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
  • 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
  • C25B3/01—Products
  • C25B3/07—Oxygen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/01—Products
  • C25B3/09—Nitrogen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/20—Processes
  • C25B3/23—Oxidation

Definitions

• the present invention relates to a process for the preparation of formaldehyde di (C 1 to C 6 alkyl) acetals, ortho-formic acid tri- (C 1 to C 6 alkyl) esters, acetaldehyde di ( C 1 - to C 6 -alkyl) - acetals or ortho-acetic tri- (C 1 - to C 6 -alkyl) esters (compounds 1) by anodic oxidation of 1,2-di- (C 1 - to C 6 - alkoxy) ethane or propane, 1,1,2,2-tetra (C 1 to C 6 alkoxy) ethane or propane, or 2,3-di- (C 1 to C 6 alkoxy) -butane (compounds II) in the presence of a C 1 - to C 6 -alkyl alcohol (compounds III) in which the cathodic depolarizer used is a customary organic compound (compounds IV) which is suitable for electrochemical reduction and in
• compounds II are 1,2-di (C 1 - to C 6 alkoxy) ethane or propane or 1,1,2,2-tetra (C 1 - to C 6 alkoxy) ethane or -propane used.
• compounds I the corresponding formaldehyde di (C 1 - to C 6 alkyl) acetals or ortho-antric acid tri (C 1 - to C 6 alkyl) esters are formed and, in the case of the propane derivatives as starting materials also acetaldehyde di- (C 1 - to C 6 alkyl) - acetals or Orthoessigklatri- (C 1 - to C 6 alkyl) ester.
• the abovementioned acetaldehyde or acetic acid derivatives can likewise be prepared from 2,3-di- (C 1 -C 6 -alkoxy) -butane.
• cathodic Depolisatoren come usual organic Compounds suitable for anodic reduction, such as aromatic hydrocarbon compounds, activated olefins, Carbonyl compounds, aromatic carboxylic acids and their derivatives and naphthalene or nucleus-substituted naphthalene derivatives.
• Suitable substituents with which the aromatic nuclei can be substituted in the abovementioned starting compounds are inert, hardly reducible groups, such as C 1 -C 12 -alkyl, C 1 -C 6 -alkoxy or halogen.
• the molar ratio of the starting compounds for cathode and Anode reaction and the products formed in these reactions in electrolytes to each other is not critical.
• Conducting salts which are contained in the electrolysis solution are generally alkali, tetra (C 1 - to C 6 -alkyl) -ammonium or tri- (C 1 - to C 6 -alkyl) -benzylammonium salts.
• Suitable counterions are sulfate, hydrogensulfate, alkyl sulfates, alkyl sulfonates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate or perchlorate.
• MTBS methyltributylammonium methylsulfate
• methyltriethylammonium methylsulfate methyltriethylammonium methylsulfate
• methyl tripropylmethylammonium methyl sulfates Preference is given to methyltributylammonium methylsulfate (MTBS), methyltriethylammonium methylsulfate or methyl tripropylmethylammonium methyl sulfates.
• the electrolysis solution is subjected to customary cosolvents to. These are those in organic chemistry Commonly used inert solvents with a high oxidation potential. Examples include dimethyl carbonate or Propylene carbonate.
• the process of the invention can be in all the usual undivided Electrolysis cell types are performed. Preferably works one continuously with undivided flow cells. Especially plate stack cells with serially designed stacking electrodes are suitable, as described for example in DE-A-19533773 are.
• the current densities at which the process is carried out are generally 1 to 1000, preferably 10 to 100 mA / cm 2 .
• the temperatures are usually -20 to 60 ° C, preferably 0 to 60 ° C. In general, working at atmospheric pressure. Higher pressures are preferably used when operating at higher temperatures to avoid boiling of the starting compounds or cosolvents.
• Suitable anode materials are, for example, noble metals such as platinum or metal oxides such as ruthenium or chromium oxide or mixed oxides of the type Ruo x Tio x . Preference is given to graphite or carbon electrodes.
• cathode materials are, for example, iron, steel, stainless steel, Nickel or precious metals such as platinum and graphite or carbon materials into consideration.
• the system is graphite Anode and cathode as well as graphite as anode and nickel, stainless steel or steel as a cathode.
• the electrolyte solution is after worked up general separation methods.
• the electrolysis solution generally distilled first and the individual Compounds separated in the form of different fractions won. Further purification can be carried out, for example, by crystallization, Distillation or by chromatography.
• 11 ring disk electrodes each having a surface area of 140 cm 2 and an outer diameter of 14 cm are arranged so as to form a stack. By spacers, the discs are set to a distance of 1 mm, resulting in 10 gaps between the annular discs.
• the electrode material is graphite. Under electrolysis conditions, the inner 0.5 cm thick disks are bipolar.
• the top electrode is anodically contacted by means of a graphite punch and a cover plate, the bottom electrode is cathodically contacted, the cathodic contact extends over the bottom plate of the cell.
• the electrolyte flows through the central bore of the bottom plate into the cell, spreads over the column and leaves the cell above the top electrode.
• the cell is part of a circulating apparatus in which the electrolyte is circulated, heated or cooled.
• the electrolysis effluent contained 24.4% butanetetracarboxylic acid methyl ester, 14.2% trimethyl orthoformate, 25.6% tetramethoxyethane and 1.7% maleic dimethyl ester.
• the selectivity the orthoester formation was 82%.
• the composition of the electrolysis discharge was determined by gas chromatograph and is in area% (GC area%).

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (3)

Publications (2)

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• 2000
  • 2000-11-24 DE DE10058304A patent/DE10058304A1/de active Pending
• 2001
  • 2001-11-22 CA CA002429450A patent/CA2429450A1/en not_active Abandoned
  • 2001-11-22 JP JP2002545221A patent/JP3906153B2/ja not_active Expired - Fee Related
  • 2001-11-22 ES ES01994702T patent/ES2238501T3/es not_active Expired - Lifetime
  • 2001-11-22 DE DE50105570T patent/DE50105570D1/de not_active Expired - Fee Related
  • 2001-11-22 AT AT01994702T patent/ATE290616T1/de not_active IP Right Cessation
  • 2001-11-22 EP EP01994702A patent/EP1348043B1/de not_active Expired - Lifetime
  • 2001-11-22 CN CNB018194397A patent/CN1329556C/zh not_active Expired - Fee Related
  • 2001-11-22 US US10/432,249 patent/US6822124B2/en not_active Expired - Fee Related
  • 2001-11-22 AU AU2002224874A patent/AU2002224874A1/en not_active Abandoned
  • 2001-11-22 WO PCT/EP2001/013587 patent/WO2002042524A2/de not_active Ceased
• 2003
  • 2003-05-23 NO NO20032335A patent/NO20032335L/no unknown

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