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EP1608797A2 - Procede d'alcoxylation anodique de composes organiques - Google Patents

Procede d'alcoxylation anodique de composes organiques

Info

Publication number
EP1608797A2
EP1608797A2 EP04722184A EP04722184A EP1608797A2 EP 1608797 A2 EP1608797 A2 EP 1608797A2 EP 04722184 A EP04722184 A EP 04722184A EP 04722184 A EP04722184 A EP 04722184A EP 1608797 A2 EP1608797 A2 EP 1608797A2
Authority
EP
European Patent Office
Prior art keywords
membrane
methoxylated
mea
alkoxylation
reactor
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.)
Granted
Application number
EP04722184A
Other languages
German (de)
English (en)
Other versions
EP1608797B1 (fr
Inventor
Christian Reufer
Konrad Möbus
Thomas Lehmann
Christoph Weckbecker
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.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP1608797A2 publication Critical patent/EP1608797A2/fr
Application granted granted Critical
Publication of EP1608797B1 publication Critical patent/EP1608797B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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

Definitions

  • the invention relates to a process for the anodic alkoxylation of organic compounds, in particular cyclic ethers, N-substituted amides,
  • Carbonyl compounds, alkyl aromatics and h ⁇ t ⁇ roaromatics are carried out in an electrolysis cell divided by a membrane electrode insert (MEA) in the absence of a mediator.
  • MEA membrane electrode insert
  • Alkoxylation reactions of saturated and unsaturated cyclic ethers and of N-alkylamides and alkylaromatics and alkylheteroaromatics are of technical importance since the resulting products or their hydrolysis products are valuable raw materials for pharmaceuticals and pesticides.
  • Various processes for the anodic alkoxylation of organic compounds are known.
  • U.S. Patent 2,714,576 teaches the electrolytic preparation of 2,5-dialkoxy-2,5-dihydrofurans, wherein furan or a substituted furan is electrolyzed in an aliphatic alcohol having 1 to 5 carbon atoms in the presence of a soluble electrolyte.
  • the electrolyte used is ammonium bromide, the effect of which is that it acts as a mediator.
  • the substrate to be alkoxylated is therefore not alkoxylated directly, but indirectly, namely via the intermediate step of bromination.
  • a major disadvantage of the anodic alkoxylation in the presence of a mediator, such as in particular a halogen compound, is that the mediator itself is used for the increased formation of
  • Ion exchange membrane works as an ion conductor.
  • the electrocatalytic layers' may be applied directly to the membrane (porous electrode layer attached) or porous, possibly coated electrodes can be pressed without clearance (zero gap) on the diaphragm.
  • the electrode layers for the alkoxylation were porous platinum layers electrochemically applied to a polyfluorinated cation exchange membrane.
  • the membrane electrode unit is a Nafion® membrane (sulfonated poly-fluorinated polymer or copolymer from E.I Du Pont) with chemically or electrochemically deposited platinum on the surfaces. Platinum / iridium nets or graphite felt are used as collectors.
  • the electrocatalyst layer the membrane electrode assembly was on or within the surface of the Nafion® membrane.
  • the electro-catalyst layer was either deposited as a porous layer on the Nafion® membrane by means of a chemical / electrochemical process or produced by means of an indirect printing process and pressed onto the membrane. In the indirect process, the electrocatalyst was dispersed in a Nafion® solution and this mixture was applied to a Teflon film; after evaporation of the solvent mixture at elevated
  • the catalyst layer including the carrier film was pressed onto the membrane by means of a hot press; the carrier film was then removed.
  • the cell voltage rose to unacceptably high values within a very short time.
  • the aforementioned electrosynthesis could be improved by the addition of various co-solvents, but this made the work-up of the reaction mixture more difficult.
  • the explanations in this document suggest that the type of electrocatalyst layer is a cause for the unsatisfactory behavior of electrosynthesis in the absence of co-solvents.
  • a plate stack cell with series-connected stack electrodes is used for the electrolytic oxidation, including an anodic alkoxylation of alkyl aromatics, ethers and carbonic acid acids used, at least one stack electrode made of a graphite felt plate, one
  • Carbon felt plate or a fabric made of carbon-covered 'educt contact surface is expediently a solid electrolyte.
  • the technical effort of the plate stack cell is considerable since the cell has a specific structure and a suitable peripherals required. Although high selectivities can be achieved in some cases, the current yields leave something to be desired. There is therefore a potential for further improvements.
  • WO 97/13006 teaches a membrane electrode assembly which has an oxidizing catalyst on one side of a polymeric perfluorosulfonic acid membrane and a reducing catalyst on the other side, which has at least one of the following elements in elemental form or in the form of compounds, namely Zn, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lo, Bi and In.
  • the oxidizing catalyst advantageously contains one Palladium, platinum and iridium element.
  • the membrane electrode assembly is produced by direct coating with a suspension which contains a catalyst-containing carbon black and an ionomeric binder in a liquid medium such as propylene carbonate.
  • this document is directed to a process for the production of hydrogen peroxide from hydrogen and oxygen.
  • alkenes can also be epoxidized and sulfur dioxide can be oxidized to sulfuric acid.
  • Another possible application is the conversion of organic nitro compounds into amine dyes and the extraction of phenol from benzene.
  • the present invention accordingly relates to an improved process for the alkoxylation of organic compounds, in particular those from the series of cyclic ethers, N-substituted amides,
  • anodic alkoxylation can be carried out in an electrolysis cell containing a membrane electrode unit in the absence of a mediator with a high current efficiency.
  • the anodic alkoxylation should be among the practical ones
  • Operating conditions can be carried out at a cell voltage below 25 volts.
  • the membrane electrode assembly which on a fluorinated cation exchange membrane or a non-ionomeric microporous polypropylene membrane has a carbon black and / or graphite-containing coating on both sides, which in addition to the carbon black or graphite and possibly a heavy metal catalyst also contains an ionomer ,
  • a process for the anodic alkoxylation of an organic compound was found in which a mixture containing the organic compound and an alcohol having 1 to 4 carbon atoms, in particular methanol and ethanol, passed through the anode compartment, into an anode compartment and through a membrane electrode assembly (MEA) Is guided cathode space separate reactor and wherein the MEA comprises a membrane, the two sides of which are provided with an electrode layer, which is characterized in that one uses a reactor with an MEA with a cation exchange membrane or a microporous polypropylene membrane, one or both electrode layers of which have been produced using a carbon black and / or graphite, which may be heavy metal doped, and a sulfonated polyfluorinated polymer or copolymer in a suspension containing a liquid suspension medium.
  • MEA membrane electrode assembly
  • Embodiments of the method according to the invention in particular on execution forms of the coating and on the organic substrates to be preferably alkoxylated.
  • alkoxylating with isopropanol it should be noted that the stability of a Nafion® membrane in this medium is limited.
  • MEA Membrane electrode unit
  • the reactor comprises a container which can be passed through.
  • the current collectors consist of an electrically highly conductive porous material, for example a graphite paper, graphite felt or a mesh made of a noble metal or a metal alloy.
  • the layer of the current collector opposite the electrode layer borders on the cathode compartment or the anode compartment.
  • the reactor further comprises in each case an inlet and an outlet into / from the cathode compartment and into / from the anode compartment.
  • the compound to be alkoxylated is passed through the anode compartment in a solution of the alcohol used for the alkoxylation.
  • auxiliaries 1 for the stability of the voltage curve can be added to the solution in an effective amount which does not substantially reduce the selectivity. Examples are water, H 2 S0 4 . Solutions with a co-solvent, such as sulfolane, alkyl amides, can also be used.
  • the reaction mixture to be alkoxylated or an already alkoxylated reaction mixture can be used to remove the hydrogen formed on the cathode.
  • the cathode chamber medium in particular in the case of continuous processes, other liquid media or a gaseous medium which contains constituents, as a result of which the effectiveness of the membrane is not adversely affected, can be used as the cathode chamber medium.
  • the mixture to be alkoxylated is first passed through the anode compartment and then also through the cathode compartment.
  • the latter can be passed through the anode compartment again. This cycle is repeated until the desired conversion of the compound to be alkoxylated or the desired charge conversion have been reached.
  • the processing of the alkoxylated reaction mixture depends on the material data of the reaction components contained therein.
  • the workup usually comprises steps from the series of distillation and extraction.
  • Target products as suitable cosolvents to increase the selectivity. Accordingly, it can be advantageous to add up to 35 mol% of the alkoxylated product to the feed mixture at the very beginning of the electrosynthesis.
  • the anodic alkoxylation in particular a methoxylation or ethoxylation, is advantageously carried out at a current density in the range from 1 to 500 ⁇ iA / cm 2 , preferably 10 to 50 mA / cm 2 .
  • the reactor is operated at a voltage in the range of 1 to 50 volts, preferably 5 to 25 volts.
  • the use concentration of the compound to be alkoxylated in the alcohol used for the alkoxylation is not very critical; an application concentration in the range from 0.1 to 5 mol / 1, in particular 0.5 to 3 mol / 1, is preferred.
  • the membrane (MEA) is preferably an ionomeric membrane with cation exchange properties.
  • fluorinated membranes which contain sulfonic acid groups as a cation exchanger group have proven successful.
  • preferred polymers and copolymers can also have those chain elements or branches which contain ether bridges.
  • Such polymers and copolymers are commercially available in the form of films, for example under the name Nafion® (EI Du Pont) and Gore Asselect® (WL Gore and Sociates). The one designed as a membrane
  • Solid-state electrolyte of the MEA can consist of one or more layers and preferably has a thickness in the range from 25 to 300 ⁇ .
  • microporous nonionic membranes in particular microporous polyolefin membranes, such as preferably a polypropylene membrane, are also suitable.
  • the selectivity of the alkoxylation is admittedly using the microporous ones used by the inventors
  • Polypropylene membrane slightly lower than when using an ionomer membrane, however the chemical stability of the membrane is much higher than that of the Nafion® membranes.
  • any sufficiently conductive carbon black as well as graphite or any mixtures of carbon black and graphite known per se for such purposes can be used to produce the electrode layers.
  • the carbon black or graphite to be used can also be doped in an effective amount with a catalytically active heavy metal, in particular a metal from the series gold, platinum, palladium and iridium.
  • the suspension used to produce the electrode layers contains an ionomeric, in particular a polyfluorinated, sulfonated polymer or copolymer in dissolved form or in the form of swollen, very small particles. Solvents respectively
  • Swelling agents can be used in pure form or in the form of mixtures. Suitable agents are, for example, alcohols, such as isopropanol, isobutanol and tert. -Butanol, and also esters, especially cyclic esters, such as propylene carbonate. Solved and with the above
  • Solvents that can be further diluted based on perfluorinated sulfonated polymers and copolymers are commercially available. Ionomers in the Na + form are available in aqueous solvent systems.
  • the polymer or copolymer in dissolved form mostly not in the form of the free one Sulfonic acid before, but in the form of a salt, for example a sodium salt or preferably a tetrabutylammonium salt.
  • the solution of the polymer or copolymer can additionally contain water.
  • the suspension is added in a manner known per se
  • the indirect printing process can also be used, in which case first an inert support is coated and then the layer is transferred to the ionomeric support. Coating is particularly expediently carried out using screen printing. After coating the membrane with the suspension, the solvent contained in the suspension is evaporated at elevated temperature, and then the membrane, together with one or both electrode layers, is subjected to a thermal treatment at a temperature in the range from 75 ° C. to about 85 ° C. subjected. After the heat treatment, the electrode layer, if it was in salt form, is converted into the protonated form in a manner known per se.
  • the method for producing the membrane electrode assembly with the generic electrode layers is disclosed in US Pat. No. 5,211,984, which is hereby incorporated into the description.
  • the anodic alkylation according to the invention is particularly accessible to organic compounds from the series of cyclic ethers, N-substituted amides, carbonyl compounds, such as in particular ketones, alkyl aromatics and alkyl heteromats.
  • a first class of substrates that are easy to alkoxylate are cyclic ethers, which can be saturated, unsaturated or heteroaromatic.
  • the ring system containing oxygen expediently has 5 to 7 ring members, preferably 5 or 6 ring members with one O atom, but further saturated or unsaturated ring systems, in particular benzene nuclei, can be fused to this ring system.
  • Examples of substances from the classes mentioned are furan, and furans substituted one to four times, and the dihydro and tetrahydro compounds derived therefrom, such as, for example, tetahydrofuran.
  • cyclic ethers are 1,2- and 1,4-pyrans and their di- and tetrahydro derivatives; Finally, 1,4-pyrones and their di- and tetrahydro derivatives are also available for anodic alkoxylation.
  • 1,2-Pyrones can also be alkoxylated, but these are lactams.
  • the substituents are in particular alkyl groups, which in turn can have a functional group such as hydroxyl, acetoxy, alkoxycarbonyl, amidocarbonyl, carboxyalkyl, nitrile and amino. Such a functional group is expediently bound to the heterocyclic ring via a methylene or ethylene bridge.
  • substituents are alkoxy, halogen, carboxyl, acyl and the aldehyde group. If non-aromatic cyclic ethers are alkoxylated, they must have at least one abstractable H atom on a C atom adjacent to the ether oxygen.
  • the corresponding 2, 5-dihydro-2, 5-dialkoxyfurans are formed by the anodic alkoxylation according to the invention with a generally high material yield and a very high current yield.
  • the hydrogenated furans or other cyclic ethers such as pyrans, pyrones, dioxane and morpholine, the corresponding mono- and / or dialkoxy derivatives are formed, the
  • Alkoxy groups are on the carbon atom (s) adjacent to the ether oxygen.
  • linear and cyclic N-substituted amides can be alkoxylated.
  • the amide nitrogen atom has one or two alkyl substituents which can also form a saturated or unsaturated, optionally heteroaromatic ring with the N atom.
  • at least one carbon atom bound to nitrogen has at least one abstractable hydrogen atom, or the nitrogen atom is a ring member of a heteroaromatic ring.
  • amides examples include lactams with 5 to 7 ring members, where the amide nitrogen can also be alkylated.
  • the lactams are, for example, N-alkylpyrrolidone, and the heterocyclic ring can additionally contain one or more substituents.
  • the alkyl group bonded to the nitrogen is particularly preferably methyl. Further examples are N-alkylvalerolactam and N-alkylcaprolactam.
  • N-acylated saturated and unsaturated N-heterocycles which have at least one abstractable carbon atom on at least one of the carbon atoms adjacent to the nitrogen
  • N-acylated pyrroles pyrrolines and pyrrolidines optionally substituted on the ring one or more times.
  • the acyl group is, for example, formyl, acetyl, propionyl, benzoyl.
  • the substituents which are bonded to one or more carbon atoms of the N-heterocyclic ring are those as previously listed in connection with the cyclic ethers.
  • the substituents are particularly preferably an alkyl group having 1 to 4 carbon atoms, in particular methyl or ethyl, hydroxymethyl, acetoxymethyl and carboxymethyl.
  • open-chain N-alkyl or N, N-dialkyl fatty acid amides in particular amides of fatty acids with 1 to 6 carbon atoms, can also be alkoxylated. It is also possible to use substrates which have two N-alkylamide structural elements in one molecule.
  • ketones with a methyl group or methylene group bonded to the carbonyl carbon atom are alkoxylated, in particular methoxylated or ethoxylated.
  • alkoxylated in particular methoxylated or ethoxylated.
  • Examples are aliphatic ketones with 3 to 12 carbon atoms, aromatic-aliphatic ketones, such as
  • alkylated aromatic and heteroaromatic compounds are alkoxylated, the carbon atom of an alkyl group bonded to the aromatic or heteroaromatic must have at least one abstractable hydrogen atom.
  • the substrates can additionally have substituents other than alkyl.
  • the aromatic preferably contains or
  • the corresponding alkoxyalkyl aromatics or heteroaromatics are formed by the alkoxylation according to the invention.
  • the reactor used in the example below had a structure similar to that of fuel cells.
  • a membrane electrode unit with an electrode area of 50 cm 2 per electrode was used.
  • the MEA included one
  • Cation exchange membrane namely Nafion®117 and soot particles embedded in Nafion® on both sides.
  • soot particles that were doped with platinum or with platinum-ruthenium particles were used.
  • the MEA is produced in the manner described above.
  • the membrane was contacted on both sides with graphite paper as a current collector.
  • the electrolyte was successively circulated in the discontinuous process described, i.e. first pumped into the anode compartment and from there directly into the cathode compartment and back into the anode compartment, until the desired conversion was achieved.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé amélioré d'alcoxylation anodique d'un composé organique avec un alcool ayant 1 à 4 atomes de carbone, notamment du méthanol, dans un réacteur comportant une unité électrode à membrane (MEA). Selon l'invention, on utilise un réacteur pourvu d'une unité électrode à membrane, cette unité électrode à membrane étant une membrane d'échange cationique ou une membrane de polypropylène poreuse et produit une ou deux couches d'électrodes à l'aide de suie, graphite ou suie dopée aux métaux lourds et un polymère ou copolymère polyfluoré sulfoné dans une suspension contenant un agent de suspension liquide.
EP04722184A 2003-04-03 2004-03-20 Procede d'alcoxylation anodique de composes organiques Expired - Lifetime EP1608797B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10315186A DE10315186A1 (de) 2003-04-03 2003-04-03 Verfahren zur anodischen Alkoxylierung von organischen Verbindungen
DE10315186 2003-04-03
PCT/EP2004/002950 WO2004087999A2 (fr) 2003-04-03 2004-03-20 Procede d'alcoxylation anodique de composes organiques

Publications (2)

Publication Number Publication Date
EP1608797A2 true EP1608797A2 (fr) 2005-12-28
EP1608797B1 EP1608797B1 (fr) 2006-06-21

Family

ID=33016130

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04722184A Expired - Lifetime EP1608797B1 (fr) 2003-04-03 2004-03-20 Procede d'alcoxylation anodique de composes organiques

Country Status (4)

Country Link
US (1) US20060272952A1 (fr)
EP (1) EP1608797B1 (fr)
DE (2) DE10315186A1 (fr)
WO (1) WO2004087999A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100800305B1 (ko) 2006-06-05 2008-02-01 (주)씨엔디환경 수처리용 분리막 장치 및 이를 포함하는 수처리 시스템
DE102009001008A1 (de) * 2009-02-19 2010-08-26 Evonik Degussa Gmbh Reaktivextraktion von freien organischen Säuren aus deren Ammoniumsalzen
CN105198840B (zh) * 2015-09-28 2018-06-26 乐平市康鑫医药化工有限公司 固定床法制备2,5-二甲氧基二氢呋喃的方法
CN113897627B (zh) * 2020-07-06 2023-03-03 万华化学集团股份有限公司 一种电化学制备五元杂环二烷氧基化合物的方法
CN114214648B (zh) * 2022-01-10 2023-05-26 万华化学集团股份有限公司 一种制备1,1,4,4-四甲氧基-2-丁烯的电化学合成方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2714576A (en) * 1949-12-29 1955-08-02 Sadolin And Holmblad As Electrolytic preparation of 2,5-dialkoxy-2,5-dihydrofurans
US5211984A (en) * 1991-02-19 1993-05-18 The Regents Of The University Of California Membrane catalyst layer for fuel cells
US5476580A (en) * 1993-05-17 1995-12-19 Electrochemicals Inc. Processes for preparing a non-conductive substrate for electroplating
DE19962102A1 (de) * 1999-12-22 2001-06-28 Basf Ag Verfahren zur elektrochemischen Oxidation von organischen Verbindungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004087999A2 *

Also Published As

Publication number Publication date
WO2004087999A2 (fr) 2004-10-14
US20060272952A1 (en) 2006-12-07
WO2004087999A3 (fr) 2005-04-28
EP1608797B1 (fr) 2006-06-21
DE502004000843D1 (de) 2006-08-03
DE10315186A1 (de) 2004-10-21

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