EP0339523B1 - Procédé de préparation d'esters d'acides hydroxycarboxyliques - Google Patents

Procédé de préparation d'esters d'acides hydroxycarboxyliques Download PDF

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Publication number
EP0339523B1
EP0339523B1 EP89107289A EP89107289A EP0339523B1 EP 0339523 B1 EP0339523 B1 EP 0339523B1 EP 89107289 A EP89107289 A EP 89107289A EP 89107289 A EP89107289 A EP 89107289A EP 0339523 B1 EP0339523 B1 EP 0339523B1
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Prior art keywords
electrochemical oxidation
formula
carried out
bromide
acid esters
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EP89107289A
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German (de)
English (en)
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EP0339523A1 (fr
Inventor
Michael Dr. Steiniger
Heinz Hannebaum
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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
    • C25B3/20—Processes
    • C25B3/23—Oxidation

Definitions

  • This invention relates to a new process for the preparation of hydroxy carboxylic acid esters by electrochemical oxidation of hydroxy aldehydes.
  • J. Org. Chem. 53, 218-219 (1988) describes a process in which 3-hydroxy-2,2-dimethylpropanal is oxidized electrochemically to 3-hydroxipivalic acid methyl ester in methanol in the presence of potassium iodide and a strong base such as sodium methoxide .
  • a disadvantage of this process is that the electrolysis is carried out in a divided electrolysis cell on platinum anodes. Compared to undivided electrolysis cells, this means not only a higher investment, but also a higher energy consumption, since the low conductivity of the organic electrolyte at the separator (diaphragm) results in a high voltage drop.
  • Another disadvantage is that this method, which presupposes the presence of sodium methoxide, allows only those aliphatic aldehydes to be oxidized which cannot undergo aldol condensation.
  • R1 and R2 are hydrogen atoms, hydroxyl groups, alkoxy groups or aliphatic or olefinic, straight-chain, branched or ring-shaped hydrocarbon radicals, where R1 and R2 can also together represent an alkylene radical, and the hydrocarbon radicals can also be substituted by halogen atoms, hydroxyl, epoxy or nitrile groups, and R3 represents a low molecular weight alkyl radical, particularly advantageously by electrochemical oxidation of hydroxy aldehydes of the general formula in the presence of alcohols of the formula R3OH, where n, R1, R2 and R3 have the meaning given above, if the electrochemical oxidation is carried out in the presence of ionogenic bromides or chlorides in an undivided electrolysis cell.
  • the hydroxy carboxylic acid esters are obtained with high selectivity and high current yields.
  • This advantageous result is surprising since in J. Electrochem. Soc. 125 , 1401-1403 (1978) describes that the electrochemical oxidation of primary alcohols in undivided electrolysis cells on graphite electrodes in the presence of chloride and bromide ions leads to aldehydes. Accordingly, ⁇ , ⁇ -dialkoxy carboxylic acid esters or dicarboxylic acid esters would have been expected as reaction products of the process according to the invention.
  • n is a number from 0 to 10, preferably 0 to 5.
  • the aliphatic or olefinic straight-chain or branched hydrocarbon radicals mentioned as radicals R 1 and R 2 are, for example, alkyl or alkylene groups having 1 to 10, in particular 1 to 6, preferably 1 to 4 carbon atoms, such as methyl, ethyl, n or iso-propyl, n, iso or tert-butyl groups.
  • Substituted hydrocarbon radicals of the type mentioned are, for example, hydroximethyl, chloromethyl or hydroxyethyl groups.
  • Annular hydrocarbons are, for example, cycloalkyl radicals having 3 to 8, in particular 5 and 6, carbon atoms. Both radicals R 1 and R 2 also come together to represent an alkylene radical, which can consist, for example, of 2 to 5 methyl groups.
  • R3 represents a low molecular weight alkyl radical, in particular an alkyl radical having 1 to 5 carbon atoms, preferably a methyl or ethyl radical.
  • alkyl radical having 1 to 5 carbon atoms, preferably a methyl or ethyl radical.
  • n- or iso-propanol, n-butanol, n-pentanol and preferably methanol or ethanol can be used.
  • Salts of hydrobromic and hydrochloric acid are suitable as ionogenic halides. Salts of hydrobromic acid, such as alkali, alkaline earth bromides and quaternary ammonium, especially tetraalkylammonium bromides are preferred.
  • the cation does not play an essential role in the invention, therefore other ionic metal halides can also be used, but cheap halides will advantageously be chosen.
  • examples include sodium, potassium, calcium and ammonium bromide, and di-, tri- and tetramethyl- or tetraethylammonium bromide.
  • the process according to the invention can be carried out in the industrially customary electrolysis cells. It can advantageously be carried out in an undivided flow cell, which makes it possible to keep the electrode spacing very small in order to minimize the cell voltage.
  • the preferred electrode spacing is 1 mm or less, in particular 0.25 to 0.5 mm.
  • the preferred anode material is graphite. However, other anode materials which are stable under the reaction conditions can also be used.
  • the cathode material is e.g. from metals such as lead, iron, steel, nickel or precious metals such as platinum.
  • the preferred cathode material is also graphite.
  • the composition of the electrolyte can be chosen within wide limits.
  • the electrolyte consists of 1 to 80% by weight of hydroxy aldehyde of the formula II 10 to 95 wt% R3OH 0.1 to 10 wt% halide
  • a solvent can be added to the electrolyte, for example to improve the solubility of the hydroxy aldehyde or the halide.
  • Suitable solvents are, for example, nitriles such as acetonitrile and ethers such as tetrahydrofuran.
  • the solvents are added, for example, in amounts of up to 30% by weight, based on the electrolyte.
  • the current density is not a limiting factor for the process according to the invention, it is, for example, 1 to 25 A / dm 2.
  • Electrolysis is preferably carried out at 3 to 12 A / dm 2. When the electrolysis is operated without pressure, the temperature is expediently chosen so that it is at least 5 to 10 ° C.
  • the electrolysis discharges can be worked up by methods known per se.
  • the electrolysis discharge is expediently worked up by distillation. Excess alkanol and any cosolvent used are first distilled off.
  • the halides are made in a known manner, e.g. separated by filtration or extraction, and the hydroxy carboxylic acid esters are distilled or recrystallized. Alkanol, possibly unreacted hydroxy aldehyde and cosolvents as well as halides can advantageously be recycled to the electrolysis.
  • the process according to the invention can be carried out batchwise or continuously.
  • hydroxy carboxylic acid esters produced by the process according to the invention are versatile intermediates for the synthesis of crop protection agents or polymers.
  • the electrooxidation was carried out in an undivided electrolysis cell with anodes and cathodes made of graphite at temperatures of 20 to 25 ° C.
  • the composition of the electrolyte used and the electrolysis conditions are summarized in the table.
  • the electrolyte was pumped through the cell at 200 l / h via a heat exchanger.

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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)

Claims (5)

1.- Procédé de préparation d'esters d'acides hydroxycarboxyliques de formule générale
Figure imgb0008
 dans laquelle n représente un nombre entier de 0 à 10, R¹ et R² représentent des atomes d'hydrogène, des groupements hydroxy, des groupements alcoxy ou des restes hydrocarbonés aliphatiques ou oléfiniques en chaîne linéaire, ramifiée ou cyclique, R¹ et R² pouvant aussi être mis ensemble pour un reste alkylène et les restes hydrocarbonés pouvant être encore substitués par des atomes d'halogène ou par des groupements hydroxy, époxy ou nitrile, et R³ est mis pour un reste alkyle inférieur, par oxydation électrochimique d'hydroxy-aldéhydes de formule générale
Figure imgb0009
 en présence d'alcools de formule R³OH, n, R¹, R² et R³ ayant les significations susmentionnées, caractérisé en ce qu'on conduit l'oxydation électrochimique en présence de bromures ou de chlorures ionogènes dans une cellule d'électrolyse non partagée.
2.- Procédé selon la revendication 1, caractérisé en ce qu'on utilise, comme bromure ionogène, un bromure de métal alcalin ou alcalino-terreux ou un bromure d'ammonium quaternaire.
3.- Procédé selon la revendication 1, caractérisé en ce qu'on procède à l'oxydation électrochimique sur des anodes de graphite.
4.- Procédé selon la revendication 1, caractérisé en ce qu'on utilise, comme alcool de formule R₃OH, du méthanol ou de l'éthanol.
5.- Procédé selon la revendication 1, caractérisé en ce qu'on procède à l'oxydation électrochimique avec des densités de courant de 1 à 25 A/dm².
EP89107289A 1988-04-29 1989-04-22 Procédé de préparation d'esters d'acides hydroxycarboxyliques Expired - Lifetime EP0339523B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3814498 1988-04-29
DE3814498A DE3814498A1 (de) 1988-04-29 1988-04-29 Verfahren zur herstellung von hydroxicarbonsaeureestern

Publications (2)

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EP0339523A1 EP0339523A1 (fr) 1989-11-02
EP0339523B1 true EP0339523B1 (fr) 1992-08-26

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EP89107289A Expired - Lifetime EP0339523B1 (fr) 1988-04-29 1989-04-22 Procédé de préparation d'esters d'acides hydroxycarboxyliques

Country Status (4)

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US (1) US4990227A (fr)
EP (1) EP0339523B1 (fr)
JP (1) JP2799339B2 (fr)
DE (2) DE3814498A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018031889A1 (fr) * 2016-08-12 2018-02-15 California Institute Of Technology Oxydation d'hydrocarbures par électrocatalyseurs d'oxydation d'eau dans des solvants non aqueux
US10840504B2 (en) 2017-02-23 2020-11-17 California Institute Of Technology High performance inorganic complexes for next-generation redox flow batteries

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2699937B1 (fr) * 1992-12-29 1995-03-17 Ard Sa Procédé de préparation de l'acide galactarique et cellule d'électrolyse utilisée à cet effet.
US5648387A (en) * 1995-03-24 1997-07-15 Warner-Lambert Company Carboxyalkylethers, formulations, and treatment of vascular diseases
US6251256B1 (en) * 1999-02-04 2001-06-26 Celanese International Corporation Process for electrochemical oxidation of an aldehyde to an ester
EP2748353B1 (fr) * 2011-08-24 2017-04-26 Basf Se Procédé de préparation électrochimique d'esters d'acide gamma-hydroxycarboxylique et de gamma-lactones

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4402804A (en) * 1982-05-17 1983-09-06 Ppg Industries, Inc. Electrolytic synthesis of aryl alcohols, aryl aldehydes, and aryl acids
DE3443303A1 (de) * 1984-11-28 1986-06-05 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von 3-hydroxy-3-methylglutarsaeure
DE3603376A1 (de) * 1986-02-05 1987-08-06 Basf Ag Verfahren zur herstellung von pyrazolen
DE3713732A1 (de) * 1987-04-24 1988-11-17 Basf Ag Neue benzaldehyddialkylacetale, ihre herstellung und verwendung

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018031889A1 (fr) * 2016-08-12 2018-02-15 California Institute Of Technology Oxydation d'hydrocarbures par électrocatalyseurs d'oxydation d'eau dans des solvants non aqueux
US11352705B2 (en) 2016-08-12 2022-06-07 California Institute Of Technology Hydrocarbon oxidation by water oxidation electrocatalysts in non-aqueous solvents
US10840504B2 (en) 2017-02-23 2020-11-17 California Institute Of Technology High performance inorganic complexes for next-generation redox flow batteries

Also Published As

Publication number Publication date
JP2799339B2 (ja) 1998-09-17
US4990227A (en) 1991-02-05
EP0339523A1 (fr) 1989-11-02
JPH01312094A (ja) 1989-12-15
DE58902114D1 (de) 1992-10-01
DE3814498A1 (de) 1989-11-09

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