EP4337809A1 - Elektrochemische hydrierung spezifischer alkine - Google Patents

Elektrochemische hydrierung spezifischer alkine

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Publication number
EP4337809A1
EP4337809A1 EP22728230.8A EP22728230A EP4337809A1 EP 4337809 A1 EP4337809 A1 EP 4337809A1 EP 22728230 A EP22728230 A EP 22728230A EP 4337809 A1 EP4337809 A1 EP 4337809A1
Authority
EP
European Patent Office
Prior art keywords
electrochemical hydrogenation
linear
branched
hydrogenation
electrochemical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22728230.8A
Other languages
English (en)
French (fr)
Inventor
Werner Bonrath
Earl Lawrence Vincent Goetheer
Roman GOY
Roman LATSUZBAIA
Jonathan Alan Medlock
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DSM IP Assets BV
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DSM IP Assets BV
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Filing date
Publication date
Application filed by DSM IP Assets BV filed Critical DSM IP Assets BV
Publication of EP4337809A1 publication Critical patent/EP4337809A1/de
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction

Definitions

  • the present invention relates to an electrochemical selective hydrogenation of spe cific alkynes to the corresponding alkenes.
  • the electrochemical process can be carried out in a very green and sustainable way (for example using renewable energy resulting in a significant reduction in carbon dioxide emissions, no H 2 gas is needed, use of non-toxic solvents, minimizing waste). Therefore, such a way of hydrogenation has some very great advantages.
  • R is H; linear or branched CrCs-alkyl; linear or branched C 2 - Cs-alkenes; phenyl; or substituted phenyl; and Ri is H; linear or branched Ci-Cs-alkyl; linear or branched C 2 - Cs-alkenes; phenyl; or substituted phenyl; and
  • R 2 is H; linear or branched CrCs-alkyl, which can be substituted by OH; linear or branched C 2 - Cs-alkenes; phenyl; or substituted phenyl, with the proviso that when R 2 is H then either R or Ri or both are not H, by using electrochemical means.
  • R is H; linear or branched CrCs-alkyl; linear or branched C 2 - Cs-alkenes; phenyl; or substituted phenyl; and
  • Ri is H; linear or branched CrCs-alkyl; linear or branched C 2 - Cs-alkenes; phenyl; or substituted phenyl; and
  • R 2 is H; linear or branched CrCs-alkyl, which can be substituted by OH; linear or branched C 2 - Cs-alkenes; phenyl; or substituted phenyl, with the proviso that when R 2 is H then either R or Ri or both are not H, to the corresponding alkene compounds of formula (II) wherein the substituents have the same meanings as in formula (I).
  • the present invention relates to the selective electrochemical hydrogena tion (EH) of compounds of formula (I) wherein
  • R is H; linear or branched CrCs-alkyl; linear or branched C 2 - Cs-alkenes; phenyl; or substituted phenyl; and
  • Ri is H; linear or branched Ci-Cs-alkyl; linear or branched C 2 - Cs-alkenes; phenyl; or substituted phenyl; and
  • R 2 is H; linear or branched CrCs-alkyl, which can be substituted by OH; linear or branched C 2 - Csalkenes; phenyl; or substituted phenyl, with the proviso that when R 2 is H then either R or Ri or both are not H, wherein the compound of formula (I) is hydrogenated on a Pd containing electrode.
  • Hydrogenation according to the present invention is carried out without applying any H 2 gas and/or H 2 containing gas. This means that no H 2 and/or H 2 -contaning gas it added from external into the cell (by means such as i.e. pumping, bubbling etc).
  • the present invention relates to the selective electrochemical hydrogena tion (EH’), which is electrochemical hydrogenation (EH) wherein the hydrogenation is carried out characterised in that no H 2 gas (pure or as a mixture) is added (supplied) into the cell of the hydrogenation).
  • EH electrochemical hydrogena tion
  • Preferred compounds of formula (I) are those wherein
  • R is H; linear or branched CrC 4 -alkyl; or linear or branched C 2 - C6-alkenes; and Ri is H; linear or branched Ci-C 4 -alkyl; or linear or branched C 2 - C6-alkenes; and R 2 is H; linear or branched Ci-C 4 -alkyl, which can be substituted by OH; linear or branched C 2 - C6-alkenes, with the proviso that when R 2 is H then either R or Ri or both are not H.
  • More preferred compounds of formula (I) are those wherein R is H; Ci-C 2 -alkyl; and Ri is H; Ci-C 2 -alkyl; and
  • R 2 is H; linear or branched Ci-C 4 -alkyl, which can be substituted by OH, with the proviso that when R 2 is H then either R or Ri or both are not H.
  • the present invention relates to an electrochemical hydrogenation (EH1), which is the electrochemical hydrogenation (EH) or (EH’), wherein compounds of for mula (I) wherein
  • R is H; linear or branched CrC 4 -alkyl; or linear or branched C 2 - C 6 -alkenes; and Ri is H; linear or branched CrC 4 -alkyl; or linear or branched C 2 - C 6 -alkenes; and
  • R 2 is H; linear or branched Ci-C 4 -alkyl, which can be substituted by OH; linear or branched C2 - C6-alkenes, with the proviso that when R 2 is H then either R or Ri or both are not H, are used.
  • EHT electrochemical hydrogenation
  • EH electrochemical hydrogenation
  • EH electrochemical hydrogenation
  • R 2 is H; linear or branched CrC 4 -alkyl, which can be substituted by OH, with the proviso that when R 2 is then either R or Ri or both are not H, are used. Therefore, the present invention relates to an electrochemical hydrogenation (EH1”), which is the electrochemical hydrogenation (EH) or (EH’), wherein compound of for mula (la) or compound of formula (lb) is used. Therefore, the present invention relates to an electrochemical hydrogenation (EHT”), which is the electrochemical hydrogenation (EH) or (EH’), wherein compounds of for mula (I) wherein the compound of formula (lb) is used.
  • EH1 electrochemical hydrogenation
  • EHT electrochemical hydrogenation
  • a palladium (Pd) containing electrode is used.
  • Such an electrode can be made out of pure Pd (which means that the no other metal or material is added to the Pd on purpose. (It may contain traces of other material) or the electrode can be Pd on a carrier material (such as carbon for example).
  • the electrode can also be a Pd alloy. This alloy can be used as such or can be used on a carrier material.
  • the electrode is made out of pure Pd.
  • the present invention relates to an electrochemical hydrogenation (EH2), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”) or (EHT”), wherein the electrode is made out of pure Pd. Therefore, the present invention relates to an electrochemical hydrogenation (EH2’), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”) or (EHT”), wherein the electrode is Pd on a carrier material.
  • the present invention relates to an electrochemical hydrogenation (EH2”), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”) or (EHT”), wherein the electrode is made out of a Pd alloy.
  • the present invention relates to an electrochemical hydrogenation (EH2’”), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”) or (EHT”), wherein the electrode is a Pd alloy on a carrier material.
  • EH2 electrochemical hydrogenation
  • the electrode can be in the form of a wire, a rod, a cell, a mesh, a grid, a sponge, or any other design, which is usually used.
  • the present invention relates to an electrochemical hydrogenation (EH3), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”) or (EH2’”), wherein the electrode is in the form of a wire, a rod, a cell, a mesh, a grid, a sponge, or any other design, which is usually used.
  • the size (which also means the surface area) of the electrode is not essential for the present invention.
  • the size of the electrodes should and can be adapted to the size of the electrochemical reactor (cell).
  • the cell also known as voltaic cells or galvanic cells, used in the process according the present invention can be any one of those known by a person skilled in the art. Usually and preferably it is a two compartment electrochemical H-cell.
  • aqueous medium means 100 wt % water, or a mixture of water with at least one fully or partially water-miscible solvent in which the amount of water is from 50 to 99 wt %, particularly from 70 and 99 wt %, and more particularly from 85 and 99 wt %.
  • Suitable fully or partially water-miscible solvents are those which are not electroactive under the electrolysis conditions of the present invention.
  • alkylene car bonates such as propylene carbonate and butylene carbonate
  • polyethylene glycol N-methyl-2-pyrrolidone
  • methanol acetone
  • sulpholane dimethylsulphoxide
  • tetrahy- drofuran dimethylformamide
  • hexa-methylphosphoramide acetonitrile
  • dichloro- methane pyridine and hexafluoro-2-propanol.
  • EH4 electrochemical hydrogenation
  • EH4 electrochemical hydrogenation
  • EH1 electrochemical hydrogenation
  • EHT electrochemical hydrogenation
  • EH2 electrochemical hydrogenation
  • EH3 electrochemical hydrogenation
  • the present invention relates to an electrochemical hydrogenation (EH5), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3) or (EH4), wherein the electrochemical hydrogenation is carried out in an aqueous medium.
  • EH5 electrochemical hydrogenation
  • non-aqueous media i.e. linear or branched C1-C10 alcohols, preferably linear or branched Ci - C5 alcohols, most preferred is methanol.
  • non-aqueous means that no water is added to the solvent on purpose. It might be possible that the solvent comprises traces of water (usually below 5 wt-%, based on the total weight of the solvent).
  • EH6 electrochemical hydrogenation
  • EH1 electrochemical hydrogenation
  • EH2 electrochemical hydrogenation
  • EH3 electrochemical hydrogenation
  • EH4 electrochemical hydrogenation
  • EH5 electrochemical hydrogenation
  • the present invention relates to an electrochemical hydrogenation (EH6’), which is the electrochemical hydrogenation (EH6), wherein the non-aqueous medium is at least one linear or branched C 1 -C 10 alcohol (preferably at least one linear or branched Ci - C 5 alcohol, most preferably methanol).
  • EH6 electrochemical hydrogenation
  • the reaction medium usually and preferably comprises at least one supporting elec trolyte. That can be added to the reaction medium in the form of a salt and/or in form of an acid. Any commonly known and commonly used supporting electrolyte can be used.
  • Suitable supporting electrolytes are i.e. HCI, H 2 SO 4 , Na 2 SC> 4 , NaCI, NaHSC , phosphoric acid, phosphates and tetrabutylammonium acetate (NBU 4 OAC).
  • a concentration of up to 1 M of at least one supporting electrolyte is used (preferably 0.05 - 1 M, more preferably 0.5 to 1 M).
  • the present invention relates to an electrochemical hydrogenation (EH7), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5) or (EH6), wherein the reaction medium of the electrochemical hydrogenation comprises at least one sup porting electrolyte.
  • EH7 is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5) or (EH6), wherein the reaction medium of the electrochemical hydrogenation comprises at least one sup porting electrolyte.
  • the present invention relates to an electrochemical hydrogenation (EH7’), which is the electrochemical hydrogenation (EH7), wherein the at least one supporting electrolyte is an acid and/or a salt.
  • the present invention relates to a electrochemical hydrogenation (EH7”), which is the electrochemical hydrogenation (EH7) or (EH7’), wherein at least one supporting electrolyte is chosen from the group consisting of HCI, H2SO4, Na2SC>4, NaCI, NaHS04, phosphoric acid, phosphates and NBU4OAC. Therefore, the present invention relates to an electrochemical hydrogenation (EH7’”), which is the electrochemical hydrogenation (EH7), (EH7’) or (EH7”), wherein the at least one proton source is used in an amount of up to 1.0 M (preferably 0.05 - 1 M, more preferably 0.5 to 1 M).
  • the pH value of the reaction medium of the electrochemical hydrogenation according to the present invention is preferably between 0 and 7.
  • an electrochemical hydrogenation which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5), (EH6), (EH7), (EH7’), (EH7”) or (EH7’”), wherein the reaction medium has a pH value of 0 to 7.
  • the electrochemical hydrogenation according to the present invention is carried out at a temperature range of 10 to 75 °C (preferably 15 to 60 °C).
  • the present invention relates to an electrochemical hydrogenation (EH9), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5), (EH6), (EH7), (EH7’), (EH7”), (EH7’”) or (EH8), wherein the electrochemical hydrogenation is carried out at a temperature range of 10 to 75 °C (preferably 15 to 60 °C).
  • the electrochemical hydrogenation according to the present invention is usually car ried out at ambient pressure.
  • the present invention relates to an electrochemical hydrogenation (EH 10), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5), (EH6), (EH7), (EH7’), (EH7”), (EH7’”), (EH8) or (EH9), wherein the electrochemical hydrogenation is carried out at ambient pressure.
  • the electrochemical hydrogenation according to the present invention can be carried out batchwise or in a continuous way. The continuous pro cess is preferred.
  • the present invention relates to an electrochemical hydrogenation (EH11), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5), (EH6), (EH7), (EH7’), (EH7”), (EH7’”), (EH8), (EH9) or (EH10), wherein the electrochemical hydrogenation is carried out batchwise or in a continuous way.
  • EH12 electrochemical hydrogenation
  • EH12 electrochemical hydrogenation
  • EH1 electrochemical hydrogenation
  • EHT electrochemical hydrogenation
  • EH2 electrochemical hydrogenation
  • EH3 electrochemical hydrogenation
  • EH4 electrochemical hydrogenation
  • EH5 electrochemical hydrogenation
  • EH6 electrochemical hydrogenation
  • EH7 electrochemical hydrogenation
  • EH7 electrochemical hydrogenation
  • EH7 electrochemical hydrogenation
  • EH8 electrochemical hydrogenation
  • the current density used in the electrochemical hydrogenation according to the pre sent invention is preferably between 1 - 1000 mA/cm 2 .
  • the present invention relates to an electrochemical hydrogenation (EH13), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5), (EH6), (EH7), (EH7’), (EH7”), (EH7’”), (EH8), (EH9), (EH10), (EH11) or (EH12), wherein the electrochemi cal hydrogenation is carried out at a current density of between 1 - 1000 mA/cm 2 .
  • the electrical potential between the anode and cathode may be 10 V or less.
  • a suit able range is 0.5 - 10 V, preferred is 0.5 - 8 V; more preferred is 0.5-5 V; most pre ferred is 0.5-3 V.
  • EH14 electrochemical hydrogenation (EH14), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5), (EH6), (EH7), (EH7’), (EH7”), (EH7’”), (EH8), (EH9), (EH10), (EH11), (EH12) or (EH13), wherein the elec trical potential between the anode and cathode is 10 V or less.
  • EH 14 is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5), (EH6), (EH7), (EH7’), (EH7”), (EH7’”), (EH8), (EH9), (EH10), (EH11), (EH12) or (EH13), wherein the elec trical potential between the anode and cathode is 0.5 - 8 V.
  • EH 14 an electrochemical hydrogenation (EH 14”), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5), (EH6), (EH7), (EH7’), (EH7”), (EH7’”), (EH8), (EH9), (EH10), (EH11), (EH12) or (EH13), wherein the elec trical potential between the anode and cathode is 0.5-5 V.
  • EH 14 is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5),
  • an electrochemical hydrogenation (EH14’”), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5), (EH6), (EH7), (EH7’), (EH7”), (EH7’”), (EH8), (EH9), (EH10), (EH11), (EH12) or (EH13), wherein the electrical potential between the anode and cathode is 0.5-3 V.
  • the electrochemical hydrogenation according to the present invention can be carried out in galvanostatic or potentiostatic mode.
  • EH15 is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5), (EH6), (EH7), (EH7’), (EH7”), (EH7’”), (EH8), (EH9), (EH10), (EH11), (EH12), (EH13), (EH14), (EH14’), (EH 14”) or (EH 14”’), wherein the electrochemical hydrogenation is carried out in gal vanostatic mode.
  • EH16 an electrochemical hydrogenation (EH16), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EH1’”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4), (EH5), (EH6), (EH7), (EH7’), (EH7”), (EH7’”), (EH8), (EH9), (EH10), (EH11), (EH12), (EH13), (EH14), (EH14’), (EH 14”) or (EH 14’”), wherein the electrochemical hydrogenation is carried out in po- tentiostatic mode.
  • reaction products (the alkenes) can be isolated from the reaction medium using commonly methods.
  • Nafion® 117 proton exchange membrane was used as a separator.
  • Palladium wire (5 cm 2 ) electrode was used as a catalyst for the hydrogenation.
  • Electrolysis was carried out galvanostatically by applying cathodic current of -20 mAcnr 2 at room temperature (measured cathode potential -0.85V vs Ag/AgCI). As a result, an overall 70% yield MBE and a 50% Faraday efficiency was achieved.
  • Aqueous electrochemical hydrogenation reaction of MBY to MBE was carried out in a two-compartment electrochemical flow cell (10 cm 2 geometric area) in 0.1 M sulfuric acid with 0.05 M MBY; 0.1 M sulfuric acid was used as anolyte.
  • Nafion® 117 proton exchange membrane was used as a separator.
  • Palladium wire (5 cm 2 ) electrode was used as a catalyst for the hydrogenation.
  • Electrolysis was carried out galvanostatically by applying cathodic current of -20 mAcnr 2 at 60 °C (measured cathode potential -0.6V vs Ag/AgCI). As a result, an overall 10% yield MBE and 70% selectivity were achieved.
  • Nafion® 117 proton exchange membrane was used as a separator.
  • Palladium wire (5 cm 2 ) electrode was used as a catalyst for the hydrogenation.
  • Electrolysis was carried out galvanostatically by applying cathodic current of -10 mAcnr 2 at room temperature. As a result, selectivities >95% towards BED and 20% Faraday efficiency were achieved at conversion of -40%.
  • Example 4 Example 4:
  • National® 117 proton exchange membrane was used as a separator.
  • Palladium wire (5 cm 2 ) electrode was used as a catalyst for the hydrogenation.
  • Electrolysis was carried out galvanostatically by applying cathodic current of -10 mAcnr 2 at room temperature. As a result, a yield of 50% BED and a selectivity of 90% were achieved.
  • Nafion® 117 proton exchange membrane was used as a separator.
  • Copper wire (5 cm 2 ) electrode was used as a catalyst for the hydrogenation.
  • Electrolysis was carried out galvanostatically by applying cathodic current of -20 mAcnr 2 at room temperature (measured cathode potential increased from -1.3 to -1 0V vs Ag/AgCI). As a result, an overall 5% yield of MBE at 20% conversion and 2.5% Faraday efficiency were achieved.
  • Nafion® 117 proton exchange membrane was used as a separator.
  • a zinc wire electrode was used as a catalyst for the hydrogenation. Electrolysis was carried out galvanostatically by applying cathodic current of -20 mAcnr 2 at room temperature. No MBY hydrogenation products were observed.
  • National® 117 proton exchange membrane was used as a separator.
  • Copper wire (5 cm 2 ) electrode was used as a catalyst for the hydrogenation. Electrolysis was carried out potentiostatically at -1.1 V vs Ag/AgCI at room temperature. As a result, an overall 0.5% yield of MBE was obtained.
  • Nafion® 117 proton exchange membrane was used as a separator.
  • Copper wire (5 cm 2 ) electrode was used as a catalyst for the hydrogenation.
  • Electrolysis was carried out first potentiostatically (- 0.9V vs Ag/AgCI) for 4.2 hours then potentiostatically (-10 mA/cm 2 ) for an hour at room temperature. As a result, selectivities to BED of 12% and to 2,5-dihydrofuran of 4% were achieved at 18% conversion.
  • Nafion® 117 proton exchange membrane was used as a separator.
  • Lead wire (5 cm 2 ) electrode was used as a catalyst for the hydrogenation. Electrolysis was carried out potentiostatically at -0.9V vs Ag/AgCI at room temperature. As a result, a selectivity to BED of 35% was achieved at 1.3% conversion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP22728230.8A 2021-05-12 2022-05-10 Elektrochemische hydrierung spezifischer alkine Pending EP4337809A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21173455 2021-05-12
PCT/EP2022/062530 WO2022238349A1 (en) 2021-05-12 2022-05-10 Electrochemical hydrogenation of specific alkynes

Publications (1)

Publication Number Publication Date
EP4337809A1 true EP4337809A1 (de) 2024-03-20

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EP22728230.8A Pending EP4337809A1 (de) 2021-05-12 2022-05-10 Elektrochemische hydrierung spezifischer alkine

Country Status (3)

Country Link
EP (1) EP4337809A1 (de)
CN (1) CN117295849A (de)
WO (1) WO2022238349A1 (de)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19937103A1 (de) * 1998-08-21 2000-02-24 Basf Ag Verfahren zur Hydrierung von organischen Verbindungen unter Ausnutzung des NEMCA-Effekts
US20040195108A1 (en) * 2001-08-29 2004-10-07 Jorg Botzem Method of producing oxocylohexyl or oxocyclohexylene derivatives
JP7072161B2 (ja) * 2017-02-16 2022-05-20 Ｅｎｅｏｓ株式会社 シス－アルケンの製造装置及び製造方法

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CN117295849A (zh) 2023-12-26

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