EP0277048A1 - Verfahren zur elektrochemischen Herstellung von Carbonsäuren - Google Patents

Verfahren zur elektrochemischen Herstellung von Carbonsäuren Download PDF

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Publication number
EP0277048A1
EP0277048A1 EP88400025A EP88400025A EP0277048A1 EP 0277048 A1 EP0277048 A1 EP 0277048A1 EP 88400025 A EP88400025 A EP 88400025A EP 88400025 A EP88400025 A EP 88400025A EP 0277048 A1 EP0277048 A1 EP 0277048A1
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EP
European Patent Office
Prior art keywords
radical
heteroatom
carbon atom
group
chosen
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EP88400025A
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English (en)
French (fr)
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EP0277048B1 (de
Inventor
Marie-Odile Moingeon
Jacques Chaussard
Michel Troupel
Christophe Saboureau
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Societe Nationale des Poudres et Explosifs
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Societe Nationale des Poudres et Explosifs
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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
    • C25B3/20—Processes
    • C25B3/25—Reduction

Definitions

  • the present invention relates to a process for the electrosynthesis of carboxylic acids by electrochemical reduction, in the presence of carbon dioxide, of organic compounds comprising at least one simple carbon-heteroatom covalent bond, process carried out in an electrolysis cell in organic medium .
  • Carboxylic acids are products commonly used in the chemical industry, in particular as intermediates for the synthesis of pharmaceutical or phytosanitary products. Mention may in particular be made of their use for the synthesis of penicillins as well as for those of anti-inflammatories and insecticides.
  • FR 2,566,434 which the Applicant is the holder of, describes the synthesis of carboxylic acids by electrochemical reduction, in the presence of carbon dioxide, of organic halides.
  • the process is carried out in a cell which is preferably not compartmentalized, in an organic medium.
  • the anode, made of magnesium, is consumed during electrosynthesis by the electrochemical reaction of which it is the seat.
  • benzyl halides are tear gas, irritants and corrosives.
  • the most reactive are particularly unstable; paramethoxybenzyl chloride, chloromethyl and chloroethyl thiphenes spontaneously polymerize at room temperature with a significant gassing of hydrochloric acid.
  • Alpha arylchloroethanes often undergo dehydrochlorination reactions leading to undesirable styrenic derivatives. All these parasitic reactions are often accelerated due to the operating conditions of electrocarboxylation (polar solvents, presence of metal salts).
  • electrocarboxylation of paramethoxybenzyl chloride gives paramethoxyphenylacetic acid only with a yield of 50% while the raw material has completely disappeared.
  • BAIZER in JOC 37.12, 1951-60, 1972, obtains benzyl esters or allyl esters, by electrochemical reduction, in the presence of carbon dioxide, halides of corresponding benzyl or allyl, in an organic medium (dimethylformamide-DMF) in the presence of tetraethylammonium chloride as indifferent electrolyte.
  • the cathode is made of mercury and the anode of platinum.
  • allyl or benzyl esters obtained are therefore completely stable with respect to electrocarboxylation since they are isolated with excellent yields.
  • the method according to the invention allows, compared to the method described in FR 2 566 434 to retain all the advantages, and in particular those mentioned in the application FR 2 566 434 itself , without having the disadvantages and in particular those mentioned above linked to the use of organic halides.
  • the process for the electrosynthesis of carboxylic acids by electrochemical reduction, in the presence of carbon dioxide, of organic compounds comprising at least one simple carbon-heteroatom covalent bond process carried out in an organic medium in a cell.
  • electrolysis provided with electrodes is characterized in that the anode is made of a metal chosen from the group consisting of reducing metals and their alloys and in that the heteroatom is chosen from the group consisting of oxygen, nitrogen, sulfur and phosphorus.
  • alloys means any alloy containing at least one reducing metal.
  • the reducing metal is chosen from the group consisting of magnesium, aluminum, zinc and their alloys.
  • the organic compounds comprising at least one simple carbon-heteroatom covalent bond which can be used in the context of the present invention correspond to the general formula RY in which R is an organic radical and Y a heteroatomic radical, the heteroatom chosen from the group consisting of l Oxygen, nitrogen, sulfur and phosphorus being directly linked to a carbon atom of the organic radical R by a simple covalent bond.
  • Carboxylic acids of general formula R-COOH are thus obtained by breaking in R-Y of the simple covalent bond connecting the heteroatom of the radical Y to a carbon atom of the radical R and fixing of CO2 on this carbon atom.
  • Y is necessarily an ammonium radical
  • Y is necessarily a phosphonium radical
  • Y is for example a radical
  • Y is for example a radical
  • radicals R1, R2 and R3 are aliphatic, aromatic or heterocyclic hydrocarbon radicals, substituted or unsubstituted. They can also form rings, with each other or with the radical R.
  • unsaturated carboxylic acids are obtained.
  • the carbon atom of the organic radical R which is directly linked to the heteroatom of the radical Y is hybridized "sp3" (it is sometimes said that such a carbon atom is a “saturated” carbon atom) and to the at least one of the carbon atoms of the radical R in beta position with respect to the heteroatom of the radical Y is hybridized “sp2". (It is sometimes said that such a carbon atom is an "ethylenically unsaturated” carbon atom).
  • “sp3" hybridization is a tetrahedral hybridization
  • sp2" hybridization is a plane trigonal hybridization.
  • This hybridized "sp2" carbon atom of the radical R in the beta position with respect to the heteroatom is particularly preferably an ethylenic carbon atom or a carbon atom forming part of a substituted or unsubstituted aromatic ring or heterocycle.
  • the radical R is preferably an aliphatic radical containing 3 to 10 carbon atoms. This is the case for example when R is an allylic radical.
  • the hybridized carbon atom "sp2" of the radical R in the beta position with respect to the heteroatom is part of a substituted or unsubstituted aromatic ring
  • the hybridized carbon atom "sp3" of the radical R which is directly linked to the heteroatom preferably bears either 2 hydrogen atoms, or a hydrogen atom and a methyl or ethyl or isopropyl group.
  • the radical R is a benzyl radical.
  • this aromatic heterocycle is preferably thiophene, N-methyl pyrrole, indole or pyridine.
  • This carbon atom of the radical R in the beta position can also be an acetylene carbon (hybridized "sp1") or that of a carbonyl or nitrile group.
  • the organic radical R can comprise at least one non-reducible functional group under the conditions of electrosynthesis. Mention may be made, for example, of carbonyl, nitrile, tertiary amines, amides and fluorine groups.
  • the anode can have any shape and in particular all the classic forms of metal electrodes (twisted wire, flat bar, cylindrical bar, square section bar, plate, renewable bed, canvas, grid, ribbon, balls, shot, powder, etc).
  • a cylindrical bar of diameter adapted to the dimensions of the cell is used.
  • the purity of the metal (or alloy) constituting the anode is not an important parameter and the industrial qualities are suitable.
  • the cathode is any metal such as stainless steel, nickel, platinum, gold, copper, or graphite. It is preferably formed by a grid or a cylindrical plate arranged concentrically around the anode. For economic reasons, stainless steel is preferably used.
  • the electrodes are supplied with direct current via a stabilized power supply.
  • the organic solvents used in the context of this invention are all the low-protic solvents usually used in organic electrochemistry. Examples that may be mentioned are hexamethylphosphorotriamide (HMPT), tetrahydrofuran (THF), THF-HMPT mixtures, N-methylpyrrolidone (NMP), tetramethylurea (TMU), dimethylformamide (DMF), acetonitrile.
  • HMPT hexamethylphosphorotriamide
  • THF tetrahydrofuran
  • NMP N-methylpyrrolidone
  • TU tetramethylurea
  • DMF dimethylformamide
  • acetonitrile acetonitrile
  • the indifferent electroytes used to make the medium conductive or more conductive can be those usually used in organic electrochemistry. Mention may be made, for example, of tetrabutylammonium tetrafluoroborate (BF4 NBu4), lithium perchlorate (LiClO4), tetrabutylammonium chloride (ClNBu4), tetraethylammonium chloride (ClNEt4, tetrabutylammonium perchlorate (ClO4Nu) and zinc salts magnesium or aluminum.
  • BF4 NBu4 tetrabutylammonium tetrafluoroborate
  • LiClO4 lithium perchlorate
  • ClNBu4 tetrabutylammonium chloride
  • ClNEt4 tetraethylammonium chloride
  • ClO4Nu zinc salts magnesium or aluminum.
  • the indifferent electrolyte is an ammonium salt
  • the latter is at least partially carboxylated according to the invention but on the one hand the quantity of indifferent electrolyte can be low compared to the derivative RY and on the other by the acid formed by carboxylation of the electrolyte is easily separated from the desired acid obtained by carboxylation of the derivative RY.
  • an indifferent electrolyte is not necessary when the R-Y compound to be reduced is itself ionic, as is the case, for example, for ammonium, sulfonium or phosphonium salts.
  • its concentration in the organic solvent is preferably between 5 10 ⁇ 3 M and 5 10 ⁇ 2 M.
  • the concentration of the R-Y compound to be reduced in the organic solvent is between 10 ⁇ 1 M and 1 M. This concentration can therefore be relatively high, which is quite unusual in electrosynthesis. This observation is of course very interesting from an economic point of view.
  • the carboxylic acid formed, and optionally the unprocessed starting product, are isolated.
  • the upper glass part is equipped with 5 tubes allowing the arrival and the exit of carbon dioxide, the electrical passages and the possible samples of solution during electrolysis.
  • the lower part consists of a stopper fitted with a seal, screwed onto the upper glass part.
  • the total volume of the cell is 150 cm3.
  • the anode is a cylindrical bar of magnesium whose diameter is 1 cm. It is introduced into the cell through the central tube and immersed in the solution over a length of approximately 20 cm. The initial working surface of this electrode is 63 cm2.
  • the cathode is a cylindrical stainless steel fabric arranged concentrically around the anode.
  • DMF dimethylformamide
  • CO2 is bubbled through the solution using a tube immersed in this solution.
  • the CO2 pressure is atmospheric pressure.
  • the solution is stirred via a magnetic bar and the temperature is maintained at around 10 ° C.
  • the electrodes are supplied with direct current via a stabilized power supply and a constant current of 2 A is then imposed, ie a current density of 32 mA / cm2 on the magnesium anode.
  • reaction medium After electrolysis and evaporation of the DMF, the reaction medium is hydrolyzed with aqueous hydrochloric acid.
  • the organic compounds are then extracted with ethyl ether, then the acids are recovered by alkaline extraction.
  • the products obtained are identified according to conventional analytical methods, namely in particular NMR, IR, CPG and mass spectrometry.
  • Electrolysis chloride paramethoxybenzyl, ethyl, dimethyl ammonium is effected under the same conditions as for Example No. 23, but in a stainless steel cell under a pressure of 5 bar and CO2 at a temperature of 30 ° C .
  • a solution of dimethylbenzylacetylammonium chloride is prepared by adding, at 5 ° C, 9 g of acetyl chloride to a solution of 15 g of dimethylbenzylamine in 110 g of DMF.

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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)
EP88400025A 1987-01-09 1988-01-07 Verfahren zur elektrochemischen Herstellung von Carbonsäuren Expired - Lifetime EP0277048B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8700134 1987-01-09
FR8700134A FR2609474B1 (fr) 1987-01-09 1987-01-09 Procede de synthese electrochimique d'acides carboxyliques

Publications (2)

Publication Number Publication Date
EP0277048A1 true EP0277048A1 (de) 1988-08-03
EP0277048B1 EP0277048B1 (de) 1991-04-10

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EP88400025A Expired - Lifetime EP0277048B1 (de) 1987-01-09 1988-01-07 Verfahren zur elektrochemischen Herstellung von Carbonsäuren

Country Status (5)

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US (1) US4824532A (de)
EP (1) EP0277048B1 (de)
JP (1) JP2688416B2 (de)
DE (1) DE3862306D1 (de)
FR (1) FR2609474B1 (de)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE9703314D0 (sv) * 1997-09-15 1997-09-15 Sangtec Medical Ab Capacity affinity sensor
JP4613066B2 (ja) * 2002-09-10 2011-01-12 ソルヴェイ（ソシエテ アノニム） 有機塩及び電気化学反応における試薬としてのその使用
DE10326047A1 (de) * 2003-06-10 2004-12-30 Degussa Ag Verfahren zur Herstellung alpha-substituierter Carbonsäuren aus der Reihe der alpha-Hydroxycarbonsäuren und N-substituierten-alpha-Aminocarbonsäuren
US8313634B2 (en) 2009-01-29 2012-11-20 Princeton University Conversion of carbon dioxide to organic products
US20110114502A1 (en) * 2009-12-21 2011-05-19 Emily Barton Cole Reducing carbon dioxide to products
US8500987B2 (en) 2010-03-19 2013-08-06 Liquid Light, Inc. Purification of carbon dioxide from a mixture of gases
US8845877B2 (en) 2010-03-19 2014-09-30 Liquid Light, Inc. Heterocycle catalyzed electrochemical process
US8721866B2 (en) 2010-03-19 2014-05-13 Liquid Light, Inc. Electrochemical production of synthesis gas from carbon dioxide
US8524066B2 (en) 2010-07-29 2013-09-03 Liquid Light, Inc. Electrochemical production of urea from NOx and carbon dioxide
US8845878B2 (en) 2010-07-29 2014-09-30 Liquid Light, Inc. Reducing carbon dioxide to products
US8568581B2 (en) 2010-11-30 2013-10-29 Liquid Light, Inc. Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide
US8961774B2 (en) 2010-11-30 2015-02-24 Liquid Light, Inc. Electrochemical production of butanol from carbon dioxide and water
US9090976B2 (en) 2010-12-30 2015-07-28 The Trustees Of Princeton University Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction
US8562811B2 (en) 2011-03-09 2013-10-22 Liquid Light, Inc. Process for making formic acid
CA2841062A1 (en) 2011-07-06 2013-01-10 Liquid Light, Inc. Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates
CA2839004A1 (en) 2011-07-06 2013-01-10 Liquid Light, Inc. Carbon dioxide capture and conversion to organic products
CN114381749B (zh) * 2022-01-10 2023-05-30 万华化学集团股份有限公司 一种合成薄荷甲酸的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0189120A1 (de) * 1985-01-21 1986-07-30 Consiglio Nazionale Delle Ricerche Verfahren für die Elektrocarboxylierung von Carbonylverbindungen zur Herstellung von alpha-Hydroxycarbonylsäuren

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4028201A (en) * 1972-11-13 1977-06-07 Monsanto Company Electrolytic monocarboxylation of activated olefins
US4072583A (en) * 1976-10-07 1978-02-07 Monsanto Company Electrolytic carboxylation of carbon acids via electrogenerated bases
FR2566434B1 (fr) * 1984-06-21 1986-09-26 Poudres & Explosifs Ste Nale Procede d'electrosynthese d'acides carboxyliques

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0189120A1 (de) * 1985-01-21 1986-07-30 Consiglio Nazionale Delle Ricerche Verfahren für die Elektrocarboxylierung von Carbonylverbindungen zur Herstellung von alpha-Hydroxycarbonylsäuren

Also Published As

Publication number Publication date
DE3862306D1 (de) 1991-05-16
JP2688416B2 (ja) 1997-12-10
FR2609474B1 (fr) 1991-04-26
JPS63190186A (ja) 1988-08-05
EP0277048B1 (de) 1991-04-10
FR2609474A1 (fr) 1988-07-15
US4824532A (en) 1989-04-25

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