EP1230433B1 - Verfahren zur elektrolytischen umwandlung von furan oder furanderivaten - Google Patents
Verfahren zur elektrolytischen umwandlung von furan oder furanderivaten Download PDFInfo
- Publication number
- EP1230433B1 EP1230433B1 EP00966039A EP00966039A EP1230433B1 EP 1230433 B1 EP1230433 B1 EP 1230433B1 EP 00966039 A EP00966039 A EP 00966039A EP 00966039 A EP00966039 A EP 00966039A EP 1230433 B1 EP1230433 B1 EP 1230433B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- furan
- electrode
- electrodes
- hydrogenation
- electrolysis
- 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.)
- Expired - Lifetime
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 Furan or one or more furan derivatives.
- One goal of preparative organic electrochemistry is that of one Processes occurring on both electrodes parallel to electrochemical processes use.
- Of particular interest are those procedures in which the two Electrode processes that take place in an undivided cell for the implementation of chemical compounds can be used.
- Another example is the coupled synthesis of phthalide and t-butylbenzaldehyde (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 are, for example, the production of butyric acid (Y. Chen, T. Chou, J. Chin. Inst. Chem. Eng. 27 (1996) pages 337-345), the anodic dissolution of iron, that 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) page 239).
- An object of the present invention is therefore an electrochemical method To provide, which preferably takes place in an undivided electrolytic cell and in which Furan or a substituted furan in an electrode process while maintaining the heterocyclic ring structure is oxidized and this oxidation product with hydrogen is hydrogenated, the hydrogen being the product in the other electrode process arises or as hydrogen equivalent in the sense of an electrocatalysis on the Furan derivative is transferred.
- the process preferably takes place in an undivided electrolysis cell.
- furan in addition to furan, the following compounds, for example, are preferred as substituted furans: Furfural (furan-2-aldehyde), alkyl-substituted furans, furans with -CHO, -COOH, -COOR, in which R represents an alkyl, benzyl or aryl group, in particular a C 1 - to C 4 -alkyl group, -CH (OR 1 ) (OR 2 ), where R 1 and R 2 can be the same or different and R 1 and R 2 each represent an alkyl, benzyl, aryl group, in particular a C 1 to C 4 alkyl group, and -CN groups in 2-, 3-, 4- or 5-position.
- Furfural furan-2-aldehyde
- alkyl-substituted furans furans with -CHO, -COOH, -COOR
- R represents an alkyl, benzyl or aryl group, in particular a C 1 - to C 4
- electrolyte salts can be used, as described in H. Lund, MM Baizer, (ed.) "Organic Electrochemistry", 3 rd Edition, Marcel Dekker, New York 1991.
- the oxidation is preferably carried out in the presence of methanol or in Presence of ethanol or a mixture thereof, but preferably in the presence of Methanol.
- substrates can be reactant and solvent at the same time.
- the following can be used as conductive salts in the process of the invention, for example also alkali and / or alkaline earth metal halides, with bromides, chlorides as halides and iodides are conceivable. Ammonium halides are also suitable used.
- Pressure and temperature can depend on the conditions used in catalytic hydrogenations are customary to be adjusted.
- the starting materials are introduced into the undivided electrolysis cell intermediate products are supplied.
- the intermediate product is at least one product which is obtained in step (i) of the process described above by electrolytic oxidation of furan or a substituted furan or a mixture of two or more thereof as a furan derivative (B) and is therefore in the electrolysis cycle.
- concentration of the additional intermediates is adjusted by conventional 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 undivided cell.
- At least one electrode is in Contact with at least one hydrogenation catalyst.
- the at least one hydrogenation catalyst is part of an embodiment Gas diffusion electrode.
- at least one electrode is a graphite electrode coated with noble metal from sheets, nets or felt.
- the hydrogenation catalyst in the form of a suspension in the electrolyte constantly brought into contact with at least one electrode.
- Precoat electrode is described for example in DE 196 20 861.
- a gas diffusion electrode is used for at least one of the electrodes, then basically processed the material from which the gas diffusion electrode is made be that the gas diffusion electrode can be used as an electrode without support material can.
- at least one of the used electrodes are a composite body, which is at least one conventional Includes electrode material and at least one material for a gas diffusion electrode.
- the composite body, the conventional Electrode material and the material of the gas diffusion electrode comprises, as one electrode in the process according to the invention together with one or more suitable Counter electrodes are used.
- further electrode materials uses that include carbon.
- a C-C double bond is used in the process according to the invention using the hydrogen obtained in step (i) electrocatalytically or with the corresponding hydrogen equivalents in the sense of a Hydrolysis of electrolysis.
- This hydrogenation preferably takes place so that the hydrogenation Connection is brought into contact with one or more hydrogenation catalysts.
- the method according to the invention has no restrictions. All from the Catalysts known in the art can be used. Among other things are included to name the metals of subgroups I, II and VIII of the periodic table, 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 use.
- 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 S, Se, Te, Ge, Ga, P, Pb, As, Bi or Sb can contain.
- the described hydrogenation-active materials can of course also be a mixture of comprise two or more of the hydrogenation metals mentioned, optionally with For example, one or more of the above elements can be mixed.
- the hydrogenation material on an inert Carrier is applied.
- Activated carbon for example, Graphite, carbon black, silicon carbide, aluminum oxide, silicon dioxide, titanium dioxide, Zirconium dioxide, magnesium oxide, zinc oxide or mixtures of two or more of which, e.g. B. as a suspension or as finely divided granules.
- the hydrogenation Material applied to gas diffusion electrode base material is not limited to the hydrogenation Material.
- the present invention also relates to a method as described above, which is characterized in that the gas diffusion electrode base material with a hydrogenated active material is loaded.
- the Gas diffusion electrode material is loaded with hydrogenation material and in addition hydrogenated material is used, which is the same or different to that with which is loaded with the gas diffusion electrode material.
- the method according to the invention is particularly noteworthy characterized in that it essentially leaves the choice whether the electrocatalytic effective electrode, d. H. the electrode that is in contact with a hydrogenation catalyst, is used as a cathode or as an anode or as a cathode and anode.
- the present invention also relates to a method as described above, which is characterized in that the electrocatalytically active electrode, such as for example a gas diffusion electrode, used as a cathode and / or as an anode becomes.
- the electrocatalytically active electrode such as for example a gas diffusion electrode
- the present invention relates to a method as described above, wherein the prepared furan derivative (B) converted to at least one ring-open butane derivative becomes.
- the at least one ring-open butane derivative is preferably 1,1,4,4-tetramethoxybutane or a substituted 1,1,4,4-tetramethoxybutane.
- An undivided cell with 6 ring-shaped electrodes with a surface per side of 15.7 cm 2 was used.
- the electrodes were separated from each other by 5 spacer networks 0.7 mm thick.
- the top and bottom electrodes were in contact with a power connector.
- the top one Electrode was connected anodically, the bottom one was cathodic, the middle electrodes bipolar.
- the electrodes consisted of graphite disks, each 5 mm thick, which were covered on one side with gas diffusion electrode material. This material in turn was coated with 10 g platinum / m 2 .
- the gas diffusion electrode was switched as the cathode.
- the electrolysis batch consisted of 30 g furan, 57.63 g 2,5-dimethoxydihydrofuran, 2 g NaBr and 112 g methanol.
- the electrolysis was carried out at 0.47 A and a temperature of 15 ° C. During the Implementation increased the cell voltage from 13.0 V to 17.4 V. The electrolysis was followed by gas chromatography.
- Example 2 The cell arrangement corresponded to that of Example 1. Instead of a Pt-loaded gas diffusion cathode, a gas diffusion electrode loaded with 5.2 g / m 2 Pd was used.
- the electrolysis batch consisted of 60 g furan, 126.2 g 2,5-dimethoxydihydrofuran, 2 g NaBr and 234.4 g of methanol.
- the electrolysis was carried out at 0.47 A and a temperature of approx. 18 ° C.
- the cell tension rose from 19.1 V to 26.4 V.
- the electrolysis was monitored by gas chromatography.
- the cell arrangement corresponded to that of Example 1. 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 of methanol.
- the electrolysis was carried out at 0.48 A and a temperature of 17 ° C.
- the cell tension rose from 16.3 V to 19.5 V.
- the electrolysis was followed by gas chromatography.
- a cell with 5 ring-shaped electrodes with a surface area of 44 cm 2 was used.
- the electrodes were separated from each other by 2 spacer networks of 1 mm thickness.
- the electrodes consisted of graphite disks, each 5 mm thick, which were coated on the sides facing the electrolyte both anodically and cathodically with gas diffusion electrode material. This material was loaded with 0.5 mg Pd / cm 2 .
- the electrolysis batch consisted of 120 g furan, 229.9 g 2,5-dimethoxydihydrofuran, 8 g NaBr and 542.5 g MeOH.
- the electrolysis was carried out at 1.32 A up to a current of 2 F / mol furan Electrolysis temperature was 17 ° C. The electrolysis was followed 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)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Hybrid Cells (AREA)
Description
Hinsichtlich der Verfahren, in denen ein Furanderivat in einer ungeteilten Elektrolysezelle umgesetzt wird und die beiden Elektrodenprozesse genutzt werden, ist die Oxidation von Furancarbonsäure mit anschließender Ringöffnung zu 1-Carboxymethyl-4,4-dimethoxypropen, das in einer weiteren Stufe zum gesättigten Propanderivat hydriert wird, beschrieben (T. Iwasaki et al., J. Org. Chem. 47 (1982) Seiten 3799 ff.). Es handelt sich hierbei allerdings nicht um eine katalytische Hydrierung, sondern um eine direkte Elektroreduktion. In diesem Fall setzt sich jedoch nicht das Furan um, sondern der α,β-ungesättigte Ester, d. h. eine Substanzklasse, deren elektrochemische Reduktion bekannt ist. Außerdem erfolgt die Ringöffnung und die anschließende Hydrierung nicht direkt aus dem anodisch erzeugten Produkt sondern aus einer um ein C-Atom ärmeren, fragmentierten Stufe, die eine weitere Oxidation erlitten hat.
Furfural(Furan-2-aldehyd), alkylsubstituierte Furane, Furane mit -CHO, -COOH, -COOR, worin R für eine Alkyl-, Benzyl- oder Arylgruppe, insbesondere für eine C1- bis C4-Alkylgruppe steht, -CH(OR1)(OR2), wobei R1 und R2 gleich oder unterschiedlich sein können und R1 und R2 jeweils für eine Alkyl-, Benzyl-, Arylgruppe, insbesondere für eine C1- bis C4-Alkylgruppe stehen und -CN-Gruppen in 2-, 3-, 4- oder 5-Stellung.
werden, Zwischenprodukte zugeführt. Als Zwischenprodukt wird dasjenige mindestens eine Produkt bezeichnet, das in Schritt (i) des oben beschriebenen Verfahrens durch elektrolytische Oxidation von Furan oder eines substituierten Furans oder eines Gemisches aus zwei oder mehreren davon als Furanderivat (B) erhalten wird und sich deshalb im Elektrolysekreislauf befindet. Die Konzentration der zusätzlichen Zwischenprodukte wird durch übliche elektrochemische und elektrokatalytische Parameter, wie beispielsweise Stromdichte, Katalysatorart und -menge, eingestellt, oder das Zwischenprodukt wird dem Kreislauf zugegeben.
Claims (11)
- Verfahren zur elektrolytischen Umwandlung mindestens einer auf Furan basierenden Ausgangsverbindung (A) in einem Elektrolysekreis, das die beiden Schritte (i) und (ii) umfasst:(i) Elektrolytische Oxidation von Furan oder eines substituierten Furans oder eines Gemisches aus zwei oder mehreren davon unter Erhalt(a) mindestens einer im heterocyclischen Fünfring eine C-C-Doppelbindung aufweisenden alkoxylierten Furanverbindung (B), und(b) Wasserstoff;(ii) Hydrierung dieser C-C-Doppelbindung unter Verwendung des in Schritt (i) parallel an der Kathode erhaltenen Wasserstoffs oder von dem Elektrolysekreis von außen zugeführtem Wasserstoff oder durch elektrokatalytische Hydrierung,
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Verfahren in einer ungeteilten Elektrolysezelle abläuft.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass mindestens eine Elektrode mit mindestens einem Hydrierkatalysator, insbesondere mit einem Edelmetall, in Kontakt ist.
- Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass der Hydrierkatalysator, insbesondere das Edelmetall, auf einem Graphitfilz aufgebracht ist.
- Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass der Hydrierkatalysator auf die mindestens eine Elektrode angeschwemmt ist.
- Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass der Hydrierkatalysator in Form einer Suspension in Kontakt zu der mindestens einen Elektrode gebracht wird.
- Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass mindestens eine der verwendeten Elektroden eine Gasdiffusionselektrode ist.
- Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass mindestens eine der verwendeten Elektroden einen Verbundkörper darstellt, der mindestens ein herkömmliches Elektrodenmaterial und mindestens ein Material für eine Gasdiffusionselektrode umfaßt.
- Verfahren nach einem der Ansprüche 3 bis 8, dadurch gekennzeichnet, dass die mindestens eine Elektrode, die mit einem Hydrierkatalysator in Kontakt ist, als Kathode oder als Anode oder als Kathode und Anode verwendet wird.
- Verfahren nach einem der vorhergehenden Ansprüche 1 bis 9, wobei die im Schritt (i) hergestellte alkoxylierte Furanverbindung (B) im Schritt (ii) zu mindestens einem ringoffenen Butanderivat umgesetzt wird.
- Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass das mindestens eine ringoffene Butanderivat 1,1,4,4-Tetramethoxybutan oder ein substituiertes 1,1,4,4-Tetramethoxybutan ist.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19944989A DE19944989A1 (de) | 1999-09-20 | 1999-09-20 | Verfahren zur elektrolytischen Umwandlung von Furanderivaten |
DE19944989 | 1999-09-20 | ||
PCT/EP2000/009072 WO2001021857A1 (de) | 1999-09-20 | 2000-09-15 | Verfahren zur elektrolytischen umwandlung von furan oder furanderivaten |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1230433A1 EP1230433A1 (de) | 2002-08-14 |
EP1230433B1 true EP1230433B1 (de) | 2003-07-09 |
Family
ID=7922628
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00966039A Expired - Lifetime EP1230433B1 (de) | 1999-09-20 | 2000-09-15 | Verfahren zur elektrolytischen umwandlung von furan oder furanderivaten |
Country Status (8)
Country | Link |
---|---|
US (1) | US6764589B1 (de) |
EP (1) | EP1230433B1 (de) |
JP (1) | JP2003509593A (de) |
AT (1) | ATE244778T1 (de) |
CA (1) | CA2385240A1 (de) |
DE (2) | DE19944989A1 (de) |
ES (1) | ES2203514T3 (de) |
WO (1) | WO2001021857A1 (de) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10324192A1 (de) * | 2003-05-28 | 2004-12-23 | Basf Ag | Verfahren zur Herstellung von alkoxylierten 2,5-Dihydrofuran-oder tetra-1,1,4,4-alkoxylierten But-2-enderivaten |
US8216956B2 (en) | 2003-10-10 | 2012-07-10 | Ohio University | Layered electrocatalyst for oxidation of ammonia and ethanol |
US8216437B2 (en) * | 2003-10-10 | 2012-07-10 | Ohio University | Electrochemical cell for oxidation of ammonia and ethanol |
US8221610B2 (en) * | 2003-10-10 | 2012-07-17 | Ohio University | Electrochemical method for providing hydrogen using ammonia and ethanol |
JP5241488B2 (ja) * | 2005-05-06 | 2013-07-17 | オハイオ ユニバーシティ | 固体燃料スラリーから水素を生成する方法 |
DE102005036687A1 (de) * | 2005-08-04 | 2007-02-08 | Basf Ag | Verfahren zur Herstellung von 1,1,4,4,-Tetraalkoxy-but-2-enderivaten |
JP2009515036A (ja) * | 2005-10-14 | 2009-04-09 | オハイオ ユニバーシティ | アルカリ媒体中におけるアンモニア及びエタノールを酸化するためのカーボンファイバー電極触媒、ならびに水素生成、燃料電池および精製プロセスへのその適用 |
EP2861785A2 (de) * | 2012-06-15 | 2015-04-22 | Basf Se | Anodische oxidation organischer substrate in gegenwart von nukleophilen |
WO2020068872A1 (en) * | 2018-09-24 | 2020-04-02 | Massachusetts Institute Of Technology | Electrochemical oxidation of organic molecules |
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 (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1132194B (it) * | 1980-07-15 | 1986-06-25 | Anic Spa | Processo elettrochimico per la sintesi di composti organici |
US4673933A (en) * | 1983-11-14 | 1987-06-16 | American Microsystems, Inc. | Switch matrix encoding interface using common input/output parts |
US5668544A (en) * | 1996-02-26 | 1997-09-16 | Holtek Microelectronics, Inc. | Compound type of keyboard detector |
DE19618854A1 (de) | 1996-05-10 | 1997-11-13 | Basf Ag | Verfahren zur Herstellung von Phthaliden |
DE19625730A1 (de) * | 1996-06-27 | 1998-01-02 | Teves Gmbh Alfred | Verwendung einer Berührungssensormatrix als Sensor in Kraftfahrzeugen |
-
1999
- 1999-09-20 DE DE19944989A patent/DE19944989A1/de not_active Withdrawn
-
2000
- 2000-09-15 JP JP2001525013A patent/JP2003509593A/ja not_active Withdrawn
- 2000-09-15 WO PCT/EP2000/009072 patent/WO2001021857A1/de active IP Right Grant
- 2000-09-15 CA CA002385240A patent/CA2385240A1/en not_active Abandoned
- 2000-09-15 AT AT00966039T patent/ATE244778T1/de not_active IP Right Cessation
- 2000-09-15 US US10/088,075 patent/US6764589B1/en not_active Expired - Fee Related
- 2000-09-15 DE DE50002862T patent/DE50002862D1/de not_active Expired - Fee Related
- 2000-09-15 EP EP00966039A patent/EP1230433B1/de not_active Expired - Lifetime
- 2000-09-15 ES ES00966039T patent/ES2203514T3/es not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CA2385240A1 (en) | 2001-03-29 |
DE19944989A1 (de) | 2001-03-22 |
ES2203514T3 (es) | 2004-04-16 |
ATE244778T1 (de) | 2003-07-15 |
EP1230433A1 (de) | 2002-08-14 |
WO2001021857A1 (de) | 2001-03-29 |
US6764589B1 (en) | 2004-07-20 |
DE50002862D1 (de) | 2003-08-14 |
JP2003509593A (ja) | 2003-03-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1111094A2 (de) | Verfahren zur elektrochemischen Oxidation von organischen Verbindungen | |
EP1230433B1 (de) | Verfahren zur elektrolytischen umwandlung von furan oder furanderivaten | |
EP0457320B1 (de) | Verfahren zur teilweisen elektrolytischen Enthalogenierung von Di-und Trichloressigsäure sowie Elektrolyselösung | |
DE3872566T2 (de) | Verfahren zur herstellung von 2-arylpropionsaeuren. | |
EP1348043B1 (de) | Verfahren zur herstellung von alkoxylierten carbonylverbindungen durch ein anodisches oxidationsverfahren unter nutzung der kathodischen koppelreaktion zur organischen synthese | |
DE3127975C2 (de) | Elektrochemisches Verfahren zur Herstellung von acetoxylierten aromatischen Verbindungen | |
EP2411564B1 (de) | Elektrochemisches verfahern zur herstellung von 3-tert.-butylbenzaldehyd-dimethylacetal | |
EP0902846B1 (de) | Verfahren zur herstellung von phthaliden | |
DE3132726A1 (de) | Verfarhen zur herstellung von alkylsubstituierten benzaldehyden | |
WO2002042249A1 (de) | Herstellung von butantetracarbonsäurederivaten mittels gekoppelter elektrosynthese | |
EP0638665B1 (de) | Verfahren zur Herstellung von Bezaldehyddialkylacetalen | |
DE2855508A1 (de) | Verfahren zur herstellung von benzaldehyden | |
WO2001021858A1 (de) | Verfahren zur elektrolytischen umwandlung von organischen verbindungen | |
DE60107281T2 (de) | Elektrochemisches verfahren zur selektiven umsetzung von alkylaromatischen verbindungen zu aldehyden | |
EP2534281A2 (de) | Verfahren zur herstellung von 4-isopropylcyclohexylmethanol | |
DE2208155A1 (de) | Verfahren zur herstellung von 4-endotricyclo(5,2,1,0 hoch 2,6-endo)-decylamin | |
EP0382106B1 (de) | Verfahren zur Herstellung von Thiophenderivaten | |
DE2331712A1 (de) | Verfahren zur herstellung von 2methoxy-3,6-dichlorbenzoesaeure | |
EP0030588B1 (de) | Verfahren zur Herstellung von p-tert. Butylbenzaldehyd | |
DE2547464A1 (de) | Verfahren zur herstellung von hydrochinondimethylaethern | |
EP0278219A2 (de) | Verfahren zur Herstellung von (Poly)oxatetramethylendicarbonsäuren | |
DE10045664A1 (de) | Verfahren zur elektrochemischen Regenerierung von Mediatoren an Diamantelektroden | |
DE2618276B2 (de) | Verfahren zur elektrochemischen dihydrierung von naphthylaethern | |
DD271700A1 (de) | Verfahren zur herstellung von 1,1-dichlor-4-methyl-penta-1,3-dien |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20020419 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030709 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030709 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 50002862 Country of ref document: DE Date of ref document: 20030814 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: GERMAN |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030915 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030915 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030915 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20031009 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20031009 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20031209 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2203514 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20040414 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20080915 Year of fee payment: 9 Ref country code: IT Payment date: 20080926 Year of fee payment: 9 Ref country code: NL Payment date: 20080903 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20080917 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20081002 Year of fee payment: 9 Ref country code: DE Payment date: 20080926 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20080922 Year of fee payment: 9 Ref country code: ES Payment date: 20081021 Year of fee payment: 9 Ref country code: SE Payment date: 20080908 Year of fee payment: 9 |
|
BERE | Be: lapsed |
Owner name: *BASF A.G. Effective date: 20090930 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20100401 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
EUG | Se: european patent has lapsed | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20090915 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20100531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100401 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090930 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100401 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090930 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090915 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090915 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090916 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20110714 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110704 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090916 |