WO2004042117A1 - Process for electrochemical oxidation of ferrocyanide to ferricyanide - Google Patents
Process for electrochemical oxidation of ferrocyanide to ferricyanide Download PDFInfo
- Publication number
- WO2004042117A1 WO2004042117A1 PCT/EP2003/050641 EP0350641W WO2004042117A1 WO 2004042117 A1 WO2004042117 A1 WO 2004042117A1 EP 0350641 W EP0350641 W EP 0350641W WO 2004042117 A1 WO2004042117 A1 WO 2004042117A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aqueous phase
- ferrocyanide
- ferricyanide
- electrochemical cell
- coupling reaction
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- ferricyanide IV
- WO-96/ 12692 WO-96/31458
- Preferred organic solvents are aromatic hydrocarbons such as toluene.
- the aqueous base is preferably an alkali metal carbonate or hydrogen carbonate.
- the oxidant is preferably potassium ferricyanide or K 3 Fe(CN) 6 (IV).
- Galantamine (I) is commercially available as Reminyl ® (Galantamine hydrobromide) which is approved for the treatment of mild to moderate Alzheimer's Disease and is under development for other indications such as Vascular Dementia, Alzheimer's Disease with cerebrovascular disease, mild cognitive impairment, schizophrenia, Parkinson's Disease and other diseases wherein cognition is impaired.
- ferrocyanide or 4 Fe(CN) 5 (V) aqueous phase waste stream which has to be incinerated, has a major impact on the cost of the end product galantamine (I).
- I end product galantamine
- ferricyanide (IV) is a relatively expensive reagent with only few suppliers, which makes recovery economically worthwhile.
- the problem to be solved therefore concerns finding a practical process to re-oxidize an aqueous phase comprising ferrocyanide (V) which is recovered from an oxidative phenolic coupling reaction, to an aqueous phase comprising ferricyanide (IV), (a) while avoiding chemical processes which would introduce by-products in the aqueous phase and (b) allowing repeated recycling of the aqueous phase comprising ferricyanide (IV) in an other oxidative phenolic coupling reaction, more in particular in the reaction of intermediate (II) to intermediate (III) in the total synthesis of galantamine (I).
- the present inventors provide herein a practical process for oxidizing an aqueous phase comprising ferrocyanide (V), which is recovered from an oxidative phenolic coupling reaction, to an aqueous phase comprising ferricyanide (IV), which does not use a chemical process which would introduce by-products in the aqueous phase, which allows repeated recycling of the aqueous phase comprising ferricyanide (IV) in an other oxidative phenolic coupling reaction, and which is readily adaptable to an industrial scale.
- V ferrocyanide
- IV ferricyanide
- the present invention provides a process for electrochemical oxidation of an aqueous phase comprising ferrocyanide (V), which is recovered from an oxidative phenolic coupling reaction to an aqueous phase comprising ferricyanide (IV), in a divided electrochemical cell, comprising preparing an anolyte comprising pretreating the aqueous phase comprising ferrocyanide (V) which is recovered from an oxidative phenolic coupling reaction by decantation or extraction or filtration; placing the anolyte in contact with an anodic electrode of the divided electrochemical cell; placing a catholyte in contact with a cathodic electrode of the divided electrochemical cell; and applying electrical power to the divided electrochemical cell, wherein the electrical power has an amperage or voltage and wherein the applying is for a time period sufficient to oxidize the ferrocyanide (V) to ferricyanide (IV).
- oxidation of ferro- (V) to ferricyanide (IV) is a reversible process
- high conversion rates can only be obtained by use of a divided cell, that is a cell wherein the anolyte and catholyte are separated by a membrane.
- the membrane dividing the electrochemical cell is a cation selective membrane which preferably has high chemical and mechanical resistance. Materials permeable to cations, but largely impermeable to reactants and products, are used for membranes of divided eiectrochemically cells.
- the membrane performs as a separator and solid electrolyte in an electrochemical cell which requires the membrane to transport selectively cations across the cell junction.
- a perfluorinated polymer membrane such as perfluoropolyethylenesulfonic acid (Nafion ® ,DuPont).
- Other membranes materials include polytetrafluoroethylene (PFTE, e.g. Teflon ® ), polypropylene (e.g. Celgard ® ) membranes.
- PFTE polytetrafluoroethylene
- PFTE polytetrafluoroethylene
- polypropylene e.g. Celgard ®
- ferrocyanide (V) nor ferricyanide (IV) can migrate through the membrane to the cathode, but cations such as K + are let through the membrane, generating a K + transport from anolyte to catholyte.
- Untreated aqueous phases contain from about 2% to about 4% organic material and suspended free iron in the form of iron hydroxides. Whilst the impact of the organic material on the electro-oxidation process is currently not understood, the suspended free iron appears to block the electro-oxidation process by precipitating on the membrane of the divided cell and on the electrodes.
- a conceptually easy - practically difficult, albeit not infeasible - method concerns pretreating the aqueous phase which comprises ferrocyanide (V) which is recovered from an oxidative phenolic coupling reaction, by storing it at 60°C or more during a period of time sufficient to let precipitate suspended particles, and decanting the supernatant aqueous phase so as to separate it from the precipitated particles.
- a temperature of 60°C or more is indicated to prevent the ferrocyanide (V) from precipitating from the aqueous phase.
- aqueous phase comprising ferrocyanide (V) which is recovered from an oxidative phenolic coupling reaction, by extracting it with an organic solvent, preferably an aromatic hydrocarbon such as toluene which is the solvent used in the oxidative phenolic coupling reaction we are mainly interested in.
- an organic solvent preferably an aromatic hydrocarbon such as toluene which is the solvent used in the oxidative phenolic coupling reaction we are mainly interested in.
- Such a pretreated aqueous phase does not present the problem experienced with an untreated aqueous phase. This is very remarkable for two reasons. First, we observed that an aqueous phase pretreated by extraction with an organic solvent such as toluene still contains suspended particles, but these do not seem to hinder the electro-oxidation reaction any longer.
- Another practical solution to the problem outlined in the previous paragraphs comprises pretreating the aqueous phase comprising ferrocyanide (V) which is recovered from an oxidative phenolic coupling reaction, by filtering it.
- V ferrocyanide
- this is a filtration using for example a Buchner filter filled with cold filter aid, e.g. dicalite.
- the filtration step comprises adding the filter aid to the water layer and filtering over a preheated mono plate or multiplate filter.
- catholyte should allow current transport and should be conductive. It should not contribute significantly to side reactions.
- catholyte is prepared by dissolving an alkali metal hydroxide (e.g. KOH) or an alkali metal salt (e.g. K 2 CO 3 , KHCO 3 , KCI, KCN) in water to give a 0.0001 M to 1 M solution.
- the catholyte may further comprise miscible organic solvents such as alkanols, e.g. methanol or ethanol.
- cathodic electrodes were tested as well and as a result of these experiments it was concluded that some would not work, for example a lead electrode, though various others would, for example cathodic electrodes selected from the group of copper, nickel, stainless steel and graphite electrodes. Best results were obtained using a copper cathodic electrode or a graphite cathodic electrode
- the previously described process may occasionally tend to go wrong.
- one or more monitoring steps may be added to the in process control system. Firstly, during the electro-oxidation process, the conversion of ferro (V) to ferricyanide (IV) may be blocked by precipitation of extraneous material on either the membrane or the electrodes. Such mishap may be monitored by recording of the current through the cell and aborting the process when the current drops.
- ferrocyanide (V) concentration in the anolyte fails to decay or that that of ferricyanide (IV) fails to raise during the process.
- concentration of the ferrocyanide (V) and ferricyanide (IV) in the anolyte is therefore advantageously recorded during the process.
- the process of the present invention will advantageously comprise monitoring steps in which all of the described phenomena are recorded and which trigger appropriate events such as process shutdown.
- FTIR Fourier Transform Infrared
- On-line measurements can be accomplished by coupling the infrared spectrometer to an ATR-probe (Attenuated total reflection) which avoids sampling of the anolyte and also improves speed of analysis.
- ATR-probe Attenuated total reflection
- provision may be made of a cerometric titration which involves a redox titration Ce 4+ + Fe(CN) ⁇ Mn ° 4 > Ce 3+ + Fe(CN) 3 6 50°C ; wherein ferroine indicator changes from orange-red to green.
- the present invention concerns aqueous phases comprising ferricyanide (IV) obtainable by processes as described hereinbefore.
- the invention concerns the re-use of aqueous phases comprising ferricyanide (IV) obtainable by processes as described hereinbefore, for effecting oxidative phenolic coupling reactions on substrates susceptible to such reaction.
- Said re-use is particularly interesting for cyclizing a substrate of formula (II) to an intermediate of formula (III), which may be further converted into galantamine (I).
- the scheme of the electrochemical cell and the auxiliary equipments are given in Fig. 1.
- the MP-cell ElectroCell
- the anode and cathode compartments were separated by a Nafion ® membrane and the gap between the electrodes and the membrane was 5 mm.
- P a , P c diaphragm pumps Teflon ® pump-head, Cole- Parmer, USA
- the fluids leaving the compartments were led to glass storage vessels Sa, Sc equipped with openings for sampling and introduction of sensors (e.g. pH electrode). From the storage vessels the liquids entered the heat exchange coils placed in the same heating-cooling thermostat (Cole-Parmer, USA). From the coils they were introduced into the pumps. Only Teflon ® tubing was applied.
- the power supply was a 40 A capacity potentiostat P.S., operating in controlled cell voltage mode.
- a computer controlled data logger D.L. (Grant Co., UK) served for data collection. It read cell voltage, current, temperature and the pH in preset intervals till the reading was stopped.
- the thermostat was heated to the required temperature, then the cathode storage vessel was filled with 500 ml of 0.5M NaCI solution. Thermometer, temperature probe and pH electrode were placed and circulation of catholyte was started to reach the required temperature. 250ml process water heated to about 70°C was placed into the Sa anode storage vessel and its circulation was started.
- the potentiostat and the data logger program were set, and as the temperature of the liquids were equilibrated the reading by the data logger was initiated and the current was switched on with the required cell voltage.
- Toluene extracted process water was more "pleasant", as there appeared to be no transport of Fe ions through the membrane into the catholyte and layer formation in the anodic compartment was not disturbing.
- brown powder like precipitate accumulated during standing, which proved to be Fe-oxide. Determination by filtering out the sediment from 390 ml water, washing it with alkaline solution and drying gave 0.251 g/dm 3 i.e. 0.00157 mole/I iron oxide.
- the cell was equipped with Cu cathode and graphite anode since according to our preliminary work they were the most suitable couple. Beside these electrodes, stainless steel cathode and graphite felt covered graphite anode and Ni anode were tested, as well. The electrodes could be replaced without difficulty.
- the initial work with the MP-cell was done with "old" process water. This water was stored for about a year. The reproducibility of the electro-oxidation process was quite good. In the initial period, the currents increased with the cell voltage since there was
- the aim of trying a graphite felt anode was to increase the current density.
- the graphite felt was glued to the surface of a solid graphite providing very high surface area.
- the electrolysis carried out at 2.20 V was running with larger current as compared to the solid graphite anode and it remained constant for nearly the whole time of electrolysis with a steep drop towards the end.
- the flow of the anolyte and catholyte fluids was controlled to have the same rate. Different flow rate (slower or faster catholyte flow) did not effect the current.
- the volumes of anolyte were 250 ml but at 500 ml/min. flow rate we had to use 500 ml volume to prevent air intake due to the fast suction. An increase in flow rate did not affect the current in the initial period, but did towards the end of the reaction due to the larger transport. Thus, faster anolyte flow can be beneficial. In our set up, the flow rate could not be increased further. In the experimental work we applied 405 ml/min.
- the "old” water can be disregarded since it was used as an introductory sample and the "fresh” and the “toluene extracted” waters are of importance.
- the strong tendency of the "fresh” water to form layers of precipitates illustrates the importance of treating the aqueous phase waste stream before it is recycled in the cell.
- Extraction with toluene provides an aqueous phase suitable as an anolyte. It apparently modified the free Fe ion content and no precipitation occurred in the catholyte. The extraction also modified the organic content and although with this water there was some layer formation, too, it did not block the anode and the membrane.
- the amount of H 2 can be calculated from the current by the Faraday-rule.
- V ferrocyanide
- the ferrocyanide (V) content of 250 ml process water required about 20000 As and 2.48 I H 2 formed at the expense of reaction of 1.86 g (about 1.86 ml) water. That amount is too small to see the change in the volume of 500 ml catholyte, especially if we consider that with the transport of K + ions through the membrane, water transport occurs as well, even overcompensating the loss.
- the effect of temperature was measured at 2.20 V cell voltage with 405 ml/min. flow rate. The effect was small and a positive effect could be seen only in the initial period, while at the final period the current was larger at lower temperature since in the initial period less complex was transferred. It might be considered that the operative temperature could be up to 70°C. In our experiments we applied 60°C.
- the anolyte resulting from the electro-oxidation may be rendered basic by addition of an appropriate amount of the catholyte solution resulting from the electro-oxidation, instead of adding K 2 CO 3 as in the example above.
- ferricyanide was obtained from ferrocyanide which is less expensive, and we performed 5 cycles of electro-oxidation and oxidative phenolic coupling reaction.
- the warm water layer was filtered over decalite, analysed for impurities (Table C) and reconstituted with depleted reagents (Table D), and then subjected to electro- oxidation as described hereinbefore (50°C, 2.6 V) (ELOX2).
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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)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Physical Water Treatments (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/533,098 US20060049064A1 (en) | 2002-11-04 | 2003-09-19 | Process for electrochemical oxidation of ferrocyanide to ferricyanide |
JP2004549167A JP2006505390A (en) | 2002-11-04 | 2003-09-19 | Electrooxidation of ferrocyanide to ferricyanide. |
NZ540003A NZ540003A (en) | 2002-11-04 | 2003-09-19 | Process for electrochemical oxidation of ferrocyanide to ferricyanide |
AU2003274116A AU2003274116A1 (en) | 2002-11-04 | 2003-09-19 | Process for electrochemical oxidation of ferrocyanide to ferricyanide |
BR0315802-0A BR0315802A (en) | 2002-11-04 | 2003-09-19 | Process for electrochemical oxidation of ferrocyanide to ferricyanide |
CA002503118A CA2503118A1 (en) | 2002-11-04 | 2003-09-19 | Process for electrochemical oxidation of ferrocyanide to ferricyanide |
EP03758098A EP1560947A1 (en) | 2002-11-04 | 2003-09-19 | Process for electrochemical oxidation of ferrocyanide to ferricyanide |
NO20052533A NO20052533L (en) | 2002-11-04 | 2005-05-26 | Process for Electrochemical Oxidation of Ferrocyanide to Ferricyanide |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2002/012325 WO2004042116A1 (en) | 2002-11-04 | 2002-11-04 | Process for electrochemical oxidation of ferrocyanide to ferricyanide |
EPPCT/EP02/12325 | 2002-11-04 |
Publications (1)
Publication Number | Publication Date |
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WO2004042117A1 true WO2004042117A1 (en) | 2004-05-21 |
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ID=32309276
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/012325 WO2004042116A1 (en) | 2002-11-04 | 2002-11-04 | Process for electrochemical oxidation of ferrocyanide to ferricyanide |
PCT/EP2003/050641 WO2004042117A1 (en) | 2002-11-04 | 2003-09-19 | Process for electrochemical oxidation of ferrocyanide to ferricyanide |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/012325 WO2004042116A1 (en) | 2002-11-04 | 2002-11-04 | Process for electrochemical oxidation of ferrocyanide to ferricyanide |
Country Status (14)
Country | Link |
---|---|
US (1) | US20060049064A1 (en) |
EP (1) | EP1560947A1 (en) |
JP (1) | JP2006505390A (en) |
KR (1) | KR20050072092A (en) |
CN (1) | CN1694979A (en) |
AU (2) | AU2002351836A1 (en) |
BR (1) | BR0315802A (en) |
CA (1) | CA2503118A1 (en) |
NO (1) | NO20052533L (en) |
NZ (1) | NZ540003A (en) |
PL (1) | PL375606A1 (en) |
RU (1) | RU2005117353A (en) |
WO (2) | WO2004042116A1 (en) |
ZA (1) | ZA200503519B (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US7713401B2 (en) * | 2007-08-08 | 2010-05-11 | Battelle Energy Alliance, Llc | Methods for performing electrochemical nitration reactions |
JP2011506967A (en) * | 2007-12-10 | 2011-03-03 | バイエル・ヘルスケア・エルエルシー | Method and system for producing a reagent with reduced background current |
KR102253905B1 (en) | 2013-10-16 | 2021-05-18 | 록히드 마틴 에너지, 엘엘씨 | Method and apparatus for measuring transient state-of-charge using inlet/outlet potentials |
CN105993091B (en) | 2013-11-01 | 2020-05-29 | 洛克希德马丁能量有限公司 | Apparatus and method for determining state of charge in a redox flow battery via limiting current |
KR102253907B1 (en) | 2013-11-15 | 2021-05-18 | 록히드 마틴 에너지, 엘엘씨 | Methods for determining state of charge and calibrating reference electrodes in a redox flow battery |
JP2018504614A (en) * | 2014-12-08 | 2018-02-15 | ロッキード・マーティン・アドバンスト・エナジー・ストレージ・エルエルシーLockheed Martin Advanced Energy Storage, LLC | Electrochemical system and method incorporating spectroscopic identification of in-situ state of charge |
US10903511B2 (en) | 2016-11-29 | 2021-01-26 | Lockheed Martin Energy, Llc | Flow batteries having adjustable circulation rate capabilities and methods associated therewith |
WO2018160727A1 (en) * | 2017-03-01 | 2018-09-07 | Axine Water Technologies Inc. | Stack of electrochemical cells for wastewater treatment with isolated electrodes |
CN113060801A (en) * | 2021-03-29 | 2021-07-02 | 山东理工大学 | Electrochemical device for treating cyanide-containing wastewater and preparation method and application thereof |
Citations (4)
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US4032415A (en) * | 1974-08-16 | 1977-06-28 | The Mead Corporation | Method for promoting reduction oxidation of electrolytically produced gas |
US4290862A (en) * | 1979-11-14 | 1981-09-22 | Edinen Centar P Chimia | Method for the preparation of narwedine-type enones |
RU2051203C1 (en) * | 1992-09-17 | 1995-12-27 | Научно-исследовательский и проектный институт мономеров с опытным заводом | Method for obtaining potassium ferricyanide |
US6407229B1 (en) * | 1994-10-21 | 2002-06-18 | Sanochemia Pharmazeutika Ag | Processes for the preparation of derivatives of 4a,5,9,10,11,12-hexahydro-6H-benzofuro-[3a,3,2-ef][2] benzazapine |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US5302257A (en) * | 1992-02-21 | 1994-04-12 | Sepracor, Inc. | Electrocatalytic asymmetric dihydroxylation of olefinic compounds |
-
2002
- 2002-11-04 WO PCT/EP2002/012325 patent/WO2004042116A1/en not_active Application Discontinuation
- 2002-11-04 AU AU2002351836A patent/AU2002351836A1/en not_active Abandoned
-
2003
- 2003-09-19 KR KR1020057005060A patent/KR20050072092A/en not_active Application Discontinuation
- 2003-09-19 RU RU2005117353/15A patent/RU2005117353A/en not_active Application Discontinuation
- 2003-09-19 WO PCT/EP2003/050641 patent/WO2004042117A1/en active Application Filing
- 2003-09-19 BR BR0315802-0A patent/BR0315802A/en not_active IP Right Cessation
- 2003-09-19 AU AU2003274116A patent/AU2003274116A1/en not_active Abandoned
- 2003-09-19 CN CNA038248506A patent/CN1694979A/en active Pending
- 2003-09-19 JP JP2004549167A patent/JP2006505390A/en not_active Withdrawn
- 2003-09-19 US US10/533,098 patent/US20060049064A1/en active Pending
- 2003-09-19 PL PL03375606A patent/PL375606A1/en not_active Application Discontinuation
- 2003-09-19 NZ NZ540003A patent/NZ540003A/en unknown
- 2003-09-19 EP EP03758098A patent/EP1560947A1/en active Pending
- 2003-09-19 CA CA002503118A patent/CA2503118A1/en not_active Abandoned
-
2005
- 2005-05-03 ZA ZA200503519A patent/ZA200503519B/en unknown
- 2005-05-26 NO NO20052533A patent/NO20052533L/en not_active Application Discontinuation
Patent Citations (4)
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US4032415A (en) * | 1974-08-16 | 1977-06-28 | The Mead Corporation | Method for promoting reduction oxidation of electrolytically produced gas |
US4290862A (en) * | 1979-11-14 | 1981-09-22 | Edinen Centar P Chimia | Method for the preparation of narwedine-type enones |
RU2051203C1 (en) * | 1992-09-17 | 1995-12-27 | Научно-исследовательский и проектный институт мономеров с опытным заводом | Method for obtaining potassium ferricyanide |
US6407229B1 (en) * | 1994-10-21 | 2002-06-18 | Sanochemia Pharmazeutika Ag | Processes for the preparation of derivatives of 4a,5,9,10,11,12-hexahydro-6H-benzofuro-[3a,3,2-ef][2] benzazapine |
Non-Patent Citations (4)
Title |
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CZOLLNER L ET AL: "New Kilogram-Synthesis of the Anti-Alzheimer Drug (-)-Galanthamine", TETRAHEDRON LETTERS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 39, no. 15, 9 April 1998 (1998-04-09), pages 2087 - 2088, XP004110636, ISSN: 0040-4039 * |
DATABASE WPI Section Ch Week 198751, Derwent World Patents Index; Class E31, AN 1987-357539, XP002260103 * |
DATABASE WPI Section Ch Week 199640, Derwent World Patents Index; Class E31, AN 1996-400688, XP002260102 * |
POSCHALKO A ET AL: "Synthesis of (+/-)-6H-benzofuro[3a,3,2,ef][3]benzazepine: an unnatural analog of (-)-galanthamine", TETRAHEDRON, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 58, no. 8, 18 February 2002 (2002-02-18), pages 1513 - 1518, XP004336387, ISSN: 0040-4020 * |
Also Published As
Publication number | Publication date |
---|---|
CA2503118A1 (en) | 2004-05-21 |
AU2003274116A1 (en) | 2004-06-07 |
CN1694979A (en) | 2005-11-09 |
NO20052533D0 (en) | 2005-05-26 |
EP1560947A1 (en) | 2005-08-10 |
WO2004042116A1 (en) | 2004-05-21 |
NO20052533L (en) | 2005-05-26 |
KR20050072092A (en) | 2005-07-08 |
US20060049064A1 (en) | 2006-03-09 |
JP2006505390A (en) | 2006-02-16 |
PL375606A1 (en) | 2005-12-12 |
AU2002351836A1 (en) | 2004-06-07 |
ZA200503519B (en) | 2006-08-30 |
NZ540003A (en) | 2006-06-30 |
BR0315802A (en) | 2005-09-20 |
RU2005117353A (en) | 2006-01-20 |
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