EP4253602A1 - Oxydation électrochimique des cycloalcènes et des cycloalcanes en acides alpha,oméga-dicarboniques ou en acides cétocarboniques et en composés de cycloalkanones - Google Patents

Oxydation électrochimique des cycloalcènes et des cycloalcanes en acides alpha,oméga-dicarboniques ou en acides cétocarboniques et en composés de cycloalkanones Download PDF

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Publication number
EP4253602A1
EP4253602A1 EP22164755.5A EP22164755A EP4253602A1 EP 4253602 A1 EP4253602 A1 EP 4253602A1 EP 22164755 A EP22164755 A EP 22164755A EP 4253602 A1 EP4253602 A1 EP 4253602A1
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Prior art keywords
unsubstituted
group
mono
monosubstituted
alkyl
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English (en)
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Erfindernennung liegt noch nicht vor Die
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Evonik Operations GmbH
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Evonik Operations GmbH
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Priority to EP22164755.5A priority Critical patent/EP4253602A1/fr
Priority to PCT/EP2023/057344 priority patent/WO2023186661A1/fr
Publication of EP4253602A1 publication Critical patent/EP4253602A1/fr
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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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/13—Single electrolytic cells with circulation of an electrolyte
    • C25B9/15—Flow-through cells
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof

Definitions

  • the invention relates to a process for the preparation of unsubstituted or at least monosubstituted ⁇ , ⁇ -dicarboxylic acids or ketocarboxylic acids and unsubstituted or at least monosubstituted cycloalkanones by electrochemical oxidation of unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated cycloalkenes and unsubstituted or at least monosubstituted, saturated ones cycloaliphatic hydrocarbons in the presence of an inorganic or organic nitrate salt in an electrolysis cell in a reaction medium in the presence of oxygen.
  • ⁇ , ⁇ -dicarboxylic acids, ketocarboxylic acids and cycloalkanone compounds represent important starting materials for organic synthetic chemistry as well as monomer building blocks for polymer synthesis and are therefore highly relevant for industrial applications.
  • the conventional access to these substrates is essentially from cycloalkanes and cycloalkenes via transition metal-catalyzed reactions and using chemical oxidants.
  • the method according to the invention thus enables the simplification of industrially relevant processes and further leads to possible process optimization from a sustainable perspective.
  • the present invention enables synthetically relevant oxo-functionalization of basic chemicals in a resource-saving manner, largely eliminating the use of environmentally harmful transition metals and oxidizing agents.
  • the selective conversion to the desired products and the effective use of conductive salt and mediator in a dual function significantly reduce the amount of costly reagent waste.
  • the present invention allows electrochemical synthesis access to aliphatic ⁇ , ⁇ -carboxylic acids, ketocarboxylic acids and cycloalkanones via an effective, convergent electrolysis in which both electrode reactions provide synthetic utility.
  • the process according to the invention is characterized in particular by high selectivity, small amounts of auxiliary chemicals used, the use of electric current as an oxidizing agent and, associated with this, by a reduced amount of waste products.
  • the method according to the invention can be carried out under ambient pressure and ambient temperature, which also has an advantageous effect on energy efficiency and thus also environmental compatibility.
  • Unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated cycloalkenes that are monocyclic or bicyclic can be used in the process according to the invention. Preference is given to unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated monocyclic Cycloalkenes are used, with unsubstituted or at least monosubstituted, monounsaturated monocyclic cycloalkenes being particularly preferred.
  • the location of the unsaturated bonds can be endocyclic or exocyclic, with endocyclic unsaturated bonds being preferred.
  • the unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated monocyclic cycloalkenes used in the process according to the invention can preferably have 5 to 12 C atoms, particularly preferably 6 to 12 C atoms, very particularly preferably 8 to 12 C atoms in the ring system. These cycloalkenes can be monounsaturated or polyunsaturated, with monounsaturated cycloalkenes being preferred. These cycloalkenes can each be unsubstituted or mono- or poly-substituted.
  • substituents independently of one another, each selected from the group consisting of methyl, phenyl or benzyl.
  • the phenyl or benzyl substituents themselves can each be unsubstituted or mono- or polysubstituted, with 1, 2 or 3 substituents, independently of one another, each selected from the group consisting of F, Cl, Br, and NO 2 .
  • the unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated bicyclic cycloalkenes used in the process according to the invention can preferably have 7 to 18 C atoms, particularly preferably 7 to 12 C atoms, very particularly preferably 7 to 10 C atoms in the ring system.
  • These cycloalkenes can be monounsaturated or polyunsaturated, with monounsaturated cycloalkenes being preferred.
  • These cycloalkenes can each be unsubstituted or mono- or poly-substituted.
  • substituents independently of one another, each selected from the group consisting of methyl, phenyl or benzyl.
  • the phenyl or benzyl substituents themselves can each be unsubstituted or mono- or polysubstituted, with 1, 2 or 3 substituents, independently of one another, each selected from the group consisting of F, Cl, Br, and NO 2 .
  • the mono- or bicyclic cycloalkenes used according to the invention or their substituents are alkyl radicals with more than one carbon atom in the side chain have, undesirable side reactions occur at these substituents when carrying out the process according to the invention.
  • the monocyclic cycloalkene can very particularly preferably be selected from the group consisting of cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene and 1-phenylcyclohex-1-ene.
  • Particularly preferred bicyclic cycloalkenes can be selected from the group consisting of bicylo[2.2.1]hept-2-ene, ⁇ -pinene and carene.
  • Unsubstituted or at least monosubstituted, saturated cycloaliphatic hydrocarbons which are monocyclic or bicyclic, preferably bicyclic, can be used in the process according to the invention.
  • Monocyclic cycloaliphatic hydrocarbons are particularly preferably used in the process according to the invention.
  • the monocyclic or polycyclic, in particular monocyclic or bicyclic, saturated cycloaliphatic hydrocarbons used in the process according to the invention can preferably have 5 to 18 C atoms in the ring system.
  • These cycloaliphatic hydrocarbons can each be unsubstituted or mono- or poly-substituted. If they are substituted once or multiple times, they are preferably substituted with 1, 2, 3, 4 or 5 substituents, independently of one another, each selected from the group consisting of methyl, phenyl or benzyl.
  • phenyl or benzyl substituents themselves can each be unsubstituted or mono- or polysubstituted, with 1, 2 or 3 substituents, independently of one another, each selected from the group consisting of F, Cl, Br, and NO 2 . If the cycloaliphatic hydrocarbons used according to the invention or their substituents have alkyl radicals with more than one carbon atom in the side chain, undesirable side reactions occur at these substituents when carrying out the process according to the invention.
  • Particularly preferred in the process according to the invention are monocyclic saturated hydrocarbons with 6 to 12 carbon atoms in the ring, preferably with 8 to 12 carbon atoms in the ring, which are unsubstituted or substituted once or multiple times with 1 as unsubstituted or at least monosubstituted, saturated cycloaliphatic hydrocarbons , 2, 3, 4 or 5 substituents, independently of one another, each selected from the group consisting of methyl, phenyl or benzyl.
  • monocyclic saturated hydrocarbons with 8 to 12 carbon atoms in the ring in the process according to the invention, which are unsubstituted or mono- or di- or tri-substituted with a methyl group.
  • the saturated monocyclic hydrocarbon is unsubstituted and is selected from the group consisting of cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane and cyclododecane, even more preferably selected from the group consisting of cyclooctane, cyclononane, cyclodecane, cycloundecane and cyclododecane, the hydrocarbon cyclododecane is most preferred.
  • the cycloalkene is particularly preferably selected from the group consisting of cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, 1-phenylcyclohex-1-ene, bicylo[2.2.1]hept-2-ene, ⁇ -pinene and carene and the saturated cycloaliphatic hydrocarbon selected from the group consisting of cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane and cyclododecane.
  • cycloalkene cyclododecene and the saturated cycloaliphatic hydrocarbon cyclododecane.
  • step (a-1) The provision of at least one unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated cycloalkene according to step (a-1) and the provision of at least one unsubstituted or at least monosubstituted, saturated cycloaliphatic hydrocarbon according to step (a-2) can preferably be carried out in the process according to the invention Combination, particularly preferably as a mixture.
  • preliminary products from large-scale industrial processes that contain these two components can be used directly in the process according to the invention.
  • the quantitative ratio of the unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated cycloalkene and the unsubstituted or at least monosubstituted saturated cycloaliphatic hydrocarbon in the process according to the invention can vary over a wide range.
  • the molar proportion of the unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated cycloalkene is preferably 40 to 95 mol%, preferably 45 to 55 mol%, particularly preferably 47 to 53 mol%, in each case based on the total amount of unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated cycloalkene and unsubstituted or at least monosubstituted saturated cycloaliphatic hydrocarbon used.
  • the molar proportion of the unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated cycloalkene is >60 mol%, preferably >65 mol%, particularly preferably >70 mol%, in each case based on the total amount used unsubstituted or at least mono-substituted, mono- or polyunsaturated cycloalkene and unsubstituted or at least mono-substituted, saturated cycloaliphatic hydrocarbon.
  • the cycloalkene used is very particularly preferably cyclododecene in an amount of 90 to 95 mol% and the saturated cycloaliphatic hydrocarbon cyclododecane is used in an amount of 5 to 10 mol%, based on the total amount of cyclodecene and cyclodecane.
  • step (b) of the process according to the invention at least one inorganic or organic nitrate salt is provided.
  • This nitrate salt acts both as a conductive salt and as a mediator in the electrochemical oxidation process according to the invention.
  • An inorganic or organic nitrate of the general formula is preferred [Cation + ][NO 3 - ] for use, whereby the [cation + ] is selected from the group consisting of Na + , K + , ammonium ions with the general structure [R 1 R 2 R 3 R 4 N + ] with R 1 , R 2 , R 3 , R 4 , independently of one another, each selected from the group consisting of C 1 - to C 16 -alkyl, in particular C 1 - to C 8 -alkyl, straight-chain or branched, imidazolium cations with the general structure (I) with R 1 and R 2 , independently of one another, each selected from the group consisting of C 1 - to C 18 alkyl
  • Phosphonium ions with the general structure [R 1a R 2a R 3a R 4a P + ] with R 1a , R 2a , R 3a , R 4a , independently of one another, each selected from the group consisting of C 1 - to C 16 alkyl, in particular C 1 - to C 8 alkyl, straight chain or branched.
  • R 1 is C 1 - to C 18 -alkyl, straight-chain or branched, in particular C 1 - to C 8 -alkyl, straight-chain or branched
  • R 2 , R 3 and R 4 independently of one another, are each selected from the group consisting of C 1 - to C 8 alkyl, straight-chain or branched, where a single substitution in the 2-, 3- or 4-position, a double substitution in 2,4-, 2,5- or 2,6-position or a triple substitution in 2,4,6-position is preferred.
  • nitrate salts can also be used in the process according to the invention.
  • a nitrate salt according to the invention is preferably used, in particular an organic ammonium nitrate salt of the composition [R 1 R 2 R 3 R 4 N + ][NO 3 - ] or an organic phosphonium salt of the composition [R 1a R 2a R 3a R 4a P + ][NO 3 - ], with an organic ammonium nitrate salt of the composition [R 1 R 2 R 3 R 4 N + ][NO 3 - ] being particularly preferred.
  • the organic ammonium nitrate salt tetra- n -butyl ammonium nitrate or methyltri- n -octylammonium nitrate is very particularly preferred.
  • the organic phosphonium nitrate salt is most preferably tetra- n -butylphosphonium nitrate or methyltri- n -octylphosphonium nitrate.
  • the organic imidazolium nitrate salt is preferably 1-butyl-3-methylimidazolium nitrate.
  • Tetra- n -butyl ammonium nitrate or methyltri- n -octylammonium nitrate is most preferably used as the organic nitrate salt in the process according to the invention.
  • the order in which the components used in the method according to the invention are provided can vary, as can the order individual components are brought into contact with each other or with the respective reaction medium.
  • the unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated cycloalkene and the unsubstituted or at least monosubstituted saturated cycloaliphatic hydrocarbon are introduced and brought together with the reaction medium, preferably at least partially or completely dissolved in the reaction medium or mixed with it, and then the inorganic or organic nitrate salt is added.
  • the inorganic or organic nitrate salt is introduced and brought into contact with the reaction medium, preferably at least partially or completely dissolved in the reaction medium or mixed with it, and then the unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated cycloalkene and the unsubstituted or at least monosubstituted, saturated cycloaliphatic hydrocarbons, preferably in combination, are added.
  • the unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated cycloalkene and the unsubstituted or at least monosubstituted saturated cycloaliphatic hydrocarbon and the inorganic or organic nitrate salt to be added to the reaction medium simultaneously or in time succession to one another are, preferably at least partially or completely dissolved in the reaction medium or mixed with it.
  • the reaction medium used in the process according to the invention is liquid under the conditions under which the process is carried out and is suitable for partially or completely dissolving the components used, ie in particular the unsubstituted or at least monosubstituted, saturated cycloaliphatic hydrocarbon and the inorganic or organic nitrate salt. If at least one of these components is used in liquid form, the reaction medium is preferably easily miscible with this component or these components.
  • a polar aprotic reaction medium is preferably used in the process according to the invention for electrochemical oxidation. This can be used in anhydrous form, in dried form or in combination with water.
  • the reaction medium advantageously contains water, with aprotic reaction medium in combination with water being preferred.
  • the water content in the reaction medium can vary.
  • the water content is preferably up to 20% by volume, particularly preferably up to 15% by volume, very particularly preferably up to 10% by volume, even more preferably up to 5% by volume, in each case on the total amount of reaction medium.
  • the polar aprotic reaction medium is preferably selected from the group consisting of aliphatic nitriles, aliphatic ketones, cycloaliphatic ketones, dialkyl carbonates, cyclic carbonates, lactones, aliphatic nitroalkanes, and dimethyl sulfoxide, esters and ethers or a combination of at least two of these components.
  • the reaction medium is particularly preferably selected from the group consisting of acetonitrile, isobutyronitrile, adiponitrile, acetone, dimethyl carbonate, methyl ethyl ketone, 3-pentanone, cyclohexanone, nitromethane, nitropropane, tert-butyl methyl ether, dimethyl sulfoxide, gamma-butyrolactone and epsilon-caprolactone or a combination from at least two of these components.
  • the reaction medium is selected from the group consisting of acetonitrile, isobutyronitrile, adiponitrile, dimethyl carbonate and acetone or a combination of at least two of these components.
  • the reaction medium is very particularly preferably acetonitrile, isobutyronitrile or adiponitrile in dried or anhydrous form.
  • the reaction medium is also very particularly preferred: acetonitrile, isobutyronitrile or adiponitrile, optionally in combination with water.
  • the water content is preferably up to 20% by volume, particularly preferably up to 15% by volume, very particularly preferably up to 10% by volume. %, even more preferably up to 5% by volume, based on the total amount of reaction medium.
  • solubilizing components it may be advantageous to add further solubilizing components to the reaction medium.
  • Suitable advantageous components can be determined through simple preliminary tests on solution behavior.
  • Suitable solubilizing components include, for example, primary alcohols, secondary alcohols, monoketones or dialkyl carbonates or mixtures of at least two of these components, possibly in combination with water.
  • Aliphatic C 1-6 alcohols can preferably be used in the process according to the invention, with particularly preferred solubilizing components being selected from the group consisting of methanol, ethanol, isopropanol, 2-methyl-2-butanol or mixtures of at least two of these components , if necessary in combination with water.
  • dimethyl carbonate as a reaction medium can be particularly advantageous, if necessary in combination with at least one C 1-6 alcohol, in particular selected from the group consisting of methanol, ethanol, isopropanol, 2-methyl-2-butanol, if necessary in combination with be water.
  • the water content is preferably up to 20% by volume, particularly preferably up to 15% by volume, very particularly preferably up to 10% by volume more preferably up to 5% by volume, based on the total amount of solubilizing component and water.
  • the solubilizing components can preferably be added in amounts of ⁇ 50% by volume, particularly preferably ⁇ 30% by volume and very particularly preferably ⁇ 10% by volume, in each case based on the total amount of reaction medium.
  • the inorganic or organic nitrate salt is preferably used in the process according to the invention in an amount of 0.1 to 2.0, preferably 0.2 to 1.0, particularly preferably 0.3 to 0.8 and very particularly preferably 0.4 to 0 .8 equivalents, based on the amount of unsubstituted or at least mono-substituted, mono- or polyunsaturated cycloalkene used and in an amount of 0.8 to 10.0, preferably 2.5 to 10.0, particularly preferably 3.0 to 10 .0 and very particularly preferably 5.0 to 10.0 equivalents, based on the amount of unsubstituted or at least monosubstituted, saturated cycloaliphatic hydrocarbon used.
  • the electrochemical oxidation of the unsubstituted or at least monosubstituted saturated cycloaliphatic hydrocarbon takes place in the presence of the inorganic or organic nitrate salt in an electrolysis cell in a reaction medium in the presence of oxygen.
  • a gas atmosphere containing oxygen is advantageously provided in spatial connection with the reaction medium.
  • the proportion of oxygen in the gas atmosphere can vary.
  • the proportion of oxygen in the gas atmosphere is preferably 10 to 100% by volume, particularly preferably 15 to 30% by volume, particularly preferably 15 to 25% by volume, very particularly preferably 18 to 22% by volume.
  • the proportion of oxygen in the gas atmosphere can be 10 to 100% by volume, particularly preferably 15 to 100% by volume, particularly preferably 20 to 100% by volume.
  • the gas atmosphere is particularly preferably air.
  • a gas exchange is forced between the gas atmosphere and the reaction medium, preferably by introducing gas atmosphere into the reaction medium or by stirring the liquid phase in the presence of the gas atmosphere.
  • the gas exchange between the gas atmosphere and the reaction medium in particular stirring, for example via the geometry of the stirrer or the stirring speed, can be used to control the electrochemical oxidation.
  • the amount of oxygen dissolved in the reaction medium is preferably at least 1 mmol/L reaction medium, particularly preferably at least 5 mmol/L reaction medium.
  • the amount of oxygen dissolved in the reaction medium is also preferably at least 10 mmol/L reaction medium.
  • the process according to the invention for the preparation of unsubstituted or at least monosubstituted ⁇ , ⁇ -dicarboxylic acids or ketocarboxylic acids and unsubstituted or at least monosubstituted cycloalkanones by electrochemical oxidation of unsubstituted or at least monosubstituted, monounsaturated or polyunsaturated cycloalkenes and unsubstituted or at least monosubstituted, saturated cycloaliphatic hydrocarbons in the presence of an inorganic or organic nitrate salt in a reaction medium in the presence of oxygen can be carried out in both a divided and an undivided electrolysis cell, with implementation in an undivided electrolysis cell being preferred.
  • the undivided electrolysis cell which is preferably used according to the invention has at least two electrodes.
  • Anodes and cathodes of common materials can be used here, for example glassy carbon, boron-doped diamond (BDD) or graphite. The use of glassy carbon electrodes is preferred.
  • the undivided electrolysis cell preferably has at least one glassy carbon anode or at least one glassy carbon cathode. Both the anode and the cathode are preferably glassy carbon electrodes.
  • the distance between the electrodes can vary over a certain range.
  • the distance is preferably 0.1 mm to 2.0 cm, particularly preferably 0.1 mm to 1.0 cm, particularly preferably 0.1 mm to 0.5 cm.
  • process according to the invention can be carried out batchwise or continuously, preferably in an undivided flow-through electrolysis cell.
  • the method according to the invention is preferably carried out with a charge quantity of at least 190 C (2 F) to 970 C (10 F), preferably 290 C (3 F) to 870 C (9 F), particularly preferably 330 C (3.5 F) to 820 C (8.5 F), very particularly preferably 380 C (4 F) to 775 C (8 F), most preferably 380 C (4 F) to 580 C (6 F), each for 1 mmol of used unsubstituted or at least mono-substituted, mono- or polyunsaturated cycloalkene and unsubstituted or at least mono-substituted, saturated cycloaliphatic hydrocarbon.
  • the electrochemical oxidation in the process according to the invention preferably takes place at constant current intensity.
  • the current density at which the method according to the invention is carried out is preferably at least 5 mA/cm 2 or at least 10 mA/cm 2 or at least 15 mA/cm 2 or at least 20 mA/cm 2 or 20 mA/cm 2 to 50 mA/ cm 2 , whereby the area refers to the geometric area of the electrodes.
  • a significant advantage of the method according to the invention is that electric current is used as the oxidizing agent, which is a particularly environmentally friendly agent when it comes from renewable sources, i.e. in particular from biomass, solar thermal energy, geothermal energy, hydropower, wind power or photovoltaics.
  • the process according to the invention can be carried out over a wide temperature range, for example at a temperature in the range from 0 to 60 °C, preferably from 5 to 50 °C, particularly preferably 10 to 40 °C, very particularly preferably 15 to 30 °C.
  • the process according to the invention can be carried out at increased or reduced pressure. If the process according to the invention is carried out at elevated pressure, a pressure of up to 16 bar is preferred, particularly preferably up to 6 bar.
  • the process according to the invention can also preferably be carried out under atmospheric pressure.
  • the products produced by the process according to the invention can be isolated or purified by conventional processes known to those skilled in the art, in particular by extraction, crystallization, centrifugation, precipitation, distillation, evaporation or chromatography.
  • the process according to the invention is preferably carried out without the addition of catalysts, in particular without the addition of transition metal catalysts.
  • the process according to the invention is also preferably carried out in such a way that no other oxidizing agents are added other than oxygen or atmospheric oxygen.
  • Analytical grade chemicals were purchased and used from mainstream suppliers (such as TCI, Aldrich, and Acros).
  • the oxygen was purchased in 2.5 quality from NIPPON GASES GmbH, Düsseldorf, Germany and used directly.
  • NMR spectrometry of 1 H-NMR and 13 C-NMR spectra were carried out at 25 °C with a Bruker Avance II 400 (400 MHz, 5 mm BBFO head with z-gradient and ATM, SampleXPress 60 sample changer, Analytician Messtechnik, Düsseldorf, Germany).
  • the gas introduction was controlled via two mass flow controllers (MFC) model 5850S from Brooks Instrument BV, Veenendaal, Netherlands.
  • MFC mass flow controller
  • a regulator was used for the oxygen and nitrogen lines.
  • the controllers were controlled using the Smart DDE and Matlab R2017b software.
  • the volume flow control was also carried out using a DK800 variable area flowmeter from KROHNE Messtechnik GmbH, Duisburg.
  • the total volume flow was a constant 20 mL/min, which, limited by the MFCs used, also represents the maximum achievable volume flow.
  • the percentage volume flows of the two gases were set using the MFCs and their software.
  • the gas bottles were used from the following suppliers: oxygen 2.5 from NIPPON GASES GmbH, Düsseldorf, and nitrogen 4.8 from Nonetheless AG, Weg and nitrogen 5.0 from NIPPON GASES GmbH, Düsseldorf.
  • the gas distributor and the gas inlet covers of the electrolysis cells are described in the literature (M. Dörr, D. Waldmann, SR Waldvogel, GIT Labor-Fachz. 2021, 7-8, 26-28) and were manufactured by IKA (IKA-Werke GmbH & Co .KG, Staufen, Germany).
  • the cycloalkane (0.1 to 0.5 mmol), the cycloalkene (0.5 to 0.9 mmol, cumulative alkane and alkene to a total of 1 mmol) and tetrabutylammonium nitrate (0.5 eq. ) and dissolved in acetonitrile or isobutyronitrile (5 mL).
  • the cell was equipped with glassy carbon electrodes at a distance of 0.5 cm.
  • the immersion area of the electrodes is 1.8 cm 2 .
  • galvanostatic electrolysis was performed at a current density of 10 mA/cm 2 at 22 °C.
  • the conductive salt was then removed extractively using 10 mL of ethyl acetate and 10 mL of aqueous HCl solution (0.1 M).
  • the solvent in the organic phase was removed by distillation and the residue was taken up with an aqueous NaOH solution (1 M, 10 mL).
  • the aqueous phase was washed with 10 mL of diethyl ether.
  • the aqueous phase was adjusted to pH 1 with an aqueous HCl solution (1 M) and extracted from this with 2 ⁇ 10 mL ethyl acetate.
  • the dicarboxylic acid product was dried under high vacuum.

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EP22164755.5A 2022-03-28 2022-03-28 Oxydation électrochimique des cycloalcènes et des cycloalcanes en acides alpha,oméga-dicarboniques ou en acides cétocarboniques et en composés de cycloalkanones Pending EP4253602A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP22164755.5A EP4253602A1 (fr) 2022-03-28 2022-03-28 Oxydation électrochimique des cycloalcènes et des cycloalcanes en acides alpha,oméga-dicarboniques ou en acides cétocarboniques et en composés de cycloalkanones
PCT/EP2023/057344 WO2023186661A1 (fr) 2022-03-28 2023-03-22 OXYDATION ÉLECTROCHIMIQUE DE CYCLOALCÈNES ET DE CYCLOALCANES EN ACIDES α,ω-DICARBOXYLIQUES OU EN ACIDES CÉTOCARBOXYLIQUES ET EN COMPOSÉS CYCLOALCANONE

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EP22164755.5A EP4253602A1 (fr) 2022-03-28 2022-03-28 Oxydation électrochimique des cycloalcènes et des cycloalcanes en acides alpha,oméga-dicarboniques ou en acides cétocarboniques et en composés de cycloalkanones

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Citations (4)

* Cited by examiner, † Cited by third party
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US5026461A (en) 1990-01-19 1991-06-25 E. I. Du Pont De Nemours And Company Process for the preparation of dodecanedioic acid
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