EP4337809A1 - Electrochemical hydrogenation of specific alkynes - Google Patents

Electrochemical hydrogenation of specific alkynes

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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
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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
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German (de)
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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Publication of EP4337809A1 publication Critical patent/EP4337809A1/en
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    • 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)
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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The present invention relates to an electrochemical selective hydrogenation of specific alkynes to the corresponding alkenes.

Description

ELECTROCHEMICAL HYDROGENATION OF SPECIFIC ALKYNES
The present invention relates to an electrochemical selective hydrogenation of spe cific alkynes to the corresponding alkenes.
There are many ways to hydrogenate carbon-carbon triple bonds. A very common one is the hydrogenation wherein H2 gas is used (usually in combination with a cata lytic system). Such a H2 hydrogenation needs specific types of equipment for the re action as well as the working with H2 has several safety aspects that must be ad dressed.
Furthermore, due to the effort of shifting forward towards more sustainable technolo gies there is also a need to find an alternative, more sustainable way for such reac tions.
Another way of hydrogenation is the electrochemical hydrogenation. Such a hydro genation is known from the prior art. But nevertheless, the electrochemical hydro genation is not as far developed as the conventional hydrogenation processes.
But 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 H2 gas is needed, use of non-toxic solvents, minimizing waste). Therefore, such a way of hydrogenation has some very great advantages.
The goal of the present invention was to find a way to hydrogenate specifically the compounds of formula (I) wherein
R is H; linear or branched CrCs-alkyl; linear or branched C2 - Cs-alkenes; phenyl; or substituted phenyl; and Ri is H; linear or branched Ci-Cs-alkyl; linear or branched C2 - Cs-alkenes; phenyl; or substituted phenyl; and
R2 is H; linear or branched CrCs-alkyl, which can be substituted by OH; linear or branched C2 - Cs-alkenes; phenyl; or substituted phenyl, with the proviso that when R2 is H then either R or Ri or both are not H, by using electrochemical means.
The goal of such an electrochemical hydrogenation is that it is carried out selectively, which means that only the carbon-carbon triple bond is hydrogenated to a carbon- carbon double bond. It is important that the hydrogenation stops at this stage and that no over-hydrogenation takes place. Over-hydrogenation in the context of the present invention means that also the carbon-carbon double bond is hydrogenated to the car bon-carbon single bond. Another aspect of selectivity is that if another reducible group is present in the molecule, then this group is not reduced.
So, it was the goal to find an electrochemical way to hydrogenate the compounds of formula (I) wherein
R is H; linear or branched CrCs-alkyl; linear or branched C2 - Cs-alkenes; phenyl; or substituted phenyl; and
Ri is H; linear or branched CrCs-alkyl; linear or branched C2 - Cs-alkenes; phenyl; or substituted phenyl; and
R2 is H; linear or branched CrCs-alkyl, which can be substituted by OH; linear or branched C2 - Cs-alkenes; phenyl; or substituted phenyl, with the proviso that when R2 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).
It was found that when using a specific Palladium (Pd) electrode, it is possible to carry out an electrochemical hydrogenation in an aqueous media as well as in non-aqueous media in good yield and high selectivity without supplying (such as i.e. by pumping) any H2 gas.
Therefore, 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 C2 - Cs-alkenes; phenyl; or substituted phenyl; and
Ri is H; linear or branched Ci-Cs-alkyl; linear or branched C2 - Cs-alkenes; phenyl; or substituted phenyl; and
R2 is H; linear or branched CrCs-alkyl, which can be substituted by OH; linear or branched C2 - Csalkenes; phenyl; or substituted phenyl, with the proviso that when R2 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 H2 gas and/or H2 containing gas. This means that no H2 and/or H2-contaning gas it added from external into the cell (by means such as i.e. pumping, bubbling etc).
Therefore, 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 H2 gas (pure or as a mixture) is added (supplied) into the cell of the hydrogenation).
Preferred compounds of formula (I) are those wherein
R is H; linear or branched CrC4-alkyl; or linear or branched C2 - C6-alkenes; and Ri is H; linear or branched Ci-C4-alkyl; or linear or branched C2 - C6-alkenes; and R2 is H; linear or branched Ci-C4-alkyl, which can be substituted by OH; linear or branched C2 - C6-alkenes, with the proviso that when R2 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-C2-alkyl; and Ri is H; Ci-C2-alkyl; and
R2 is H; linear or branched Ci-C4-alkyl, which can be substituted by OH, with the proviso that when R2 is H then either R or Ri or both are not H.
Even more preferred are the compound of formula (la) and the compound of formula (lb)
Most preferred is the compound of formula (lb) Therefore, 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 CrC4-alkyl; or linear or branched C2 - C6-alkenes; and Ri is H; linear or branched CrC4-alkyl; or linear or branched C2 - C6-alkenes; and
R2 is H; linear or branched Ci-C4-alkyl, which can be substituted by OH; linear or branched C2 - C6-alkenes, with the proviso that when R2 is H then either R or Ri or both are not H, are 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 R is H; CrC2-alkyl; and Ri is H; CrC2-alkyl; and
R2 is H; linear or branched CrC4-alkyl, which can be substituted by OH, with the proviso that when R2 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.
The following compounds (compound of formula (lla) and compound of formula (lib)) are the most preferred reaction products (obtained from the selective hydrogenation of the compound of formula (la) and the compound of formula (lb)) An essential feature of the present invention is the electrode, which is used for the electrochemical hydrogenation according to the present invention.
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.
Preferably 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 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.
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 made out of a Pd alloy.
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 a Pd alloy on a carrier material.
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.
Therefore, 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.
The reaction is usually carried out in an aqueous medium. ln the context of the present invention the term "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. Examples of said solvents, but not limited to, are 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.
Therefore, the present invention relates to an electrochemical hydrogenation (EH4), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EHT”), (EH2), (EH2’), (EH2”), (EH2’”) or (EH3), wherein the electrochemical hydro genation is carried out in a commonly known electrochemical reactor (preferably in a two compartment electrochemical H-cell).
Therefore, 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.
It is also possible to carry out the hydrogenation according to the present invention in a non-aqueous media. Such suitable non-aqueous media are i.e. linear or branched C1-C10 alcohols, preferably linear or branched Ci - C5 alcohols, most preferred is methanol.
In the context of the present invention “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).
Therefore, the present invention relates to an electrochemical hydrogenation (EH6), which is the electrochemical hydrogenation (EH), (EH’), (EH1), (EHT), (EH1”), (EH1’”), (EH2), (EH2’), (EH2”), (EH2’”), (EH3), (EH4) or (EH5), wherein the electro chemical hydrogenation is carried out in an non-aqueous medium.
Therefore, 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 C1-C10 alcohol (preferably at least one linear or branched Ci - C5 alcohol, most preferably methanol).
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, H2SO4, Na2SC>4, NaCI, NaHSC , phosphoric acid, phosphates and tetrabutylammonium acetate (NBU4OAC).
Usually 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).
Therefore, 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.
Therefore, 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.
Therefore, 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.
Therefore, the present invention relates to an electrochemical hydrogenation (EH8), 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).
Therefore, 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.
Therefore, 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. Depending on the cell, the electrochemical hydrogenation according to the present invention can be carried out batchwise or in a continuous way. The continuous pro cess is preferred.
Therefore, 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.
Therefore, the present invention relates to an electrochemical hydrogenation (EH12), 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 in a continuous way.
The current density used in the electrochemical hydrogenation according to the pre sent invention is preferably between 1 - 1000 mA/cm2.
Therefore, 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/cm2.
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.
Therefore, the present invention relates to 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 elec trical potential between the anode and cathode is 10 V or less.
Therefore, the present invention relates to 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 - 8 V.
Therefore, the present invention relates to 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.
Therefore, the present invention relates to 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.
Therefore, the present invention relates to an electrochemical hydrogenation (EH15), 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), (EH13), (EH14), (EH14’), (EH 14”) or (EH 14”’), wherein the electrochemical hydrogenation is carried out in gal vanostatic mode.
Therefore, the present invention relates to 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.
The reaction products (the alkenes) can be isolated from the reaction medium using commonly methods.
The following examples serve to illustrate the invention. If not otherwise stated all parts are given are related to the weight and the temperature is given in °C
Examples
Example 1 :
Aqueous electrochemical hydrogenation reaction of MBY (compound of formula (la)) to MBE (compound of formula (lla) was carried out in a two-compartment electrochemical H-cell (V=130 ml_) in 0.5 M sulfuric acid with 0.02 M MBY; 0.5 M sulfuric acid was used as anolyte. Nafion® 117 proton exchange membrane was used as a separator. Palladium wire (5 cm2) electrode was used as a catalyst for the hydrogenation. Electrolysis was carried out galvanostatically by applying cathodic current of -20 mAcnr2 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.
Example 2:
Aqueous electrochemical hydrogenation reaction of MBY to MBE was carried out in a two-compartment electrochemical flow cell (10 cm2 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 cm2) electrode was used as a catalyst for the hydrogenation. Electrolysis was carried out galvanostatically by applying cathodic current of -20 mAcnr2 at 60 °C (measured cathode potential -0.6V vs Ag/AgCI). As a result, an overall 10% yield MBE and 70% selectivity were achieved.
Example 3:
Aqueous electrochemical hydrogenation reaction of BYD (compound of formula (lb) to BED (compound of formula (lib) was carried out in a two-compartment electrochemical H-cell (V=130 ml_) in 0.1 M sulfuric acid with 0.02 M BYD; 0.1 M sulfuric acid was used as anolyte. Nafion® 117 proton exchange membrane was used as a separator. Palladium wire (5 cm2) electrode was used as a catalyst for the hydrogenation. Electrolysis was carried out galvanostatically by applying cathodic current of -10 mAcnr2 at room temperature. As a result, selectivities >95% towards BED and 20% Faraday efficiency were achieved at conversion of -40%. Example 4:
Non-aqueous electrochemical hydrogenation reaction of BYD to BED was carried out in a two-compartment electrochemical H-cell (V=130 ml_) in methanol with 0.02 M BYD + 0.15 M tetrabutylammonium acetate + 0.034 M phosphoric acid; and same solution but without BYD was used as anolyte. Nation® 117 proton exchange membrane was used as a separator. Palladium wire (5 cm2) electrode was used as a catalyst for the hydrogenation. Electrolysis was carried out galvanostatically by applying cathodic current of -10 mAcnr2 at room temperature. As a result, a yield of 50% BED and a selectivity of 90% were achieved.
Example 5:
Aqueous electrochemical hydrogenation reaction of MBY to MBE was also carried out in a two-compartment electrochemical H-cell (V=130 ml_) in 0.1 M sulfuric acid with 0.02 M MBY; 0.5 M sulfuric acid was used as anolyte. Nafion® 117 proton exchange membrane was used as a separator. Copper wire (5 cm2) electrode was used as a catalyst for the hydrogenation. Electrolysis was carried out galvanostatically by applying cathodic current of -20 mAcnr2 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.
Example 6: (Comparative example)
Aqueous electrochemical hydrogenation reaction of MBY to MBE was carried out in a two-compartment electrochemical H-cell (V=130 ml_) in water with 0.1 M tetraethylammonium chloride and 0.5 M MBY; 0.5 M sulfuric acid was used as anolyte. 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 mAcnr2 at room temperature. No MBY hydrogenation products were observed.
Example 7: (Comparative example)
Aqueous electrochemical hydrogenation reaction of MBY to MBE was carried out in a two-compartment electrochemical H-cell (V=130 ml_) in 0.1 M sulfuric acid with 0.02 M MBY; 0.5 M sulfuric acid was used as anolyte. Nation® 117 proton exchange membrane was used as a separator. Copper wire (5 cm2) 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.
Example 8: (Comparative example)
Aqueous electrochemical hydrogenation reaction of BYD to BED was carried out in a two-compartment electrochemical H-cell (V=130 mL) in 0.1 M sulfuric acid with 0.02 M BYD; 0.1 M sulfuric acid was used as anolyte. Nafion® 117 proton exchange membrane was used as a separator. Copper wire (5 cm2) 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/cm2) 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.
Example 9: (Comparative example)
Aqueous electrochemical hydrogenation reaction of BYD to BED was carried out in a two-compartment electrochemical H-cell (V=130 mL) in 0.1 M sulfuric acid with 0.02 M BYD; 0.1 M sulfuric acid was used as anolyte. Nafion® 117 proton exchange membrane was used as a separator. Lead wire (5 cm2) 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.

Claims

Claims
1. Selective electrochemical hydrogenation of compounds of formula (I) wherein
R is H; linear or branched CrCs-alkyl; linear or branched C2 - Cs-alkenes; phenyl; or substituted phenyl; and
Ri is H; linear or branched CrCs-alkyl; linear or branched C2 - Cs-alkenes; phenyl; or substituted phenyl; and
R2 is H; linear or branched CrCs-alkyl, which can be substituted by OH; linear or branched C2 - Cs-alkenes; phenyl; or substituted phenyl, wherein the compound of formula (I) is hydrogenated on a Pd containing electrode.
2. Selective electrochemical hydrogenation according to claim 1 , wherein the hydrogenation is carried out without H2 gas (pure or as a mixture).
3. Selective electrochemical hydrogenation according to claim 1 or claim 2, wherein the compounds of formula (I) R is H; linear or branched Ci-C4-alkyl; or linear or branched C2 - C6-alkenes; and Ri is H; linear or branched Ci-C4-alkyl; or linear or branched C2 - C6-alkenes; and R2 is H; linear or branched CrC4-alkyl, which can be substituted by OH; linear or branched C2 - C6-alkenes, with the proviso that when R2 is H then either R or Ri or both are not H.
4. Selective electrochemical hydrogenation according to claim 1 , wherein the compounds of formula (I) are the compound of formula (la) and the compound of formula (lb)
5. Selective electrochemical hydrogenation according to any of the preceding claims, wherein the electrode is made out of pure Pd.
6. Selective electrochemical hydrogenation according to any of the preceding claims 1 - 4, wherein the electrode is Pd on a carrier material.
7. Selective electrochemical hydrogenation according to any of the preceding claims, wherein the electrode is in the form of a wire, a rod, a cell, a mesh, a grid, a sponge, or any other design.
8. Selective electrochemical hydrogenation according to any of the preceding claims, wherein the electrochemical hydrogenation is carried out in an aqueous me dium.
9. Selective electrochemical hydrogenation according to any of the preceding claims 1 - 7, wherein the electrochemical hydrogenation is carried out in a non-aque- ous medium.
10. Selective electrochemical hydrogenation according to any of the preceding claims, wherein the reaction medium of the electrochemical hydrogenation comprises at least one supporting electrolyte.
11. Selective electrochemical hydrogenation according to claim 10, wherein the at least one supporting electrolyte is used in an amount of up to 1 M.
12. Selective electrochemical hydrogenation according to any of the preceding claims, wherein the reaction medium has a pH value of 0 to 7.
13. Selective electrochemical hydrogenation according to any of the preceding claims, wherein the electrochemical hydrogenation is carried out at a temperature range of 10 to 75 °C.
14. Selective electrochemical hydrogenation according to any of the preceding claims, wherein the electrochemical hydrogenation is carried out batchwise or in a continuous way.
15. Selective electrochemical hydrogenation according to any of the preceding claims, wherein the electrochemical hydrogenation is carried out in galvanostatic or potentiostatic mode.
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