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EP1608797B1 - Procede d'alcoxylation anodique de composes organiques - Google Patents

Procede d'alcoxylation anodique de composes organiques Download PDF

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Publication number
EP1608797B1
EP1608797B1 EP04722184A EP04722184A EP1608797B1 EP 1608797 B1 EP1608797 B1 EP 1608797B1 EP 04722184 A EP04722184 A EP 04722184A EP 04722184 A EP04722184 A EP 04722184A EP 1608797 B1 EP1608797 B1 EP 1608797B1
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EP
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Prior art keywords
membrane
process according
methoxylated
mea
group
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EP04722184A
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German (de)
English (en)
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EP1608797A2 (fr
Inventor
Christian Reufer
Konrad Möbus
Thomas Lehmann
Christoph Weckbecker
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Evonik Operations GmbH
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Degussa GmbH
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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
    • 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 is directed to a process for the anodic alkoxylation of organic compounds, in particular cyclic ethers, N-substituted amides, carbonyl compounds, alkylaromatics and heteroaromatics.
  • the anodic alkoxylation in particular it is a methoxylation, is carried out in an electrolysis cell divided by a membrane electrode unit (MEA) in the absence of a mediator.
  • MEA membrane electrode unit
  • Alkoxylation reactions of saturated and unsaturated cyclic ethers and of N-alkylamides and alkylaromatics and alkyl heteroaromatics are of industrial importance, since the resulting products or their hydrolysis products are valuable raw materials for pharmaceuticals and pesticides.
  • Various methods for the anodic alkoxylation of organic compounds are known.
  • U.S. Patent 2,714,576 teaches the electrolytic production of 2,5-dialkoxy-2,5-dihydrofurans wherein furan or a substituted furan is electrolyzed in an aliphatic alcohol of 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 thus not alkoxylated directly but indirectly, namely via the intermediate step of a bromination.
  • furan derivatives in the presence of conductive salts which do not act as a mediator, For example, alcoholates to alkoxylate anodically, but in such methods, the current yields and product yields are usually very low.
  • the membrane electrode unit is a Nafion® membrane (sulfonated polyfluorinated polymer or copolymer from E.I Du Pont) with platinum deposited chemically or electrochemically on the surfaces.
  • platinum / iridium nets or graphite felt are used as collectors.
  • high current yields can only be obtained when very large cell voltages are applied, which is very disadvantageous in view of a larger plant.
  • 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 temperature, the catalyst layer including the carrier film was pressed onto the membrane by means of a hot press; then the carrier film was peeled off.
  • the addition-free furan methoxylation led to an increase in the cell tension to indiscussable high values within a very short time.
  • the said electrosynthesis could be improved by the addition of various co-solvents, but this makes it difficult to work up the reaction mixture.
  • the statements in this document suggest that the nature of the electrocatalyst layer is a cause of the unsatisfactory behavior of electrosynthesis in the absence of cosolvents.
  • a plate-stack cell with series-connected stacking electrodes is used for the electrolytic oxidation, including an anodic alkoxylation of alkylaromatics, ethers and carbonic acid amides , wherein at least one stacking electrode consists of a graphite felt plate, a carbon felt plate or a fabric of carbon-covered EduktWallet Structure.
  • the electrolyte phase contacting the carbonaceous stack electrode is a solid state electrolyte.
  • the technical complexity of the plate stacking cell is significant because the cell has a specific structure and a suitable periphery required. Although partially high selectivities are achievable, the current yields leave something to be desired. There is thus a potential for further improvements.
  • WO 97/13006 teaches a membrane electrode assembly having on one side of a polymeric perfluorosulfonic acid membrane, an oxidizing catalyst and on the other side a reducing catalyst comprising 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 suitably contains a Element of the series palladium, platinum and iridium.
  • the membrane electrode assembly is made by directly coating with a suspension containing a catalyst-containing carbon black and an ionomeric binder in a liquid medium such as propylene carbonate.
  • this document is directed to a method for producing hydrogen peroxide from hydrogen and oxygen. Further, by using a membrane electrode assembly with the aforementioned reducing catalyst, alkenes can be epoxidized and sulfur dioxide oxidized to sulfuric acid. Other possible applications include the conversion of organic nitro compounds into aminic dyes and the recovery of phenol from benzene. Advice to carry out reactions other than those mentioned and / or to use a membrane electrode assembly which has a reducing catalyst other than that mentioned can not be found in this document.
  • the present invention accordingly provides an improved process for the alkoxylation of organic compounds, in particular those from the series of cyclic ethers, N-substituted amides, carbonyl compounds, in particular ketones, alkylaromatics and alkyl heteroaromatics, wherein the anodic alkoxylation in an electrolysis cell containing a membrane electrode unit in FIG Absence of a mediator can be performed with high current efficiency.
  • the anodic alkoxylation should be able to be performed under practical operating conditions at a cell voltage below 25 volts.
  • the membrane electrode unit one which on a fluorinated cation exchange membrane or a non-ionomeric microporous polypropylene membrane on both sides of a soot and / or graphite-containing coating which contains in addition to the carbon black or graphite and optionally a heavy metal catalyst additionally an ionomer ,
  • a process has been found for the anodic alkoxylation of an organic compound by passing a mixture containing the organic compound and an alcohol having 1 to 4 carbon atoms, in particular methanol and ethanol, through the anode compartment of an anode chamber and a membrane electrode assembly (MEA) And the MEA comprising a membrane having both sides provided with an electrode layer characterized by using a reactor with an MEA having a cation exchange membrane or a microporous polypropylene membrane having one or both electrode layers formed thereon using a carbon black and / or graphite, which may be heavy metal doped, and a suspension containing a sulfonated polyfluorinated polymer or copolymer in a liquid suspension medium.
  • MEA membrane electrode assembly
  • the subclaims are directed to preferred embodiments of the method according to the invention, in particular to embodiments of the coating and to the organic substrates which are preferably to be alkoxylated.
  • alkoxylating with isopropanol it should be noted that the stability of a Nafion® membrane in this medium is limited.
  • the construction of a reactor with a membrane electrode assembly is well known to those skilled in the art:
  • the reactor comprises a container which, through an MEA disposed therein, into a cathode compartment and a Anode space is shared.
  • On both sides of the MEA are microporous current collectors, which as well as the actual electrode layers are permeable to material.
  • the current collectors consist of a highly electrically conductive porous material, such as a graphite paper, graphite felt or a network of a noble metal or a metal alloy.
  • the layer of the current collector lying opposite the electrode layer adjoins the cathode space or the anode space.
  • these spaces are in the form of a structured flow field, which may be parallel channels, meandering channels or a checkerboard-like structure enabling cross-mixing.
  • the reactor further comprises in each case an inlet and a discharge into / from the cathode space, and into / from the anode space.
  • the compound to be alkoxylated is passed through the anode space in a solution of the alcohol used for the alkoxylation.
  • the solution can be added to the solution known stability stability of the voltage in effective, the selectivity substantially not lowering amount.
  • examples are water, H 2 SO 4 .
  • solutions with a cosolvent, such as sulfolane, alkylamides can be used.
  • the mixture to be alkoxylated is first passed through the anode compartment and then also the cathode compartment. After the separation of the hydrogen from the at least partially alkoxylated reaction mixture, the latter can be redirected through the anode compartment. This cycle is repeated until the desired conversion of the compound to be alkoxylated or the desired charge conversion are achieved.
  • the work-up of the alkoxylated reaction mixture depends on the substance data of the reaction components contained therein. Usually, the workup includes steps from the series of distillation and extraction.
  • the alkoxylated target products proved to be suitable cosolvents for increasing the selectivity. Accordingly, it may be advantageous to add up to 35 mol% of the alkoxylated product to the feed mixture already at the beginning of the electrosynthesis.
  • the anodic alkoxylation in particular a methoxylation or ethoxylation, is expediently carried out at a current density in the range from 1 to 500 mA / cm 2 , preferably 10 to 50 mA / cm 2 .
  • the operation of the reactor is carried out 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 less critical; a use concentration in the range of 0.1 to 5 mol / l, in particular 0.5 to 3 mol / l is preferred.
  • the membrane (MEA) is preferably an ionomeric membrane having cation exchange properties.
  • fluorinated membranes which contain sulfonic acid groups as a cation exchanger group have proven to be useful.
  • Preferred polymers and copolymers may have, in addition to a carbon chain forming a polymer chain, also those chain elements or branches containing ether bridges. Such polymers and copolymers are commercially available in the form of films, for example under the name Nafion® (EI
  • the MEA formed as a membrane solid electrolyte may consist of one or more layers and preferably has a thickness in the range of 25 to 300 microns.
  • microporous non-ionic membranes in particular microporous polyolefin membranes, such as preferably a polypropylene membrane, are also suitable.
  • microporous polyolefin membranes such as preferably a polypropylene membrane
  • the selectivity of the alkoxylation using the microporous polypropylene membrane used by the inventors is somewhat lower than when using an ionomeric membrane, the chemical stability of the membrane is much higher than that of the Nafion® membranes.
  • the electrode layers it is possible to use any sufficiently conductive carbon black known per se for such purposes, as well as graphite or any mixtures of carbon black and graphite.
  • the carbon black or graphite to be used can also be doped with a catalytically active heavy metal, in particular a metal from the series gold, platinum, palladium and iridium, in an effective amount.
  • the suspension used to produce the electrode layers contains, in addition to the carbon black or the doped carbon black, an ionomeric, in particular a polyfluorinated, sulfonated polymer or copolymer in dissolved form or in the form of swollen very small particles. Solvents or 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 esters, in particular cyclic esters, such as Proplencarbonat.
  • Dissolved binders based on perfluorinated sulfonated polymers and copolymers, which are further dilutable with the solvents mentioned, are commercially available. Ionomers in the Na + form are available in aqueous solvent systems.
  • the polymer or copolymer in dissolved form usually not in the form of the free Sulfonic acid, but in the form of a salt, for example a sodium salt or preferably a tetrabutylammonium salt.
  • the solution of the polymer or copolymer may additionally contain water.
  • the suspension is used in a manner known per se using conventional coating techniques such as brushing, printing, dipping and spraying to form the porous electrode layers.
  • the indirect printing method is also suitable, in which case an inert carrier is first coated and then the layer is transferred to the ionomeric carrier.
  • the coating is carried out using the screen printing.
  • the solvent contained in the suspension is evaporated at elevated temperature, and then the membrane is heat-treated together with the one or both electrode layers at a temperature in the range of 75 ° C to about 85 ° C subjected.
  • the electrode layer if present in salt form, is converted in a manner known per se into the protonated form.
  • the method of making the membrane electrode assembly with the generic electrode layers is disclosed in U.S. Patent No. 5,211,984, which is incorporated herein by reference.
  • organic compounds from the series of cyclic ethers, N-substituted amides, carbonyl compounds, in particular ketones, alkylaromatics and alkylheteramines are obtainable from the anodic alkylation according to the invention.
  • a first class of well-alkoxylated substrates are cyclic ethers which may be saturated, unsaturated or heteroaromatic.
  • the oxygen-containing ring system expediently has 5 to 7 ring members, preferably 5 or 6 ring members with an 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, as well as mono- to tetra-substituted furans, as well as the dihydro and tetrahydro compounds derived therefrom, such as tetrahydrofuran.
  • 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 of anodic alkoxylation are accessible.
  • Alkoxylated are also 1,2-pyrones, which are, however, lactams.
  • the substituents are in particular alkyl groups, which in turn may have a functional group such as hydroxyl, acetoxy, alkoxycarbonyl, amidocarbonyl, carboxyalkyl, nitrile and amino. Conveniently, such a functional group is bonded 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 generally high material yield and very high current efficiency.
  • the hydrogenated furans or other cyclic ethers such as pyrans, pyrones, dioxane and morpholine
  • the corresponding mono- and / or dialkoxy derivatives are formed, wherein the alkoxy groups are adjacent to the carbon atom (s) adjacent to the ether oxygen.
  • 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 bonded to the nitrogen has at least one abstractable hydrogen atom, or the nitrogen atom is a ring member of a heteroaromatic ring.
  • amides examples include lactams having 5 to 7 ring members, wherein the amide nitrogen may additionally be alkylated.
  • the lactams are, for example, N-alkylpyrrolidone, where the heterocyclic ring may additionally contain one or more substituents.
  • the alkyl group bonded to the nitrogen is particularly preferably methyl. Further examples are N-alkyl valerolactam and N-alkyl caprolactam.
  • N-acylated saturated and unsaturated N-heterocycles which have at least one abstractable hydrogen atom on at least one of the carbon atoms adjacent to the nitrogen or are heteroaromatic.
  • Examples of the abovementioned classes are: N-acylated, optionally mono- or polysubstituted pyrroles on the ring, pyrrolines and pyrrolidines.
  • the acyl group is, for example, formyl, acetyl, propionyl, benzoyl.
  • the substituents attached to one or more carbon atoms of the N-heterocyclic ring are those substituents listed above in connection with the cyclic ethers.
  • the substituents are particularly preferably an alkyl group having 1 to 4 C atoms, in particular methyl or ethyl, hydroxymethyl, acetoxymethyl and carboxymethyl.
  • alkoxylate open-chain N-alkyl or N, N-dialkyl fatty acid amides in particular amides, of fatty acids having 1 to 6 carbon atoms. It is also possible to use those substrates which have two N-alkylamide structural elements in one molecule.
  • ketones are alkoxylated with a methyl group or methylene group bonded to the carbonyl carbon atom, in particular methoxylated or ethoxylated.
  • examples are aliphatic ketones having 3 to 12 carbon atoms, aromatic-aliphatic ketones, such as acetophenone, and methyl benzyl ketone.
  • the resulting alkoxy ketones are converted directly into the corresponding ketal.
  • alkylated aromatic and heteroaromatic compounds are alkoxylated, wherein the carbon atom of an aromatic group or heteroaromatic bound alkyl group must have at least one abstractable hydrogen atom.
  • the substrates may additionally have substituents other than alkyl.
  • the aromatic or heteroaromatic contains one or more alkyl groups from the series methyl, ethyl and n-propyl. The alkoxylation according to the invention gives rise to the corresponding alkoxyalkylaromatics or heteroaromatics.
  • the current efficiency could be significantly increased by the use of the membrane electrode unit according to the invention. It was found that a membrane coated with carbon black on both sides in the described manner gave the best results. Under the chosen test conditions, there was only a slight increase in the operating voltage. In addition, no water and no co-solvent had to be added to lower the tension to a practical level.
  • the reactor used in the following example had a fuel cell analogue construction.
  • a membrane electrode unit with an electrode area of 50 cm 2 per electrode was used.
  • the MEA included a cation exchange membrane, namely Nafion®117 and carbon black particles embedded in Nafion® on both sides. In further experiments, carbon black particles doped with platinum or with platinum-ruthenium particles were used.
  • the preparation of the MEA is carried out 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 described discontinuous process, ie first pumped into the anode compartment and from there directly into the cathode compartment and back again into the anode compartment, namely, 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)

Claims (10)

  1. Procédé pour l'alcoxylation anodique d'un composé organique, par passage d'un mélange contenant le composé organique et un alcool ayant de 1 à 4 atomes de carbone dans la chambre anodique d'un réacteur divisé par un module membrane-électrode (MEA) en une chambre anodique et une chambre cathodique et le MEA comprenant une membrane dont les deux faces sont munies d'une couche-électrode, caractérisé en ce qu'on utilise un réacteur comportant un MEA avec une membrane échangeuse de cations ou une membrane microporeuse en polypropylène dont une couche-électrode ou les deux couches-électrodes ont été produites à l'aide d'une suspension contenant du noir de carbone et/ou du graphite, qui peuvent être dopés avec des métaux lourds, et un polymère ou copolymère polyfluoré sulfoné dans un milieu liquide de mise en suspension.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise un MEA dont les deux couches-électrodes ont été produites à l'aide d'une suspension contenant du noir de carbone, du graphite ou du noir de carbone dopé au platine.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on utilise un réacteur comportant un MEA dont les couches-électrodes ont été produites à l'aide d'une suspension selon la revendication 1, comprenant l'impression directe ou indirecte de la membrane échangeuse de cations et l'élimination du solvant contenu dans le milieu liquide et le traitement thermique de la membrane revêtue des deux côtés.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on soumet à une alcoxylation anodique un composé organique de la série des éthers cycliques, des amides N-substitués, des composés carbonyle, en particulier des cétones, des composés alkylaromatiques et des composés alkylhétéroaromatiques.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on soumet à une méthoxylation ou une éthoxylation, en particulier à une méthoxylation, un éther cyclique de la série des furannes, dihydrofurannes et tétrahydrofurannes, 1,2-pyrannes et 1,4-pyrannes, et leurs composés di- et tétrahydro, ainsi que des 1,4-pyrones et leurs composés di- et tétrahydro, dans les furannes, pyrannes et pyrones au moins un atome de carbone lié à l'atome d'oxygène en fonction éther comportant un atome d'hydrogène.
  6. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on soumet à une méthoxylation ou une éthoxylation, en particulier à une méthoxylation, un amide de la série des lactames ayant de 5 à 7 chaînons formant le cycle, des N-hétérocycles N-acylés, saturés et insaturés, ainsi que des N-alkyl- ou N,N-dialkylamides d'acides gras à chaîne ouverte, un atome de carbone lié à l'atome d'azote comportant au moins un atome d'hydrogène.
  7. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on soumet à une méthoxylation ou une éthoxylation, en particulier à une méthoxylation, une cétone comportant un groupe méthyle ou un groupe méthylène lié à l'atome de carbone en fonction carbonyle.
  8. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on soumet à une méthoxylation ou une éthoxylation, en particulier à une méthoxylation, un composé aromatique ou hétéroaromatique substitué par le groupe méthyle.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce qu'on effectue l'alcoxylation dans l'alcool correspondant au groupe alcoxy, en tant que solvant, sous une tension dans la plage de 1 à 50 volts, en particulier de 1 à 25 volts.
  10. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'on fait passer le mélange alcoolique à alcoxyler dans la chambre anodique et ensuite dans la chambre cathodique.
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

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

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EP (1) EP1608797B1 (fr)
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WO (1) WO2004087999A2 (fr)

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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

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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

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EP1608797A2 (fr) 2005-12-28
WO2004087999A2 (fr) 2004-10-14
DE10315186A1 (de) 2004-10-21
WO2004087999A3 (fr) 2005-04-28
DE502004000843D1 (de) 2006-08-03
US20060272952A1 (en) 2006-12-07

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