WO2001021858A1 - Verfahren zur elektrolytischen umwandlung von organischen verbindungen - Google Patents
Verfahren zur elektrolytischen umwandlung von organischen verbindungen Download PDFInfo
- Publication number
- WO2001021858A1 WO2001021858A1 PCT/EP2000/009135 EP0009135W WO0121858A1 WO 2001021858 A1 WO2001021858 A1 WO 2001021858A1 EP 0009135 W EP0009135 W EP 0009135W WO 0121858 A1 WO0121858 A1 WO 0121858A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrode
- organic compound
- anode
- hydrogenation
- furan
- Prior art date
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
Definitions
- the present invention relates to a method for the electrolytic conversion of organic compounds, in which an electrode also serves to transfer both oxidation and reduction equivalents.
- One goal of preparative organic electrochemistry is to use the processes occurring in an electrochemical process on both electrodes in parallel.
- MM Baizer in: H. Lund, MM Baizer (ed.), Organic Electrochemistry, Marcel Dekker, New York, 1991, pages 142 ff.).
- Another example is the coupled synthesis of phthalide and t-butylbenzaldehyde, as described in DE 196 18 854.
- cathode and anode processes it is also possible to use the cathode and anode processes to produce a single product or to destroy an educt.
- electrochemical processes include the production of butyric acid (Y. Chen, T. Chou, J. Chin. Inst. Chem. Eng. 27 (1996) pages 337-345), the anodic dissolution of iron, which with the cathodic Formation of ferrocene is coupled (T. Iwasaki et al, J. Org. Chem. 47 (1982) pages 3799 ff.) Or the degradation of phenol (AP Tomilov et al., Elektrokhimiya 10 (1982) pages 239).
- a new possibility opens up when oxidation and reduction take place on one and the same electrode. This means that a substrate receives both oxidation and reduction equivalents simultaneously or in succession.
- a gradual transfer of oxidation and reduction equivalents on an electrode is possible, for example, in cyclic voltammetry, in which the potential of the electrode moves back and forth within a range between positive and negative values within a range (see BD Sawyer, A. Sobkowiak, J. Roberts Jr., Electrochemistry for Chemists, Second Ed., Pages 68-78, John Wiley & Sons, Inc. New York 1995).
- an anode is capable of transferring reduction equivalents to a substrate which has already taken up anodic redox equivalents.
- the method is not limited to the anode, but can also be carried out on the cathode under suitable conditions.
- the method according to the invention for the electrolytic conversion of at least one organic compound in an electrolysis cell, the organic compound being both oxidized and reduced at an electrode.
- the method according to the invention takes place in an undivided cell.
- the organic compound on the anode is both oxidized and reduced, preferably hydrogenated.
- the organic compound is hydrogenated with hydrogen on one electrode, the hydrogen being formed as a product on the other electrode or being supplied to the electrolysis circuit from the outside.
- the organic compound on the cathode is both reduced and oxidized, preferably oxygenated.
- the invention is explained below using the example of anodes which simultaneously oxidize and hydrogenate.
- all organic compounds with reducible groups can be used as starting materials as organic compounds in the process according to the invention, preferably a furan or a substituted furan.
- the process is not limited to furan or substituted furans, but extends to all compounds and classes of compounds which can be oxidized or reduced in the context of organic electrochemistry, or both.
- An overview of the classes of compounds are H. Lund, MM Baizer, (ed.) "Organic Electrochemistry", 3 rd edition, Marcel Dekker, New York 1,991th
- Suitable compounds of the above classes for example, containing double bonds' compounds such as 1) olefins:
- Ri to R each represent an alkyl, aryl, alkoxy group, a hydrogen atom, (substituted) amino groups, a halogen radical or cyano groups and where the substituents Rj to R 4 can be the same or different.
- the double bonds can be part of open-chain or ring-shaped connections, where they can be both part of the ring and the chain or both.
- ring-shaped systems with double bonds can in particular be aromatic systems.
- one or more element (s) of the ring structure can be an optionally substituted heteroatom, such as N, S, O, P.
- the ring-shaped compounds can contain one or more functional substituents of the following type as substituents:
- R 5 and R ⁇ each represent a hydrogen atom, an aryl, alkyl, carboxyl or alkoxycarbonyl group, where the substituents R 5 and R ⁇ s may be the same or different.
- R 7 and R 8 each represent an aryl, alkyl, alkoxy, aryloxy group and substituted amino groups or a halogen radical, where the substituents R 7 and R 8 may be the same or different.
- furan is used.
- the following compounds can preferably be mentioned as substituted furans:
- Furfural furan-2-aldehyde
- alkyl-substituted furans furans with -CHO, -COOH, -COOR
- R represents an alkyl, benzyl, aryl, in particular a Ci to C 4 - alkyl group, CH (oR (oR 2), wherein Riund R 2 may be the same or different and Ri and R2 are each an alkyl, benzyl, aryl, particularly Ci to C 4 alkyl group, and -CN groups in the 2 -, 3-, 4- or 5-position.
- the furans are preferably oxidized in the presence of methanol or in the presence of ethanol or a mixture thereof, but preferably in the presence of methanol. These substrates can be reactant and solvent at the same time.
- alkali metal and / or alkaline earth metal halides can also be used as conductive salts, bromides, chlorides and iodides being conceivable as halides.
- Ammonium halides can also be used.
- Pressure and temperature can be adapted to the conditions which are common in catalytic hydrogenations.
- the reaction temperature is T ⁇ 50 ° C., preferably T ⁇ 25 ° C., the pressure p ⁇ 3 bar and the pH in the neutral range.
- intermediate products are added.
- the intermediate product is at least one product which is obtained by the inventive electrolytic oxidation of the at least one organic compound, in particular a furan or a substituted furan or a mixture of two or more thereof, and which is therefore in the electrolysis cycle.
- concentration of the additional intermediates is adjusted by customary electrochemical and electrocatalytic parameters, such as, for example, current density, type and amount of catalyst, or the intermediate is added to the circuit.
- Graphite anodes are preferably used in the electrolysis cell.
- the anode is in contact with at least one hydrogenation catalyst.
- the at least one hydrogenation catalyst is part of a gas diffusion electrode.
- the anode is a graphite electrode coated with noble metal, consisting of plates, nets or felts.
- the hydrogenation catalyst is continuously brought into contact with the anode in the form of a suspension in the electrolyte.
- the hydrogenation catalyst i.e. H. the catalytically active material, pumped around in the cell or washed onto an appropriately structured anode.
- a precoat electrode is described, for example, in DE 196 20 861.
- an organic compound is reduced at the anode, preferably hydrogenated, using the hydrogen which is produced as a product in the cathode process.
- This hydrogenation preferably takes place in such a way that the compound to be hydrogenated is brought into contact with one or more hydrogenation catalysts which in turn are brought into contact with the anode.
- Catalysts known in the art can be used.
- the metals of the L, II. And VIII. Subgroup of the periodic table are to be mentioned, in particular Co, Ni, Fe, Ru, Rh, Re, Pd, Pt, Os, Ir, Ag, Cu, Zn and Cd.
- the metals in finely divided form, among other things.
- Examples include Raney-Ni, Raney-Co, Raney-Ag or Raney-Fe, each of which also contains other elements such as Mo, Cr, Au, Mn, Hg, Sn or also S, Se, Te, Ge, Ga, P, Pb, As, Bi or Sb can contain.
- the hydrogenation-active materials described can comprise a mixture of two or more of the hydrogenation metals mentioned, which may optionally be contaminated with, for example, one or more of the elements mentioned above.
- the hydrogenation-active material is applied to an inert carrier.
- carrier systems for example activated carbon, graphite, carbon black, silicon carbide, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide or mixtures of two or more thereof, e.g. B. as a suspension or as finely divided granules.
- the hydrogenation-active material is applied to gas diffusion electrode base material.
- the present invention also relates to a method as described above, which is characterized in that the gas diffusion electrode base material is loaded with a hydrogenation-active material.
- All hydrogenation catalysts as described above can be used as the hydrogenation-active material with which the gas diffusion electrode system is loaded. It goes without saying it is also possible to use a mixture of two or more of these hydrogenation catalysts as the hydrogenation-active material.
- the gas diffusion electrode material is loaded with hydrogenation material and additionally hydrogenation material is used which is the same or different from that with which the gas diffusion electrode material is loaded.
- the present invention relates in a general form to the use of a gas diffusion electrode for the electrolytic conversion of an organic compound, preferably an unsaturated organic compound in an electrolytic cell.
- the electrodes consisted of graphite disks, each 5 mm thick, which were covered with gas diffusion electrode material on one side. This material in turn was occupied with 5.2 g Pd / m 2 .
- the gas diffusion electrode was switched as the cathode.
- the electrolysis batch consisted of 30 g furan, 57.4 g 2,5-dimethoxydihydrofuran, 2 g NaBr and 110.6 g methanol.
- the electrolysis was carried out at 0.5 A, a temperature of approx. 17 ° C.
- the cell voltage rose from 14.6 V to 20.7 V.
- the electrolysis was monitored by gas chromatography.
- Example 2 used the arrangement from Example 1, but here the anode was equipped with electrocatalytically active material. Instead of a gas diffusion cathode, a gas diffusion electrode loaded with 5.2 g Pd / m 2 was used as the anode.
- the electrolysis batch consisted of 30 g furan, 57.4 g 2,5-dimethoxydihydrofuran, 2 g NaBr and 110.6 g methanol.
- the electrolysis was carried out at 0.5 A and a temperature of 17 ° C.
- the cell voltage rose from 16.3 V to 19.5 V.
- the electrolysis was monitored by gas chromatography.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002385246A CA2385246A1 (en) | 1999-09-20 | 2000-09-18 | Method for electrolytically converting organic compounds |
JP2001525014A JP2003509594A (ja) | 1999-09-20 | 2000-09-18 | 有機化合物を電解により変換する方法 |
EP00964197A EP1220957A1 (de) | 1999-09-20 | 2000-09-18 | Verfahren zur elektrolytischen umwandlung von organischen verbindungen |
US10/070,450 US6733652B1 (en) | 1999-09-20 | 2000-09-18 | Method for electrolytically converting organic compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19944990A DE19944990A1 (de) | 1999-09-20 | 1999-09-20 | Verfahren zur elektrolytischen Umwandlung von organischen Verbindungen |
DE19944990.2 | 1999-09-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001021858A1 true WO2001021858A1 (de) | 2001-03-29 |
Family
ID=7922629
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/009135 WO2001021858A1 (de) | 1999-09-20 | 2000-09-18 | Verfahren zur elektrolytischen umwandlung von organischen verbindungen |
Country Status (6)
Country | Link |
---|---|
US (1) | US6733652B1 (de) |
EP (1) | EP1220957A1 (de) |
JP (1) | JP2003509594A (de) |
CA (1) | CA2385246A1 (de) |
DE (1) | DE19944990A1 (de) |
WO (1) | WO2001021858A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5292718B2 (ja) * | 2007-04-12 | 2013-09-18 | トヨタ自動車株式会社 | 燃料電池システム |
AT518544B1 (de) * | 2016-04-29 | 2017-11-15 | Pro Aqua Diamantelektroden Produktion Gmbh & Co Kg | Verfahren zur elektrochemischen Konvertierung von in Reststoffen enthaltenen oder als Reststoffe anfallenden organischen Verbindungen und Verwendung einer einkammrigen als Durchflusszelle konzipierten Elektrolysezelle zur elektrochemischen Konvertierung von in Reststoffen enthaltenen oder als Reststoffe anfallenden organischen Verbindungen in einen gasförmigen Brennstoff |
DE102016218230A1 (de) | 2016-09-22 | 2018-03-22 | Siemens Aktiengesellschaft | Selektive elektrochemische Hydrierung von Alkinen zu Alkenen |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4318783A (en) * | 1978-11-30 | 1982-03-09 | Bayer Aktiengesellschaft | Process for the preparation of optionally substituted benzaldehyde dialkyl acetals |
US4544450A (en) * | 1980-07-15 | 1985-10-01 | Anic S.P.A. | Electrochemical process for the synthesis of organic compounds |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19618854A1 (de) | 1996-05-10 | 1997-11-13 | Basf Ag | Verfahren zur Herstellung von Phthaliden |
DE19620861A1 (de) | 1996-05-23 | 1997-11-27 | Basf Ag | Verfahren zur elektrochemischen Reduktion organischer Verbindungen |
-
1999
- 1999-09-20 DE DE19944990A patent/DE19944990A1/de not_active Withdrawn
-
2000
- 2000-09-18 CA CA002385246A patent/CA2385246A1/en not_active Abandoned
- 2000-09-18 EP EP00964197A patent/EP1220957A1/de not_active Withdrawn
- 2000-09-18 JP JP2001525014A patent/JP2003509594A/ja not_active Withdrawn
- 2000-09-18 WO PCT/EP2000/009135 patent/WO2001021858A1/de not_active Application Discontinuation
- 2000-09-18 US US10/070,450 patent/US6733652B1/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4318783A (en) * | 1978-11-30 | 1982-03-09 | Bayer Aktiengesellschaft | Process for the preparation of optionally substituted benzaldehyde dialkyl acetals |
US4544450A (en) * | 1980-07-15 | 1985-10-01 | Anic S.P.A. | Electrochemical process for the synthesis of organic compounds |
Non-Patent Citations (4)
Title |
---|
ACTA CHIM. ACAD. SCI. HUNG. (1978), 97(3), 313-25, 1978 * |
CHEMICAL ABSTRACTS, vol. 89, no. 22, 27 November 1978, Columbus, Ohio, US; abstract no. 187868, HORANYI, GYORGY ET AL: "Electrochemical behavior of ethylene glycol and its oxidation products at the platinum electrode. I. Electroreduction of oxo-containing bifunctional compounds with two carbon atoms in acidic media" XP002156121 * |
CHEMICAL ABSTRACTS, vol. 92, no. 20, 19 May 1980, Columbus, Ohio, US; abstract no. 171531, MONAKHOVA, I. S.: "Synthesis and reactions of some methoxy derivatives of furan compounds" XP002156120 * |
VSES. NAUCHN. KONF. KHIM. TEKHNOL. FURANOVYKH SOEDIN., [TEZISY DOKL.], 3RD (1978), 136. EDITOR(S): STRADYN, YA. P. PUBLISHER: ZINATNE, RIGA, USSR., 1978 * |
Also Published As
Publication number | Publication date |
---|---|
EP1220957A1 (de) | 2002-07-10 |
US6733652B1 (en) | 2004-05-11 |
JP2003509594A (ja) | 2003-03-11 |
DE19944990A1 (de) | 2001-03-22 |
CA2385246A1 (en) | 2001-03-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE19962102A1 (de) | Verfahren zur elektrochemischen Oxidation von organischen Verbindungen | |
EP0808920B1 (de) | Verfahren zur elektrochemischen Reduktion organischer Verbindungen | |
DE19962155A1 (de) | Verfahren zur elektrochemischen Reduktion von Küpenfarbstoffen | |
DE102004057277A1 (de) | Verfahren zur Herstellung von Menthol | |
EP1230433B1 (de) | Verfahren zur elektrolytischen umwandlung von furan oder furanderivaten | |
EP0457320B1 (de) | Verfahren zur teilweisen elektrolytischen Enthalogenierung von Di-und Trichloressigsäure sowie Elektrolyselösung | |
DE3127975C2 (de) | Elektrochemisches Verfahren zur Herstellung von acetoxylierten aromatischen Verbindungen | |
EP1348043B1 (de) | Verfahren zur herstellung von alkoxylierten carbonylverbindungen durch ein anodisches oxidationsverfahren unter nutzung der kathodischen koppelreaktion zur organischen synthese | |
WO2001021858A1 (de) | Verfahren zur elektrolytischen umwandlung von organischen verbindungen | |
EP2411564B1 (de) | Elektrochemisches verfahern zur herstellung von 3-tert.-butylbenzaldehyd-dimethylacetal | |
WO2002042249A1 (de) | Herstellung von butantetracarbonsäurederivaten mittels gekoppelter elektrosynthese | |
DE3132726A1 (de) | Verfarhen zur herstellung von alkylsubstituierten benzaldehyden | |
EP1217098A1 (de) | Bipolare quasigeteilte Elektrolysezellen | |
WO2009071478A1 (de) | Verfahren zur reduktiven hydrodimerisierung von ungesättigten organischen verbindungen mittels einer diamantelektrode | |
DE3322399A1 (de) | Verfahren zur herstellung von benz aldehyddialkylacetalen | |
DE3522304C2 (de) | Verfahren zur Herstellung von Carbonsäuren durch elektrochemische Reduktion | |
DE2710420C2 (de) | Verfahren zur elektrolytischen Herstellung von 2,5-Dialkoxy-2,5-dihydrofuranen | |
DE102010029272A1 (de) | Verfahren zur elektrochemischen Herstellung von Isophoron | |
DE2255690C3 (de) | Anode für elektrochemische Prozesse | |
DE2208155A1 (de) | Verfahren zur herstellung von 4-endotricyclo(5,2,1,0 hoch 2,6-endo)-decylamin | |
EP1913178A1 (de) | Verfahren zur herstellung von 1,1,4,4-tetraalkoxy-but-2-enderivaten | |
EP0384315B1 (de) | Verfahren zur Herstellung von Lactonen | |
EP0152801A2 (de) | Verfahren zur Herstellung von Benzaldehyddialkylacetalen | |
EP0278219A2 (de) | Verfahren zur Herstellung von (Poly)oxatetramethylendicarbonsäuren | |
DE10045664A1 (de) | Verfahren zur elektrochemischen Regenerierung von Mediatoren an Diamantelektroden |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA JP US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 2001 525014 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2385246 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10070450 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2000964197 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2000964197 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 2000964197 Country of ref document: EP |