EP1348043B1 - Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique - Google Patents

Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique Download PDF

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Publication number
EP1348043B1
EP1348043B1 EP01994702A EP01994702A EP1348043B1 EP 1348043 B1 EP1348043 B1 EP 1348043B1 EP 01994702 A EP01994702 A EP 01994702A EP 01994702 A EP01994702 A EP 01994702A EP 1348043 B1 EP1348043 B1 EP 1348043B1
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EP
European Patent Office
Prior art keywords
compounds
alkyl
derivatives
substituted
acid
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
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EP01994702A
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German (de)
English (en)
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EP1348043A2 (fr
Inventor
Hermann Pütter
Andreas Fischer
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BASF SE
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BASF SE
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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
    • 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)

Claims (5)

  1. Procédé de préparation de formaldéhyde-di-(C1-C6-alkyl)-acétals, d'esters tri-(C1-C6-alkyliques) d'acide ortho-formique, d'acétaldéhyde-di-(C1-C6-alkyl)-acétals ou d'esters tri-(C1-C6-alkyliques) d'acide ortho-acétique (composés I)
    par oxydation anodique
    de 1,2-di-(C1-C6-alcoxy)-éthane ou -propane, de 1,1,2,2-tétra(C1-C6-alcoxy)-éthane ou -propane, ou de 2,3-di(C1-C6-alcoxy)-butane (composés II)
    en présence d'un alcool alkylique en C1-C6 (composés III), dans lequel on met en oeuvre, comme dépolarisant cathodique, un composé organique usuel (composé IV) qui est approprié pour la réduction électrochimique, et dans lequel on effectue l'oxydation anodique et la réduction cathodique dans une cellule d'électrolyse non divisée, en présence d'alcools alkyliques en C1-C6.
  2. Procédé suivant la revendication 1, dans lequel les composés I sont de l'ester triméthylique d'acide ortho-formique ou du formaldéhydediméthylacétal, ces composés pouvant être également formés sous la forme d'un mélange.
  3. Procédé suivant l'une des revendications 1 et 2, dans lequel, en ce qui concerne le composé IV, il s'agit de composés d'hydrocarbures aromatiques, d'oléfines activées, d'acides carboxyliques aromatiques et de leurs dérivés, de composés carbonyle, d'imines, d'hétérocycles, de naphtalène ou de dérivés de naphtalène substitués sur le noyau.
  4. Procédé suivant la revendication 3, dans lequel, en ce qui concerne la dépolarisation cathodique, il s'agit d'une des réactions suivantes :
    a) de l'acide maléique ou des dérivés de l'acide maléique, où la fonction acide se présente sous la forme d'esters alkyliques, pour former un ester tétraalkylique d'acide butanetétracarboxylique avec hydrodimérisation,
    b) des acides benzènemono-, di-, ou tri- carboxyliques, différents de l'acide phtalique ou des dérivés de l'acide phtalique, ou respectivement des dérivés de ces composés où la fonction acide se présente sous la forme d'esters alkyliques, ou des dérivés substitués sur le noyau aromatique, pour former les composés correspondants de mono-, di- et tri-formylbenzène, dans lesquels les groupes formyle se présentent sous la forme d'un acétal,
    c) de l'acide acrylique, de l'acrylate d'alkyle, de l'acrylamide ou de l'acrylonitrile ou des homologues de ces composés pour former les produits d'hydrodimérisation correspondants,
    d) de l'acide phtalique, du phtalate d'alkyle ou des dérivés substitués sur le noyau aromatique de ces composés, pour former du phtalide ou des dérivés de phtalide substitués sur le noyau, de l'acide cyclohexane- ou cyclohexène-1,2-dicarboxylique, des esters dialkyliques d'acide cyclohexane- ou cyclohexène-1,2-dicarboxylique ou, conformément au modèle de substitution des dérivés d'acide phtalique substitués sur le noyau aromatique, des dérivés substitués sur le noyau de cyclohexane ou de cyclohexène,
    e) du naphtalène ou des dérivés de naphtalène substitués sur le noyau, pour former du 1,2,3,4-tétrahydronaphtalène ou les dérivés correspondants de 1,2,3,4-tétrahydronaphtalène,
    f) de la pyridine ou des dérivés de pyridine substitués sur le noyau pour former de la 1,4-dihydropyridine ou les dérivés correspondants de 1,4-dihydropyridine.
  5. Procédé suivant les revendications 1 à 4, dans lequel on effectue le procédé dans une cellule à pile de plateaux présentant des électrodes empilées, montées en série.
EP01994702A 2000-11-24 2001-11-22 Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique Expired - Lifetime EP1348043B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10058304 2000-11-24
DE10058304A DE10058304A1 (de) 2000-11-24 2000-11-24 Verfahren zur Herstellung von alkoxylierten Carbonylverbindungen durch ein anodisches Oxidationsverfahren unter Nutzung der kathodischen Koppelreaktion zur organischen Synthese
PCT/EP2001/013587 WO2002042524A2 (fr) 2000-11-24 2001-11-22 Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique

Publications (2)

Publication Number Publication Date
EP1348043A2 EP1348043A2 (fr) 2003-10-01
EP1348043B1 true EP1348043B1 (fr) 2005-03-09

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EP01994702A Expired - Lifetime EP1348043B1 (fr) 2000-11-24 2001-11-22 Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique

Country Status (11)

Country Link
US (1) US6822124B2 (fr)
EP (1) EP1348043B1 (fr)
JP (1) JP3906153B2 (fr)
CN (1) CN1329556C (fr)
AT (1) ATE290616T1 (fr)
AU (1) AU2002224874A1 (fr)
CA (1) CA2429450A1 (fr)
DE (2) DE10058304A1 (fr)
ES (1) ES2238501T3 (fr)
NO (1) NO20032335L (fr)
WO (1) WO2002042524A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013186094A2 (fr) 2012-06-15 2013-12-19 Basf Se Oxydation anodique de substrats organique en présence de nucléophiles

Families Citing this family (14)

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Publication number Priority date Publication date Assignee Title
DE10146566A1 (de) * 2001-09-21 2003-07-17 Basf Ag Verfahren zur Herstellung von Orthocarbonsäuretrialkylestern
DE10355087A1 (de) * 2003-11-24 2005-06-09 Basf Ag Verfahren zur elektrochemischen Herstellung eines kristallinen porösen metallorganischen Gerüstmaterials
FR2910784B1 (fr) 2006-12-27 2009-02-20 Arkema France Utilisation de composes pour la conservation du corps humain ou animal et compositions les comprenant
DE102007008668A1 (de) * 2007-02-20 2008-08-21 Tesa Ag Verfahren zum Beschriften oder Markieren von Oberflächen
US8889920B2 (en) * 2010-02-12 2014-11-18 Basf Se Process for preparing 4-isopropylcyclohexylmethanol
EP2534281B1 (fr) * 2010-02-12 2019-01-09 Basf Se Procédé de préparation de 4-isopropylcyclohexylméthanol
CN107473945B (zh) * 2016-06-08 2020-09-01 中国科学院大连化学物理研究所 一种催化甲醇直接氧化酯化制四甲氧基甲烷的方法
CN106591877A (zh) * 2016-11-14 2017-04-26 江苏科技大学 一种中心原子可变换的偶联剂及其制备方法
US20190352784A1 (en) * 2016-11-24 2019-11-21 Avantium Knowledge Centre B.V. Process for treating a furan-2,5-dicarboxylic acid composition
DE102017113141A1 (de) * 2017-06-14 2018-12-20 Westfälische Wilhelms-Universität Münster Elektrolyt für Lithium-Ionen-Batterien
DE102017012021A1 (de) 2017-12-22 2019-06-27 Friedrich-Schiller-Universität Jena Acetalischer Elektrolyt
JP7105418B2 (ja) * 2018-02-08 2022-07-25 Ｅｎｅｏｓ株式会社 シス－二置換非芳香族化合物の製造装置および製造方法
CN108677210B (zh) * 2018-04-17 2019-10-29 大连理工大学 一种酮与羧酸在电化学氢泵反应器中一步加氢酯化的方法
CN112195481B (zh) * 2020-11-02 2021-12-10 上海漫关越水处理有限公司 膜电解合成四甲氧基乙烷的方法

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DE3000243A1 (de) 1980-01-05 1981-07-09 Hoechst Ag, 6230 Frankfurt Verfahren zur elektrochemischen alkoxylierung von aliphatischen ethern
US4450055A (en) * 1983-03-30 1984-05-22 Celanese Corporation Electrogenerative partial oxidation of organic compounds
US4648948A (en) * 1985-05-23 1987-03-10 Meshbesher Thomas M Electrogenerative oxidation of lower alcohols to useful products
US5223102A (en) * 1992-03-03 1993-06-29 E. I. Du Pont De Nemours And Company Process for the electrooxidation of methanol to formaldehyde and methylal
DE19618854A1 (de) * 1996-05-10 1997-11-13 Basf Ag Verfahren zur Herstellung von Phthaliden
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013186094A2 (fr) 2012-06-15 2013-12-19 Basf Se Oxydation anodique de substrats organique en présence de nucléophiles

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Publication number Publication date
JP2004514791A (ja) 2004-05-20
CN1476491A (zh) 2004-02-18
NO20032335D0 (no) 2003-05-23
US6822124B2 (en) 2004-11-23
AU2002224874A1 (en) 2002-06-03
ES2238501T3 (es) 2005-09-01
WO2002042524A2 (fr) 2002-05-30
CA2429450A1 (fr) 2002-05-30
JP3906153B2 (ja) 2007-04-18
DE10058304A1 (de) 2002-05-29
CN1329556C (zh) 2007-08-01
ATE290616T1 (de) 2005-03-15
DE50105570D1 (de) 2005-04-14
US20040026263A1 (en) 2004-02-12
EP1348043A2 (fr) 2003-10-01
WO2002042524A3 (fr) 2003-03-13
NO20032335L (no) 2003-07-14

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