrogenation (entries 1 , 5, 16 and 17). Aliphatic alkenes (entry 3) and alkynes, either internal (entry 4) or terminal (entry 2), are moderately active. With slightly harsher conditions, however, such substrates can be converted in higher yields (Table 4). The system demonstrates a selectivity for C-C double and triple bonds over ketones (entries 10 and 1 1 ), esters (entry 5), nitriles (entry 14), arenes (entries 1 , 5, 6, 15, and 16). The system also selected against aliphatic aldehydes (entry 9) and imines (entry 13). When activated by an aromatic ring, however, aldehydes (entries 7 and 8) and imines (entry 12) could be converted. With such mild conditions, we did not have to worry about reductive elimination of aryl halides (entry 15) or reduction of nitro groups (entry 16) opening the doors for selective synthesis. Given the sensitivity of aryl halides and aryl nitro groups to reducing conditions, these two examples of chemoselectivity make the presented system very interesting from a synthetic viewpoint.
Table 3 - Functional group tolerance and selectivity3
Entry Substrate Product Yield:Selectivity (%:%)
Figure imgf000013_0001
3 67: 100
Figure imgf000013_0002
35:96
Figure imgf000013_0003
10 ft ?H 0: N/A
11 ft ft 100: 100
O 0
2 .NJO . u 00: 00
Figure imgf000013_0004
Figure imgf000014_0001
Reaction Conditions: 0.05M substrate in EtOH, 100"C, 40 bar H2, 1 mL/min, 300 mg FeNP@PS-PEG-NH2 5 Reaction Conditions: 0.05M substrate in EtOH, 100 C, 60 bar H2, 1 mL/min 300 mg FeNP@PS-PEG-NH2
Table 4 - Reactivity of variously substituted alkenes3
Entry Substitution Substrate Yield (%)
ce
Figure imgf000014_0002
Reaction conditions: 0 bar H2, 100°C, 0.5 ml/min, 0.05 M substrate in EtOH, (residence time 116 seconds)
[0068] In an effort to examine the reactivity of variously substituted, non-functionalized alkenes we used slightly harsher conditions (Table 4) because such alkenes, when not activated by an aromatic ring, do not react as quickly (Table 3). Mono-substituted alkenes (entry 1 ) proceeded in good yields. Cis alkenes (entry 2) reacted slightly faster than trans alkenes (entry 3). Geminal substitution is more problematic (entry 4). Considering this, it is not surprising that tri- substituted alkenes (entry 5) reacted exceptionally slowly and tetra-substituted alkenes provided only trace amounts of product (entry 6).
[0069] For the sake of comparing the reactivity of various styrene derivatives, we used milder reaction conditions in order to achieve greater separation of chemical yields (Table 5). This comparison suggests that sterics affect reactivity more than electronics. For example, the difference in yield between ortho (entry 6, 35%) and meta (entry 7, 58%) chloro substituted styrene overshadows the difference in yield between electron donating (NH2, entry 9, 50%) and electron withdrawing (N02, entry 10, 39%) para substituted styrene. The trend for methylstyrene further demonstrates this effect. Para methylstyrene (entry 2, 52%) and meta-methylstyrene (entry 3, 48%) both reacted faster than unsubstituted styrene (entry 1 , 45%). However, ortho- methylstyrene reacts slower (entry 2, 42%). Once in the ortho position, the negative steric effect of the methyl group outweighs the positive electron-donating effect. The example with the largest ortho substituent (Br, entry 5) exhibits the lowest overall yield (18%).
Table 5 - Activity of styrene derivatives3
Entry Substrate Product Yield:Selectivity
(%:%)
Figure imgf000015_0001
52: >99
Figure imgf000015_0002
' Reaction conditions: 0.05M substrate in EtOH, 80 C, 20 bar H2, 3 mL/min, 300 mg FeNP@PS-PEG-NH2
[0070] Ease of reaction scale-up represents one of the most attractive benefits of flow chemistry. We therefore preformed a five gram-scale up with cinnamyl acetate (Figure 6) to demonstrate this scale-up potential and robust nature of the catalyst in prolonged reactions. The hourly snapshots indicate that the yield never dipped below 94%, with an overall yield of 96%. This equates to a turn over number (TON) of 434. In a 20.7 gram scale-up of styrene this TON increased to 1685.
EXPERI MENTAL SECTION
Chemicals
[0071 ] Styrene (99.0% w/ -0.003% p-t-butylcatechol stabilizer) and p-methoxystyrene
(99% w/ 200 ppm p-t-butylcatechol stabilizer) were purchased from VVako chemicals. Cinnyml alcohol (98.0%), trans-2-heptene (99%), cis-2-heptene (97%), Fe(CO)5 (99.999%) and 1- octadecene (90%) were purchased from Aldrich. 2-phenylpropionaldehyde (98%), cinnyml acetate (99%), 4-methylstyrene (99%), benzylideneaniline (98%), and benzylcarbamate (97%) were purchased from TCI. Ethanol (99.5%) was purchased from Kanto Chemical Co. Tentagel™ S COOH, Tentagel™ S Br and Tentagel™ S NH2 were purchased from RAPP polymere. Aminomethylated polystyrene was purchased from Nova biochem. High purity water was obtained by the use of a Milli-Q- Millipore™ with 0.22μηι filter, Q-guard1 and ultrapure organex cartridge.
Instruments
[0072] The gas chromatograph fitted with a flame ionization detector (GC FID) was an
Agilent Technologies 6850 series I I Network GC system. The gas chromatography mass spectrometer (GC MS) was an Agilent 5973 Network Mass Selective Detector. High pressure hydrogenation flow reactor catalytic tests were performed on an H-Cube - Thales Nanotechnologies. The transmission electron microscope (TEM) used for imaging was a JEM- 201 OF (HR7). Microtome slices were performed with a Leica™ EMFCS. The inductively coupled plasma (ICP) measurements were recorded on a Leeman labs, inc. profile plus high dispersion ICP.
EXAMPLE 1 - Synthesis of FeNP@PS-LK by thermal decomposition:
[0073] Linker-terminated polystyrene/(polyethylene glycol) beads (Tentagel™ produced by RAPP Polymere or aminomethylated poly-styrene from Nova, 1 gram) and 1 -octadecene (60 mL, 90% Aldrich) were combined with a magnetic stir bar in a 200 mL round bottom shlenk flask. The mixture was degassed with N2 at 120°C for 30 minutes. The temperature was then raised to 180°C, at which point Fe(CO)5 (2.1 mL, 99.99%, Aldrich) was quickly injected. The reaction was stirred for 30 minutes at 180°C under a blanket of N2, then allowed to cool to room temperature. The resultant polymer-supported iron nanoparticles (FeNP@PS-(PEG)-FG) were then washed 3 times with hexanes (50 mL, 99% Aldrich) and dried under vacuum.
EXAMPLE 2 - Synthesis of FeNP@PS-(PEG)-NH2 by black tea reduction: [0074] The extract of black tea (20 g) was brewed with boiling water (1 L) and steeped until it reached room temperature At room temperature, this extract was added to a solution of amine-terminated polystyrene/polyethylene glycol beads (1 gram), FeS04 (3.767 g) and water (2 L) with a magnetic stir bar in a 4L glass jug. After stirring for 24 hours, the polymer was filtered and collected.
EXAMPLE 3 - Characterization of PS-LK supported iron nanoparticles:
[0075] To visualize the FeNP@PS-(PEG)-FG catalysts, the polymer was sliced with a
Leica EMFCS microtome. The resultant slices were loaded onto carbon/formvar grids and subjected to TEM analysis on a JEM-2010F (HR7) operated at 120 kV. The interatomic spacing was measured on Figure 3 using the measuring toll of the GI MP software over 14 lines. The lattice parameter is 2.87A for (base-centered cubic) bcc iron and 3.515 A for (face-centered cubic) fee. Both of them provide an interatomic spacing of 2.49 A using equation d = a V3/2 for bcc and d=a/V2 for fee, with "a" being the lattice parameter and "d" the interatomic spacing.
EXAMPLE 4 - PS-LK supported iron nanoparticles for Hydrogenation:
[0076] A cartridge was packed with 300 mg of PS-LK supported iron nanoparticles and connected to an H-Cube™ flow hydrogenation system. A solution of various substrates (0.05 M) in ethanol, water, or a mixture of the two was passed through the flow system at different rates, temperatures and hydrogen pressures. The resultant solution was characterized by GC-MS and quantified by GC-FID.
[0077] It should be appreciated that the invention is not limited to the particular examples and embodiments described and illustrated herein but includes all modifications and variations falling within the scope of the invention as defined in the appended claims.
REFERENCES
(1 ) Johannes G. de Vries; Elsevier, C. J. The Handbook of Homogeneous Hydrogenation; Wiley-VCH, 2008.
(2) de Vries, J. G.; Elsevier, C. J. Handbook of Homogeneous Hydrogenation; Wiley-VCH: Weinheim, 2007.
(3) Behr, A.; Neubert, P. Applied Homogeneous Catalysis; Wiley-VCH: Weinheim, Germany, 2012.
(4) Crudden, C. M.; Sateesh, M.; Lewis, R., J. Am. Chem. Soc. 2005, 127, 10045-10050.
(5) a) Chase, P. A.; Stephan, D. W., Angew. Chem. Int. Ed. 2008, 47, 7433-7437; b) Chase, P. A.; Jurca, T.; Stephan, D. W., Chem. Commun. 2008, 1701-1703.
(6) a) Morris, R. H., Chem. Soc. Rev. 2009, 38, 2282-2291 ; b) Phua, P.-H.; Lefort, L; Boogers, J. A. F.; Tristany, M.; de Vries, J. G., Chem Commun. 2009, 3747-3749.
(7) a) Bart, S. C; Hawrelak, E. J.; Lobkovsky, E.; Chirik, P. J., J. Organomet. Chem. 2005, 24, 5518-5527; b) Bart, S. C; Lobkovsky, E.; Chirik, P. J., J. Am. Chem. Soc. 2004, 126, 13794- 13807.
(8) a) Mikhailine, A.; Lough, A. J.; Morris, R. H., J. Am. Chem. Soc. 2009, 131 , 1394-1395; b) Sui-Seng, C; Freutel, F.; Lough, A. J.; Morris, R. H., Angew. Chem. -Int. Edit. 2008, 47, 940- 943.
(9) Federsel, C; Boddien, A.; Jackstell, R.; Jennerjahn, R.; Dyson, P. J.; Scopelliti, R.; Laurenczy, G.; Beller, M., Angew. Chem. Int. Ed. 2010, 49, 9777-9780.
(10) a) Enthaler, S.; Haberberger, M.; Irran, E., Chem. Asian J. 2011 , 6, 1613-1623; b) Haberberger, M.; Irran, E.; Enthaler, S., Eur. J. Inorg. Chem. 2011 , 2797-2802.
(11 ) Shylesh, S.; Schunemann, V.; Thiel, W. R., Angew. Chem. Int. Ed 2010, 49, 3428-3459.
(12) a) Armbruster, M.; Kovnir, K.; Friedrich, M.; Teschner, D. ; Wowsnick, G.; Hahne, M.; Gille, P.; Szentmiklosi, L; Feuerbacher, M.; Heggen, M.; Girgsdies, F.; Rosenthal, D.; Schlogl, R.; Grin, Y., Nature Mater. 2012, 11 , 690-693; b) Cantillo, D.; Baghbanzadeh, M.; Kappe, C. O., Angew. Chem. Int. Ed. 2012, 51 , 10190-10193; c) Sonnenberg, J. F.; Coombs, N.; Dube, P. A.; Morris, R. H., J. Am. Chem. Soc. 2012, 134, 5893-5899.
(13) Rangheard, C; de Julian Fernandez, C; Phua, P.-H.; Hoorn, J.; Lefort, L ; de Vries, J. G., Dalton Trans. 2010, 39, 8464-8471. (14) Stein, M.; Wieland, J.; Steurer, P.; Toelle, F.; Muelhaupt, R.; Breit, B., Adv. Synth. Catal. 2011 , 353, 523-527.
(15) Welther, A.; Bauer, M.; Mayer, M.; Jacobi von Wangelin, A., ChemCatChem 2012, 4, 1088-1093.
(16) Li, C.-J.; Chan, T.-H. Comprehensive Organic Reactions in Aqueous Media; Wiley, 2007.
(17) a) Li, C.-J.; Chen, L , Chem. Soc. Rev. 2006, 35, 68-82; b) Li, C. J., Chem. Rev. 1993, 93, 2023-2035.
(18) Breslow, R., Acc. Chem. Res. 1991 , 24, 159-164.
(19) Narayan, S.; Muldoon, J.; Finn, M. G.; Fokin, V. V.; Kolb, H. C; Sharpless, K. B., Angew. Chem. Int. Ed 2005, 44, 3275-3279.
(20) Ohde, H.; Wai, C. M.; Kim, H.; Kim, J.; Ohde, M., J. Am. Chem. Soc. 2002, 124, 4540- 4541.
(21 ) a) Wu, X.; Li, X.; King, F.; Xiao, J., 2005, 117, 3473-3477; b) Wu, X.; Liu, J.; Li, X.; Zanotti-Gerosa, A.; Hancock, F.; Vinci, D.; Ruan, J.; Xiao, J., Angew. Chem. Int. Ed 2006, 45, 6718-6722.
(22) a) Uozumi, Y.; Yamada, Y. M. A., Chem. Rec. 2009, 9, 51-65; b) Sarkar, S. M.; Uozumi, Y.; Yamada, Y. M. A., Angew. Chem. Int. Ed 2011 , 123, 9609-9613; c) Yamada, Y. M. A.; Sarkar, S. M.; Uozumi, Y., J. Am. Chem. Soc. 2012, 134, 3190-3198.
(23) a) Zarka, M. T.; Nuyken, O.; Weberskirch, R., Chem. Euro. J. 2003, 9, 3228-3234; b) Arakawa, Y.; Chiba, A.; Haraguchi, N.; Itsuno, S., Adv. Synth. Catal. 2008, 350, 2295-2304.
(24) Uozumi, Y.; Yamada, Y. M. A., Chem. Rec. 2009, 9, 51-65.
(25) a) Uozumi, Y.; Nakao, R., Angew. Chem. Int. Ed 2003, 42, 194-197; b) Yamada, Y. M. A.; Arakawa, T.; Hocke, H.; Uozumi, Y., Chem. Asian J. 2009, 4, 1092-1098.
(26) Putta, C. B.; Ghosh, S., Adv. Synth. Catal. 2011 , 353, 1889-1896.
(27) a) Nakao, R.; Rhee, H.; Uozumi, Y., Org. Lett. 2004, 7, 163-165; b) Yamada, Y. M. A.; Watanabe, T.; Ohno, A.; Uozumi, Y., ChemSusChem 2012, 5, 293-299.
(28) Lamblin, M.; Nassar-Hardy, L ; Hierso, J.-C; Fouquet, E.; Felpin, F.-X., Adv. Synth. Catal. 2010, 352, 33-79. (29) Hudson, R.; Riviere, A.; Cirtiu, C. M.; Luska, K. L; Moores, A., Chem. Commun. 2012, 48, 3360-3362.
(30) Jas, G.; Kirschning, A., Chem. Euro. J. 2003, 9, 5708-5723.
(31 ) a) Whitesides, G. M., Nature 2006, 442, 368-373; b) Wegner, J.; Ceylan, S.; Kirschning, A., Chem. Commun. 2011 , 47, 4583-4592.
(32) a) Singh, U. K.; Vannice, M. A., Appl. Catal., A 2001 , 213, 1-24; b) Kobayashi, J.; Mori, Y.; Okamoto, K.; Akiyama, R.; Ueno, M. ; Kitamori, T.; Kobayashi, S., Science 2004, 304, 1305- 1308; c) Ruta, M.; Laurenczy, G.; Dyson, P. J.; Kiwi-Minsker, L, J. Phys. Chem. C 2008, 112, 17814-17819.
(33) a) Peng, S.; Wang, C; Xie, J.; Sun, S., J. Am. Chem. Soc. 2006, 128, 10676-10677; b) Yoon, T.-J.; Lee, H.; Shao, H.; Weissleder, R., Angew. Chem. Int. Ed 2011 , 50, 4663-4666.
(34) Nadagouda, M. N.; Castle, A. B.; Murdock, R. C; Hussain, S. M.; Varma, R. S., Green Chem. 2010, 12, 114-122.
(35) Ridley, N.; Stuart, H., Brit. J. Appl. Phys. 1968, 2, 1291-1295.
(36) a) Gota, S.; Guiot, E.; Henriot, M.; Gautier-Soyer, M., Surf. Sci. 2000, 454-456, 796-801 ; b) Cabot, A.; Puntes, V. F.; Shevchenko, E.; Yin, Y.; Balcells, L; Marcus, M. A.; Hughes, S. M.; Alivisatos, A. P., J. Am. Chem. Soc. 2007, 129, 10358-10360.
(37) Mori, A.; Mizusaki, T.; Miyakawa, Y.; Ohashi, E.; Haga, T.; Maegawa, T. ; Monguchi, Y.; Sajiki, H., Tetrahedron 2006, 62, 11925-11932.
(38) Shim, ll-Wun et al, Bull Korean Chem. Soc. 2001 , Vol.22, No.7, pgs. 772-774.
(39) Ding, M et al, Catalysis Today, 183 (2012) pgs. 10-16.
(40) US 2007/0034052 A1 , Vanheusden, K et al, Publ. Date Feb. 15, 2007.
(41 ) WO2005/054120 A2, Wai C. et al, Int Publ Date 16 June 2005.

Claims

CLAI MS:
1. A hydrogenation catalyst comprising an amphiphilic polymer resin with a resin support; a linker attached to the support, wherein the linker comprises a functionalized group selected from COOH, NH2 a halide or combinations thereof, and an embedded iron Fe° nanoparticles.
2. A catalyst according to claim 1 , wherein the resin support is composed of polystyrene beads.
3. A catalyst according to claim 2, wherein the the linker includes a spacer.
4. The catalyst according to claim 3, wherein the spacer is polyethylene glycol (PEG).
5. A catalyst according to claim 1 , wherein the functional group is NH2.
6. A catalyst according to any one of claims 2 to 4, wherein the functional groups are attached to the polystyrene beads with a linker.
7. A catalyst according to claim 6, wherein the linker is polyethylene glycol derivative.
8. A catalyst according to any one of claims 1 to 7, wherein the embedded iron Fe° nanoparticles are loaded at a concentration from 1 to 15 mg Fe / g catalyst.
9. A catalyst according to claim 8, wherein the concentration is 12 mg Fe / g catalyst.
10. The use of a catalyst comprising an amphiphilic polymer resin with a resin support; a linker attached to the support, wherein the linker comprises a functionalized group selected from COOH, NH2 a halide or combinations thereof, and an embedded iron Fe° nanoparticles. , for hydrogenation of alkenes, alkynes, aromatic aldehydes and aromatic imines.
11. A process for the manufacture of a chemical compound comprising hydrogenation of alkenes, alkynes, aromatic aldehydes and aromatic imines functionalities in the presence of a catalystcomprising an amphiphilic polymer resin with a resin support; a linker attached to the support, wherein the linker comprises a functionalized group selected from COOH, NH2 a halide or combinations thereof, and an embedded iron Fe° nanoparticles.
12. A process for hydrogenation of chemical compounds using a catalyst comprising an amphiphilic polymer resin with a resin support; a linker attached to the support, wherein the linker comprises a functionalized group selected from COOH, NH2 a halide or combinations thereof, and an embedded iron Fe° nanoparticles.
13. A process according to claim 12, wherein the hydrogenation is carried out in a protic solvent.
14. A process according to claim 13, wherein the protic solvent is ethanol, water or a mixture thereof.
15. A process according to claim 12, wherein the hydrogenation is carried out under pressure between 10 to 60 bar.
16. A process according to claim 12, wherein the hydrogenation is carried out in at a temperature between 60 to 100°C.
17. A process according to claim 12, wherein the catalyst is used in a flow system.
18. A process according to claim 17, wherein the flow system is used with a flow rate between 0.5 ml/min to 2 ml/min.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2750796A4 (en) * 2012-04-17 2016-06-01 Momentive Performance Mat Inc High activity catalyst for hydrosilylation reactions and methods of making the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1739104A1 (en) * 2004-03-08 2007-01-03 Japan Science and Technology Agency Polymer-supported metal cluster compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1739104A1 (en) * 2004-03-08 2007-01-03 Japan Science and Technology Agency Polymer-supported metal cluster compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NAKAO ET AL.: "Hydrogenation and Dehalogenation under Aqueous Conditions with an Amphiphilic-Polymer-Supported Nanopalladium Catalyst", ORGANIC LETTERS, vol. 7, no. 1, 2005, pages 163 - 165 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2750796A4 (en) * 2012-04-17 2016-06-01 Momentive Performance Mat Inc High activity catalyst for hydrosilylation reactions and methods of making the same
US9993812B2 (en) 2012-04-17 2018-06-12 Momentive Pereformance Materials Inc. High activity catalyst for hydrosilylation reactions and methods of making the same

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