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US20060157353A1 - Method for the anodic alkoxylation of organic substances - Google Patents

Method for the anodic alkoxylation of organic substances Download PDF

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Publication number
US20060157353A1
US20060157353A1 US10/546,135 US54613505A US2006157353A1 US 20060157353 A1 US20060157353 A1 US 20060157353A1 US 54613505 A US54613505 A US 54613505A US 2006157353 A1 US2006157353 A1 US 2006157353A1
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United States
Prior art keywords
alkyl
alkoxylation
group
organic compound
methoxylated
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Abandoned
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US10/546,135
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English (en)
Inventor
Christian Reufer
Thomas Lehmann
Christoph Weckbecker
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Evonik Operations GmbH
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Degussa GmbH
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Assigned to DEGUSSA AG reassignment DEGUSSA AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEHMANN, THOMAS, WECKBECKER, CHRISTOPH, REUFER, CHRISTIAN, SANZENBACHER, RAINER
Publication of US20060157353A1 publication Critical patent/US20060157353A1/en
Abandoned legal-status Critical Current

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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
    • C25B3/20—Processes
    • C25B3/23—Oxidation

Definitions

  • the subject matter of the present invention relates to a method for the anodic alkoxylation of organic substrates, in particular cyclic ethers, such as especially furan and furan derivatives, which may also be wholly or partially hydrogenated, N-substituted amides, carbonyl compounds, alkyl aromatic hydrocarbons and alkyl heteroaromatic hydrocarbons.
  • the anodic alkoxylation more specifically the methoxylation, is carried out in an unpartitioned electrolytic cell in the absence of a solid polymer electrolyte.
  • Alkoxylation reactions of saturated and unsaturated cyclic ethers and of N-alkyl amides and alkyl aromatic hydrocarbons and alkyl heteroaromatic hydrocarbons are of industrial importance since the resulting products or the hydrolysis products thereof are valuable raw materials for pharmaceuticals and pesticides.
  • Several different methods for the anodic alkoxylation of organic compounds are known.
  • U.S. Pat. No. 2,714,576 discloses the electrolytic production of 2,5-dialkoxy-2,5-dihydrofurans during which furan or a substituted furan is electrolyzed in an aliphatic alcohol with 1-5 carbon atoms in the presence of a soluble electrolyte.
  • the electrolyte used is ammonium bromide, the effect of which is to act as a mediator.
  • the substrate to be alkoxylated thus is alkoxylated not directly but indirectly via the intermediate step of a bromination.
  • ammonium bromide other halogen compounds can be used as a supporting electrolyte salt and a mediator as well.
  • a serious drawback of the anodic alkoxylation in the presence of a mediator, such as especially a halogen compound, is that the mediator itself can lead to an increased formation of by-products and thus makes the processing and purification of the alkoxylated substrate more difficult. Undesirable halogenated by-products are formed especially when halogen compounds are used as a mediator.
  • furan derivatives can also be anodically alkoxylated in the presence of supporting electrolyte salts which do not act as a mediator, such as concentrated sulfuric acid, boron fluoride etherate, sodium formiate and sodium nitrate.
  • electrolyte salts which do not act as a mediator, such as concentrated sulfuric acid, boron fluoride etherate, sodium formiate and sodium nitrate.
  • a catholyte and an anolyte are passed through the partitioned electrolytic cell, with the anolyte used being the catholyte from a previous reduction.
  • the disadvantage is that a high cell voltage is required. Although an increase in the temperature makes it possible to reduce the cell voltage and thus to increase the current efficiency, this type of approach is not useful since the chemical stability of the methoxy compound is extremely limited.
  • the cell voltage can also be reduced by reducing the thickness of the membrane but this has the effect that the mechanical vulnerability of the membrane is considerably increased at the same time.
  • the SPE method appears to be of interest to the anodic alkoxylation because of the absence of a supporting electrolyte salt, it has so far not been possible to develop this method as a viable economic alternative to the methods which operate in an unpartitioned electrolytic cell in the presence of a mediator, in particular a halide.
  • the low current efficiency of the SPE method is at least in part attributable to the destruction of the Nafion® membrane as a result of the by-products of the reaction.
  • a mediator such as bromine or bromide
  • a plate stack cell with in-series-connected stack electrodes is used for the electrolytic oxidation, including an anodic alkoxylation, with at least one stack electrode being a graphite felt plate, a carbon felt plate or a fabric of an educt contact surface covered with carbon.
  • the electrodes and the electrolyte are designed to ensure that in the ideal case, no electrolyte ions migrate through the stack electrode.
  • the electrolyte phase in contact with the carbon-containing stack electrode is a solid polymer electrolyte.
  • the plate stack cell is technically extremely complex since the cell requires a specific configuration and a suitable periphery.
  • mediators such as are used for the electric oxidation and reduction of the most varied substrates, are regenerated electrochemically.
  • the compound used as mediator is brought into contact with a diamond film electrode which causes an exchange of a redox equivalent to take place.
  • the electrochemical regeneration is an oxidation or reduction of the compound used as a mediator, depending on whether the organic compound is to be reduced or oxidized by means of the mediator.
  • Mediators to be mentioned are those of the series of the metal salts and halogen compounds that are available in a number of oxidation stages but also organic mediators.
  • the method described in the document mentioned above is, among other things, suitable for the alkoxylation of carbonyl compounds, N-alkyl amides, alkyl aromatic hydrocarbons and heterocyclic compounds, such as furan and tetrahydrofuran and N-methylpyrrolidone-2.
  • the diamond film electrode to be used has a core comprising, for example, titanium, silicon or graphite, onto which a doped conducting diamond film is deposited.
  • diamond film electrodes are doped with a tri- to pentavalent element, such as in particular boron or phosphorus.
  • a tri- to pentavalent element such as in particular boron or phosphorus.
  • the problem to be solved by the present invention is to make available another method for the anodic alkoxylation, in particular methoxylation, of organic substrates, in particular of cyclic ethers and N-substituted amides, which method can be carried out in a simple manner and which can also be used for the industrial production of the alkoxylated products.
  • the method to be disclosed was to have neither the disadvantages known from the SPE method nor should it lead to an alkoxylation product with halogenated by-products.
  • a special advantage of the invention is that it is not necessary to use a specially designed electrolytic cell to carry out the anodic oxidation, which makes it possible to use a simple electrode configuration.
  • cell packages in a stacked configuration are possible.
  • the method for the anodic alkoxylation of an organic compound provides that a mixture comprising the organic compound and a primary alcohol with 1-4 C atoms be alkoxylated in an unpartitioned electrolytic cell in the presence of a supporting electrolyte salt that is soluble in the mixture, but in the absence of a solid polymer electrolyte, at an effective cell voltage using an oxidation-resistant anode, which method is characterized in that the anodic alkoxylation is carried out in the absence of a mediator, using a diamond film anode or a gold anode.
  • the dependent claims relate to preferred embodiments of the method according to the present invention, including the substrates to be preferably alkoxylated and the supporting electrolyte salts to be preferably used, which salts, even in a low concentration, lead to an adequate conductivity and are not oxidizable under the electrolysis conditions, thus ensuring that they do not have the effect of a mediator.
  • Suitable for use in the anodic alkylation [sic; alkoxylation] are, in particular, organic compounds of the series of cyclic ethers, N-substituted amides, carbonyl compounds, alkyl aromatic hydrocarbons and alkyl heteroaromatic hydrocarbons.
  • the first group of substrates to be readily alkoxylated are cyclic ethers which can be saturated, unsaturated or heteroaromatic.
  • the ring system containing oxygen preferably has 5-7 ring members, preferably 5 or 6 ring members with an O atom, but additional saturated or unsaturated ring systems, in particular benzene nuclei, can also be anellated to this ring system.
  • Examples of substances of the groups mentioned are furan and 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 the di- and tetrahydro derivatives thereof, 1,4-pyrones and the di- and tetrahydro derivatives thereof can also be anodically alkoxylated.
  • 1,2-pyrones which are, however, lactams can be alkoxylated.
  • 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.
  • a functional group is bound to the heterocyclic ring via a methylene or ethylene bridge.
  • Nonaromatic cyclic ethers that are to be alkoxylated must have at least one abstractable H atom on a C atom that is next to an ether oxygen.
  • the anodic alkoxylation according to the present invention makes it possible to obtain the corresponding 2,5-dihydro-2,5-dialkoxyfurans with a generally high material yield and a very high current efficiency.
  • the hydrogenated furans or other cyclic ethers, such as pyrans, pyrones, dioxane and morpholine as the starting materials, the corresponding mono- or/and dialkoxy derivatives are obtained, with the alkoxy groups being located on the carbon atom(s) next to the ether oxygen.
  • the amide nitrogen atom has one or two alkyl substituents which can also form a saturated or unsaturated, possibly heteroaromatic ring with the N atom.
  • at least one C atom bound 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 with 5-7 ring members, with the possibility that the amide nitrogen can be additionally alkylated.
  • the lactams include, for example, N-alkyl pyrrolidone, with the possibility that the heterocyclic ring in addition has one or more substituents. Most preferably the alkyl group bound to the nitrogen is methyl. Other examples are N-alkyl valerolactam and N-alkyl caprolactam.
  • N-acylated saturated and unsaturated N-heterocyclic compounds which have at least one abstractable hydrogen atom on at least one of the carbon atoms next to the nitrogen or which are heteroaromatic.
  • Examples of the previously mentioned groups are: N-acylated pyrroles, pyrrolines and pyrrolidines optionally mono- or polysubstituted on the ring.
  • the acyl group may be, for example, formyl, acetyl, propionyl or benzoyl.
  • the substituents that are bound to one or more carbon atoms of the N-heterocyclic ring are substituents such as were listed above in connection with the cyclic ethers.
  • Especially preferred substituents are an alkyl group with 1-4 C atoms, in particular methyl or ethyl, hydroxymethyl, acetoxymethyl and carboxymethyl.
  • alkoxylate open-chain N-alkyl or N,N-diallyl fatty acid amides in particular amides of fatty acids with 1-6 carbon atoms.
  • substrates which have two N-alkyl amide structural element in one molecule.
  • ketones with a methyl group or methylene group bound to the carbonyl carbon atom are alkoxylated, in particular methoxylated or ethoxylated.
  • alkoxylated examples include aliphatic ketones with 3-12 C atoms, aromatic-aliphatic ketones, such as acetophenone, and methyl benzyl ketone.
  • the resulting alkoxy ketones are generally converted directly into the corresponding ketal.
  • alkylated aromatic and heteroaromatic compounds are alkoxylated, in which case the carbon atom of an alkyl group bound to the aromatic hydrocarbon or to the heteroaromatic hydrocarbon must have at least one abstractable hydrogen atom.
  • the substrates can, in addition, have substituents other than alkyl.
  • the aromatic or heteroaromatic hydrocarbon preferably has one or more alkyl groups of the series of methyl, ethyl and n-propyl. The alkoxylation according to the present invention leads to the corresponding alkoxy alkyl aromatic and heteroaromatic hydrocarbons.
  • the substrate to be alkoxylated is dissolved using the alcohol that is used for the alkoxylation as the solvent.
  • this solution is passed through the unpartitioned electrolytic cell.
  • the reaction mixture obtained after adequate alkoxylation can be suitably processed by means of distillation and/or extraction.
  • the bottom containing the supporting electrolyte salt is returned to the process.
  • the anodic alkoxylation can be carried out by continuous or by batch operation.
  • the supporting electrolyte salt used is a substance, the ions of which are neither oxidized nor reduced in the range of the potential selected so that the supporting electrolyte salt does not act as a mediator and therefore undergoes, if any, only very insignificant secondary reactions.
  • Especially preferred supporting electrolyte salts are tetraalkyl ammonium salts.
  • the alkyl groups of the tetraalkyl ammonium ion are, in particular, alkyl with 1-6 C atoms, especially preferred are 3 or 4 C atoms.
  • Two alkyl groups together with the ammonium nitrogen can jointly form a ring system, especially a five- or six-membered ring.
  • those tetraalkyl ammonium salts in which three alkyl groups form a bicyclic ring system are also usable.
  • the anions of the supporting electrolyte salts to be preferably used according to the present invention are preferably those of the series of ClO4-, BF4-, PF6-, SbF6-, R—SO3- and R—SO4-;
  • R stands for an alkyl which can also be halogenated, especially CF3-, CC13- or CF3CH2-, R can also stand for an aryl which in turn can be substituted as well.
  • the supporting electrolyte salt used is tetra-n-butyl ammonium tetrafluoroborate.
  • the quantity of the supporting electrolyte salts used . . . [bottom line cut off] . . . an adequate conductivity of the solution to by electrolyzed is reached.
  • the quantity of the supporting electrolyte salt used is generally in a range from 0.1-5 wt %, preferably from 0.3-3 wt %, relative to the solution to be electrolyzed.
  • the anodic oxidation is generally carried out at a voltage in a range from 1-70 volt, in particular from 5-25 V.
  • the current density is preferably set to a range from 1-25 A/dm2; however, values below as well as above the threshold values are also possible.
  • the anode is one with a diamond film.
  • the substrate material for the diamond film is preferably a material of the of graphite, graphite/gold, silicon or a passivating metal, such as titanium, zirconium, niobium, tantalum, tungsten and molybdenum, or a carbide or nitride of the elements Ti, Si, Nb, Ta, Zr and Mo.
  • the material to be used for the cathode is one that is stable in the reaction medium. Especially suitable is a material of the series of graphite, platinum nickel, stainless steel and diamond film if the reaction medium is substantially anhydrous.
  • a cathode material with a high hydrogen or oxygen overvoltage is to be preferred; i.e., preferably a diamond film electrode is used.
  • Diamond film electrodes presently known can be used in the method according to the present invention.
  • Diamond film electrodes which are rendered conductive by means of a suitable dopant are highly corrosion-resistant and significantly less susceptible to electrode fouling. Based on experiences so far, in contrast to other electrodes, the diamond film electrodes to be used have not undergone any adsorption phenomena which could reduce the selectivity. Similarly good results are obtained with a gold anode.
  • the absence of a mediator makes it easier to process the electrolyte product.
  • the purity of the alkoxylation product is higher since by-products that can form as a result of the mediators, including products of a reaction between the substrate or the alkoxylation product and the mediator, are absent.
  • the configuration of an electrolysis system to be used is known in the art.
  • the cathode can be made of conventional materials, but it can also be a diamond film electrode.
  • a methanolic furan solution (furan concentration 8 wt %; molar ratio of methanol:furan 24:1) was used.
  • the volumetric flow rate through the electrolytic cell was 1 L/min.
  • the raw electrolyte product produced had a light yellowish color and was clear.
  • the anodic methoxylation of furan in the presence of sodium methylate has the advantage that a supporting electrolyte salt, the anion of which corresponds to that of the alkoxylation agent, can be used.
  • the tradeoff for this advantage is a lower material yield.
  • a higher yield is obtained with a supporting electrolyte salt of the type according to Example B1
  • the use of an alkoxylate as the supporting electrolyte salt and a diamond film electrode still results in a material yield that is more than twice as high than that obtained with the use of an alkoxide and a platinum anode (see literature citation C).
  • Example B3 in addition to the results of Examples B1 and B2, the results of another example (B3) according to the present invention and of a reference example (VB1) for the methoxylation of furan are listed.
  • the electrolytic solution of Example B3 and Reference Example VB1 contained 7-8 wt % of furan in methanol and 3 wt % of the supporting electrolyte salt; in B3 and VB1, the anode was different.
  • the results obtained with the gold anode were similarly good as the results obtained with a diamond film anode.
  • a graphite anode led to a considerably lower current efficiency.
  • the crude electrolyte product produced in Reference Example VB2 had a yellowish orange color and was clear.

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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)
US10/546,135 2003-03-25 2004-03-15 Method for the anodic alkoxylation of organic substances Abandoned US20060157353A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10313169A DE10313169A1 (de) 2003-03-25 2003-03-25 Verfahren zur anodischen Alkoxylierung von organischen Substraten
DE10313169.8 2003-03-25
PCT/EP2004/002665 WO2004085710A2 (fr) 2003-03-25 2004-03-15 Procede d'alcoxylation anodique de substrats organiques

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US (1) US20060157353A1 (fr)
EP (1) EP1606434A2 (fr)
DE (1) DE10313169A1 (fr)
WO (1) WO2004085710A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100210871A1 (en) * 2009-02-19 2010-08-19 Evonik Degussa Gmbh Reactive Extraction of Free Organic Acids from the Ammonium Salts Thereof
CN113897627A (zh) * 2020-07-06 2022-01-07 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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2714579A (en) * 1951-07-18 1955-08-02 Exxon Research Engineering Co Lubricating oil additives
US4284825A (en) * 1978-11-08 1981-08-18 Basf Aktiengesellschaft 4-Substituted benzaldehyde-dialkylacetal
US4441970A (en) * 1981-10-28 1984-04-10 Basf Aktiengesellschaft Electrochemical preparation of 2,5-dialkoxy-2,5-dihydrofurans
US4699698A (en) * 1985-08-14 1987-10-13 Basf Aktiengesellschaft Preparation of benzoic acid ortho-esters and novel compounds of this type
US5074974A (en) * 1990-06-08 1991-12-24 Reilly Industries, Inc. Electrochemical synthesis and simultaneous purification process
US6533916B1 (en) * 1999-03-16 2003-03-18 Basf Aktiengesellschaft Diamond electrodes

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3605451A1 (de) * 1986-02-20 1987-08-27 Bayer Ag Benzaldehyd-dialkylacetale
DE3708337A1 (de) * 1987-03-14 1988-09-22 Basf Ag Verfahren zur herstellung von methoxiacetaldehyddialkylacetalen

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2714579A (en) * 1951-07-18 1955-08-02 Exxon Research Engineering Co Lubricating oil additives
US4284825A (en) * 1978-11-08 1981-08-18 Basf Aktiengesellschaft 4-Substituted benzaldehyde-dialkylacetal
US4441970A (en) * 1981-10-28 1984-04-10 Basf Aktiengesellschaft Electrochemical preparation of 2,5-dialkoxy-2,5-dihydrofurans
US4699698A (en) * 1985-08-14 1987-10-13 Basf Aktiengesellschaft Preparation of benzoic acid ortho-esters and novel compounds of this type
US5074974A (en) * 1990-06-08 1991-12-24 Reilly Industries, Inc. Electrochemical synthesis and simultaneous purification process
US6533916B1 (en) * 1999-03-16 2003-03-18 Basf Aktiengesellschaft Diamond electrodes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100210871A1 (en) * 2009-02-19 2010-08-19 Evonik Degussa Gmbh Reactive Extraction of Free Organic Acids from the Ammonium Salts Thereof
CN113897627A (zh) * 2020-07-06 2022-01-07 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

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Publication number Publication date
WO2004085710A2 (fr) 2004-10-07
EP1606434A2 (fr) 2005-12-21
WO2004085710A3 (fr) 2005-04-21
DE10313169A1 (de) 2004-10-14

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