EP0028430B1 - Procédé pour la préparation électroréductrice de composés organiques - Google Patents

Procédé pour la préparation électroréductrice de composés organiques Download PDF

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EP0028430B1
EP0028430B1 EP80200992A EP80200992A EP0028430B1 EP 0028430 B1 EP0028430 B1 EP 0028430B1 EP 80200992 A EP80200992 A EP 80200992A EP 80200992 A EP80200992 A EP 80200992A EP 0028430 B1 EP0028430 B1 EP 0028430B1
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group
process according
electroreduction
hydrogen atom
carbon atoms
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EP0028430A1 (fr
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Wilhelmus Joannes Maria Van Tilborg
Cornelis Jacobus Smit
Rainer Engels
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Shell Internationale Research Maatschappij BV
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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
    • C25B3/20—Processes
    • C25B3/25—Reduction

Definitions

  • the present invention relates to electrochemical reactions which can be carried out suitably in a nonaqueous or aprotic environment.
  • the present invention relates in particular to electrochemical reductions, e.g. electrocarboxylations, which can be carried out in an aprotic environment in undivided cells.
  • electrochemical processes require the simultaneous occurrence of cathodic and anodic reactions. Since electrochemical processes are normally aimed at the production of preferably one compound at one particular electrode (the working electrode), less or virtually no interest is paid to the process or processes occurring simultaneously at the other electrode (counter electrode). In a number of cases, the reaction at the counter-electrode will not constitute a major problem. For instance, when the reaction at the counter-electrode occurs at a sufficiently low potential the products formed at the working electrode will not be destructed electrochemically at the counter-electrode.
  • diaphragms based on ion-exchange resins can be suitably used, but such diaphragms can not be used satisfactorily in a non- aqueous or an aprotic environment as they become very poorly conducting so that thermal damage may occur even at low current densities.
  • diaphragms based on the principle of diffusion limitation are unsuitable for use in non-aqueous, in particular in aprotic environments since the requirements to combine a high electrical conductivity with a little diffusion and sufficient mechanical strength appear to be incompatible.
  • the present invention therefore relates to a process for the electroreductive preparation of organic compounds in an undivided cell which comprises at the one electrode the electroreduction of an organic compound and as reaction at the counter-electrode the oxidation of anions of one or more compounds according to the general formula AB, wherein A represents an alkali or alkaline earth metal moiety; a group of formula wherein each of R 1 , R 2 , R 3 and R 4 which may be the same or different, represents a hydrogen atom, an alkyl group of up to 8 carbon atoms, or an (alk)aryl group; or a pyridinium ion and B represents an azide group or a group wherein R 5 represents a hydrogen atom, a group wherein R 6 represents a hydrogen atom, an alkyl group of up to 8 carbon atoms or a group A, or a group -CH20R7, wherein R 7 represents a hydrogen atom, an alkyl group of up to 8 carbon atoms, or an (
  • the present invention is of particular interest in that the products obtained at the counter-electrode in the electrooxidation step (i.e. carbon dioxide and nitrogen) in an undivided cell do not interfere adversely with the products obtained in the electroreduction step and are also of no environmental concern.
  • the products obtained at the counter-electrode in the electrooxidation step i.e. carbon dioxide and nitrogen
  • formate ions is of great importance in that they provide the unique system of having both carbon dioxide and protons available in a non-aqueous or even aprotic environment which opens up wide perspectives in preparative organic electrochemistry.
  • the present invention relates in particular to a process for the electroreductive preparation of organic compounds in an undivided cell in a non-aqueous or aprotic environment which comprises as reaction at the counter-electrode the oxidation of anions of one or more compounds according to the general formula AB, wherein A represents an alkali or alkaline earth metal moiety, a group of formula wherein each of R 1 , R 2 , R 3 and R', which may be the same or different, represents an alkyl group of up to 4 carbon atoms, a phenyl group or a pyridinium ion and B represents a group wherein R 5 represents a hydrogen atom, a group wherein R 6 represents a hydrogen atom, an alkyl group of up to 8 carbon atoms or a group A, or a group -CH 2 OR 7 , wherein R 7 represents a hydrogen atom or an alkyl group of up to 8 carbon atoms.
  • A represents an alkali or alkaline earth
  • Preferred processes according to the present invention are electroreductive preparations of organic compounds in an undivided cell in non- aqueous or aprotic environments, which comprise as reaction at the counter-electrode the oxidation of anions of one or more compounds according to the general formula AB, wherein A represents a group of formula wherein each of R 1 , R 2 , R 3 and R 4 , which may the same or different, represents a methyl or ethyl group, and B represents a group wherein R 5 represents a hydrogen atom or a group wherein R 6 represents a hydrogen atom, an alkyl group of up to 4 carbon atoms or a group A.
  • Examples of preferred compounds comprise oxalates and/or formates such as di-tetraethyl ammonium oxalate (DTEAOx) and tetraethyl ammonium formate (TEAF).
  • DTEAOx di-tetraethyl ammonium oxalate
  • electrocarboxylation reactions i.e. reactions in which carbon dioxide is reacted with electro-generated (carb)-anions.
  • Suitable electrocarboxylation reactions comprise the carboxylations of activated olefins, imines, and related species such as azo- compounds, ketones as well as of halogen compounds.
  • Preferred electrocarboxylations are those wherein an activated olefine is the compound to be reduced electrochemically.
  • Activated olefins which can be electrocarboxylated using the process according to the present invention can be represented by the general formula wherein R 8 , R 9 and R 10 , which may the same or different, each represents a hydrogen atom, an alkyl group of up to 8 carbon atoms, a phenyl group which may be substituted by one or more halogen atoms and/or lower alkyl groups or a group A 1 ; and A 1 represents a group -CN or a group wherein R" represents an alkyl group of up to 8 carbon atoms, or a phenyl group which may be substituted with one or more halogen atoms and/or lower alkyl groups and n is 0 or 1.
  • Preferred compounds according to the general formula I to be used in the process according to the present invention are those wherein A 1 represents a group -CN, a group wherein R11 represents a methyl group and n is 0 or 1, or a phenyl group and each of R 8 , R 9 and R 10 represents a hydrogen atom or a lower alkyl group or at least one of R 8 , R 9 and R 10 represents a group A'.
  • Especially preferred compounds according to the general formula I to be used in the process according to the present invention are those which possess two groups A 1 . Examples of preferred compounds comprise dimethyl maleate, acrylonitrile methyl vinyl ketone and alpha-methyl styrene; dimethyl maleate being especially preferred.
  • the electrocarboxylations according to the present invention can be performed using carbon dioxide generated at the anode as the sole carbon dioxide source. If desired, the electrocarboxylations can also be performed using additional carbon dioxide. Even in those events wherein a large molar excess of non-electrochemically generated carbon dioxide is used, the electrooxidation of the ' anions according to the general formula AB still generates either potential reactants (carbon dioxide), or harmless co-products (nitrogen). Moreover, the formate and oxalate ions appear to be oxidized at rather low potential (at about +1.2 V vs SCE and +0.2 V vs SCE respectively) which widens the range of electroreduction reactions applicable.
  • the products obtained by the electrocarboxylations according to the present invention are (poly)carboxylic acids.
  • the exact nature of the products depends to some extent on the particular reaction conditions and electrodes used.
  • Examples of imines which can be suitably electrocarboxylated comprise (substituted) benzalanilines which are converted into the corresponding alpha-phenyl phenyl glycines.
  • Suitable ketones comprise aromatic ketones, such as acetophenone and substituted acetophenones, benzophenone and related compounds.
  • the electrocarboxylation of aromatic ketones affords alpha-aryl-alpha-hydroxy acids as well as minor amounts of the corresponding pinacols.
  • the process according to the present invention is also of great interest for the preparation of carboxylic acids from the corresponding halogen compounds.
  • 1-bromo-2-methyl pentane could be converted almost quantitatively into 3-methyl hexanoic acid using tetraethyl ammonium oxalate as the compound AB as well as the conducting salt.
  • acid chlorides can be converted using the process according to the present invention. For instance, pivaloyl chloride was converted in a fair yield to pivalic acid ( analysesd as methyl pivalate).
  • the present invention also relates to non-carboxylating electroreductions.
  • suitable compounds which can be reduced electrochemically without the introduction of carbon dioxide (whether electrochemically generated or not) into the intermediate to give a carboxylated final product, comprise sulphonium salts, especially aromatic sulphonium salts such as (p-nitro)tosyl- sulphonium salts, and sulphonamides and 1,2-dihaloalkanes, such as 1,2-dibromo-1,2-diphenylethane and related compounds.
  • a further example comprises the electroreduction of a bis(substituted) sulphonamide of a macrocyclic (heterocyclic)polyether, especially 1,10 - bis(p - toluene sulphonyl) - 1,10 - diaza - 4,7,13,16 - tetraoxacyclooctadecane into 1,10 - diaza - 4,7,13,16 - tetraoxacyclooctadecane (also known as 1,10 diaza - 18 - crown - 6) in almost quantitative yields using tetraethyl ammonium formate as the compound AB as well as conducting salt.
  • a bis(substituted) sulphonamide of a macrocyclic (heterocyclic)polyether especially 1,10 - bis(p - toluene sulphonyl) - 1,10 - diaza - 4,7,13,16 - te
  • the process according to the present invention will normally be carried out in the presence of a solvent for the compound to be electroreduced as well as for the compound AB.
  • a solvent for the compound to be electroreduced as well as for the compound AB.
  • the choice of the solvent to be applied will depend mainly on the kind of electroreduction evisaged. For instance, when electrocarboxylation reactions are to be carried out, the solvent should be non-aqueous and preferably aprotic. Moreover, the solvent applied should preferably have a fairly high dielectric constant in order to lower the electrical resistance within the cell.
  • Suitable solvents comprise ethers such as dimethoxy ethane, diethyl ether, tetrahydrofuran and macrocyclic polyethers such as for instance the so-called crown ethers (1,4,7,10,13,16 - tetraoxacyclooctadecane and related compounds), chlorinated or fluorinated hydrocarbons, such as dichloromethane and carbon tetrachloride, nitriles such as acetonitrile, lower alkanols such as methanol or ethanol, formamides such as dimethyl formamide, sulpholane and alkylsubstituted sulpholanes, organic carbonates such as ethylene carbonate and propylene carbonate, nitromethane, N-methyl pyrolidone and hexamethylene phosphortriamide.
  • ethers such as dimethoxy ethane, diethyl ether, tetrahydrofuran and macrocyclic polyethers
  • aprotic As well as of protic solvents.
  • the solvents described hereinabove can be used suitably, preference being given to the use of lower alkanols such as methanol and ethanol.
  • lower alkanols such as methanol and ethanol.
  • the presence of water even in amounts of up to 50% v, calculated on total solvent, can be tolerated.
  • the amount of water present is rather small, e.g. less than 10% v.
  • the compound AB apart from being a reagent also will function as a supporting electrolyte.
  • the compound AB when it is dissolved at the beginning of the electrochemical process it will have a better supporting function. It is also possible to introduce a further supporting electrolyte. Use can be made of the supporting electrolytes which are well-known in the art.
  • salts of amines or quarternary ammonium salts such as tetraalkyl ammonium, heterocyclic and (alk) aryl ammonium salts, the corresponding anions comprising inorganic as well as organic anions, e.g. phosphates, halides, perchlorates, sulphates, arylsulphonates or alkylsulphonates.
  • the amount of additional supporting electrolyte present in the reaction mixture may vary within wide limits. Amounts up to 50% w on solvent/reagent applied can be used, suitable concentrations often being in the range of from 0.5% w to 15% w.
  • mixtures of two or more compounds according to the general formula AB as well as mixtures comprising at least one compound according to the general formula AB and at least one additional supporting electrolyte can be suitably used.
  • compounds according to the general formula AB an oxalate (i.e. a compound wherein B represents a group wherein R 5 represents a group wherein R 6 is as defined hereinbefore) and a formate (i.e. a compound wherein B represents a group wherein R 5 represents a hydrogen atom) are used
  • advantage can be taken from both a carbon dioxide and a proton source within the same reaction mixture. This is of special importance for electrocarboxylation reactions as the presence of protons may influence the composition of the final products.
  • the process according to the present invention can be carried out in a one-compartment electrolysis cell, i.e. in an electrolysis cell which does not have a cell divider (membrane, diaphragm) to separate the electrodes.
  • the process can be carried out batch-wise or (semi)-continuously.
  • One-compartment cells especially suited for continuous operation comprise the so-called capillary gap cells. These cells consist of a stack of circular electrode plates separated from each other by spacers and provided with a central bore. The electrolyte is pumped through the central hole and is forced to flow through the narrow gap between the electrode plates. A constant potential applied over the stack produces a dipolar electrode arrangement, each capillary gap thus serving as a separate cell.
  • capillary gap cell such as the pump cell (rotation of one of the circular electrode plates causes the electrolyte to flow outwards through the gap, the cell thus acting as its own pump) and the trickle-tower cell (consisting of layers of conducting rings separated from each other by a non-conducting gauze while the electrolyte is sprayed over the top of the column and trickles down over the rings whilst a certain voltage is maintained over the column) can be used to carry out the process according to the present invention.
  • the pump cell rotation of one of the circular electrode plates causes the electrolyte to flow outwards through the gap, the cell thus acting as its own pump
  • trickle-tower cell consisting of layers of conducting rings separated from each other by a non-conducting gauze while the electrolyte is sprayed over the top of the column and trickles down over the rings whilst a certain voltage is maintained over the column
  • the electrodes to be used in the process according to the present invention can be of any electrode material which is relatively inert under the reaction conditions. Suitable anodes are those comprising platinum or carbon although other materials (e.g. lead dioxide) can be used as well. Cadmium, lead, mercury and mercurated lead are very good materials for the cathode to be used in the process according to the present invention although other materials can be used as well. Very good results can be obtained using a platinum or carbon anode and a lead or mercurated lead cathode.
  • the choice of the electrodes will also depend to some extent on the electroreduction envisaged taking into account the oxidation of especially oxalate and/or formate anions at the anode. Also impurities present in one or both electrodes may have some impact on the products obtained.
  • the process according to the present invention can be carried out in a wide range of temperatures. It has been found that ambient temperatures can be suitably applied but higher as well as lower temperatures (e.g between +80°C and -20°C) are by no means excluded. It is sometimes found that temperatures less than ambient are to be preferred from a yield point of view. It may then be necessary to cool the reaction medium concerned. Normally, good results are obtained when the electrochemical process is carried out at ambient temperature or slightly below.
  • electrocarboxylation reactions can be carried out advantageously when carbon dioxide is available at atmospheric or higher pressures. Pressures up to 100 bar can be suitably applied, preference being given to pressures up to 50 bar. As discussed hereinbefore, it is also possible to carry out the electrocarboxylation reactions without the presence of an external carbon dioxide source when oxalates and/or formates are used as the compounds to be electro-oxidized. Non-carboxylating electroreduction reactions are normally carried out at autogeneous pressure, although higher pressures can be used as well.
  • the products obtained according to the process according to the present invention can be recovered by a variety of procedures. These procedures are well-known in the art and depend on the particular type of product to be recovered. For instance, in electrocarboxylation processes it may be useful to convert the acids produced into the corresponding alkyl esters by treatment with an alkyl halide such as methyl iodide. It may then be easier to separate the esters produced from the starting materials by chromatographic techniques or by distillation extraction or a combination of such recovery techniques. It is also possible to treat the acids obtained with a suitable base and extracting the salts obtained from the reaction mixture. When macro(hetero) cyclic polyethers are produced according to the electrochemical process according to the present invention use can be made of the well-known complexing aspects of such products for their recovery in a high yield and with a high degree of purity.
  • carboxylic acids can be used in the preparation of the corresponding esters which can be used per se, e.g. as plasticizers or serve as starting materials for the preparation of polyesters by reacting them with the appropriate polyalcohols.
  • Macro(hetero) cyclic polyethers such as 18-crown-6 or 1,10-diaza-18-crown-6 can be used for instance as solvents or as phase transfer agents.
  • the experiment described in Example II was carried out in a capillary gap cell.
  • the capillary gap cell used comprises a series of cylindrical, bipolar graphite discs with a central orifice through which the electrolyte and the appropriate substrates enter. They flow radially to the periphery of the discs where they are collected and withdrawn.
  • the carbon dioxide pressure applied was 2 bar and the flow rate of the electrolyte used was 3 I/min -1 .
  • oxalates and formates to be used in the process according to the present invention can be prepared by methods known in the art.
  • a suitable manner for preparing ditetraethyl ammonium oxalate comprises neutralizing a solution of tetraethyl ammonium hydroxide (25%) in water with the appropriate amount of oxalic acid. Water is then removed using a rotatory evaporator and the residue obtained dried further over a drying agent such as phosphorous pentoxide under reduced pressure. The dry salt obtained appears to be hygroscopic and should therefore be handled in the absence of moisture.
  • the compounds may also be prepared by reaction of tertiary amines and the appropriate alkyl esters or by cation-exchange of the carboxylic acid or the appropriate carboxylate(s).
  • the products obtained were identified by one or more of the following techniques: gas/liquid chromatography, mass spectrometry, proton magnetic resonance, 13 C magnetic resonance and infrared spectroscopy.
  • the electrocarboxylation of dimethyl maleate was carried out in a capillary gap cell as described hereinbefore.
  • the electrocarboxylation was carried out in the presence of gaseous carbon dioxide (pressure 2 bar) at a flow rate of the electrolyte system ditetraethyl ammonium oxalate/acetonitrile of 3 I.min -1 .
  • the yield of the crude polycarboxylic acids was 77%.
  • the addition of methanol caused precipitation of hexamethyl-1,1,2,3,4,4- butanehexacarboxylate (yield 20%). Distillation of the residue afforded an additional 40% yield of the following esters:
  • the electrocarboxylation of acrylonitrile (0.23 mol.l -1 ) was carried out in the vessel described in Example I using a lead cathode and a platinum anode.
  • the reduction potential was -2.14 V vs SCE and the current density was 30 mA/cm 2 .
  • the current consumed was 1.67 F.mol- 1 .
  • the compound 1-cyano- dimethyl-1,2-ethanedicarboxylate was obtained after distillation in 34% chemical yield (41% current yield).
  • Methyl vinyl ketone (0.46 mol.l -1 ) was electrocarboxylated under the conditions described in Example III at a reduction potential of -1.92 V vs SCE and at a current density of 25 mA/cm 2 . The current consumed was 0.90 F.mol -1 . After working up in the usual manner the methyl ester of levulinic acid was obtained in 4% chemical yield (9% current yield).
  • Example IV The experiment described in Example IV was repeated using alpha-methyl styrene as the compound to be electrocarboxylated.
  • the reduction potential was -2.20 V vs SCE and the current density was 18 mA/cm 2 .
  • the current consumed was 1.97 F.mol- 1 .
  • the methyl ester of 2-methyl-2-phenyl succinic acid was obtained in 19% chemical yield (19% current yield). Also a trace of the methyl ester of 3-phenyl butanoic acid could be detected.
  • Benzalaniline was electrocarboxylated in the manner as described in Example I using a lead cathode and a platinum anode.
  • concentration of benzalaniline amounted to 0.20 mol.l -1 and that of DTEAOx to 0.23 mol.l -1 , the solvent being dry acetonitrile.
  • the electrocarboxylation was performed at a reduction potential of -1.80 V vs SCE and at a current density of 20 mA/cm 2 .
  • the current consumed was 1.50 F.mol- 1 .
  • methyl-2-phenyl-2-anilino acetate was obtained in 58% chemical yield (79% current yield).
  • Example VI The experiment described in Example VI was repeated using acetophenone (0.23 mol.l -1 ) as the compound to be electrocarboxylated.
  • the reduction potential was -1.80 V vs SCE and the current density was 25 mA/cm 2 .
  • the current consumed was 1.06 F.mol- 1 .
  • the methyl ester of alphaphenyl lactic acid was obtained as the main product (40% chemical yield, 58% current yield).
  • acetophenone pinacol (2,3-dihydroxy-2,3-diphenylbutane) had been formed in 29% chemical yield (21% current yield).
  • Example VII The experiment described in Example VII was repeated using azobenzene (0.23 mol.l -1 ) as the compound to be electrocarboxylated.
  • the reduction potential was -1.31 V vs SCE and the current density was 13 mA/cm 2 .
  • the current consumed was 1.06 F.mol- 1 .
  • a mixture of the methyl esters of the mono- and dicarboxylic acid of azobenzene was obtained: :17% chemical yield (16% current yield) :40% chemical yield (38% current yield)
  • the electroreduction of p-nitrobenzyl dimethyl sulphonium chloride was performed in the vessel described in Example la. The electroreduction was carried out at room temperature using a lead cathode and a platinum anode. Methanol was used as the solvent and the concentration of the sulphonium compound amounted to 0.025 mol.l -1 whereas the concentration of the conducting salt DTEAOx amounted to 0.23 mol.l -1 .
  • the reduction potential was -1.0 V vs SCE and the current density was 3 mA/cm 2 .
  • the current consumed was 1.4 F.mol- 1 .
  • the reaction products found were para- nitrotoluene in 22% yield (55% current yield) and 4,4'-dinitrobibenzyl in 13% yield (9% current yield).

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Claims (21)

1. Un procédé pour la préparation électroréductrice de composés organiques dans une cellule non divisée qui comprend à la première électrode l'électroréduction d'un composé organique et comme réaction à l'électrode opposée l'oxydation d'anions d'un ou plusieurs composés de la formule générale AB, dans laquelle A représente une portion métal alcalin ou alcalino-terreux; un groupe de formule
Figure imgb0031
dans laquelle R1, R2, R3 et R4, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène, un groupe alcoyle ayant jusqu'à 8 atomes de carbone ou un groupe (alc)aryle; ou un ion pyridinium et B représente un groupe azide ou un groupe
Figure imgb0032
où R5 représente un atome d'hydrogène, un groupe
Figure imgb0033
où R6 représente un atome d'hydrogène, on groupe alcoyle ayant jusqu'à 8 atomes de carbone ou un groupe A, ou un groupe ―CH2OR7, où R7 représente un atome d'hydrogène, un groupe alcoyle ayant jusqu'à 8 atomes de carbone ou un groupe (alc)aryle.
2. Un procédé selon la revendication 1, dans lequel la préparation électroréductrice de composés organiques est effectuée dans une cellule non divisée dans un environnement non-aqueux ou aprotique qui comprend comme réaction à l'électrode opposée l'oxydation d'anions d'un ou plusieurs composés de la formule générale AB, où A représente une portion métal alcalin ou alcalino-terreux, un groupe de formule
Figure imgb0034
où R1, R2, R3 et R4, qui peuvent être identiques ou différents, représentent chacun un groupe alcoyle ayant jusqu'à 6 atomes de carbone, un groupe phényle ou un ion pyridinium et B représente un groupe
Figure imgb0035
où R5 représente un atome d'hydrogène, un groupe
Figure imgb0036
où R6 représente un atome d'hydrogène, un groupe alcoyle ayant jusqu'à 8 atomes de carbone ou un groupe A, ou un groupe ―CH2OR7, où R7 représente un atome d'hydrogène ou un groupe alcoyle ayant jusqu'à 8 atomes de carbone.
3. Un procédé selon la revendication 2, qui comprend comme réaction à l'électrode opposée l'oxydation d'anions d'un ou plusieurs composés de la formule générale AB, où A représente un groupe de formule
Figure imgb0037
dans laquelle R1, R2, R3 et R4, qui peuvent être identiques ou différents, représentent chacun un groupe méthyle ou éthyle et B représente un groupe
Figure imgb0038
où R5 représente un atome d'hydrogène ou un groupe
Figure imgb0039
où R6 représente un atome d'hydrogène, un groupe alcoyle ayant jusqu'à 4 atomes de carbone ou un groupe A.
4. Un procédé selon la revendication 3, qui comprend comme réaction à l'électrode opposée l'oxydation d'ions oxalate et/ou formiate.
5. Un procédé selon l'une quelconque des revendications précédentes, qui comprend comme réaction d'électroréduction l'électro- carboxylation d'oléfines activées, d'imines, de cétones ou de composés halogénés.
6. Un procédé selon la revendication 5, qui comprend l'électrocarboxylation d'une oléfine activée de la formule générale:
Figure imgb0040
dans laquelle R8, R9 et R10, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène, un groupe alcoyle ayant jusqu'à 8 atomes de carbone, un groupe phényle qui peut être substitué par un ou plusieurs atomes d'halogènes et/ou groupes alcoyle inférieur ou un groupe A1; et A1 représente un groupe -CN ou un groupe
Figure imgb0041
où R11 représente un groupe alcoyle ayant jusqu'à 8 atomes de carbone, ou un groupe phényle qui peut être substitué par un ou plusieurs atomes d'halogènes et/ou groupes alcoyle inférieur et n est 0 ou 1.
7. Un procédé selon la revendication 6, qui comprend l'électrocarboxylation de composés de la formule générale I, dans laquelle A1 représente un groupe -CN, un groupe
Figure imgb0042
où R11 représente un groupe méthyle et n est 0 ou 1, ou un groupe phényle et R8, R9 et R10 représentent chacun un atome d'hydrogène ou un groupe alcoyle inférieur ou au moins un d'entre eux représente un groupe A1.
8. Un procédé selon la revendication 7, qui comprend l'électrocarboxylation de maléate de diméthyle, d'acrylonitrile, de méthylvinylcétone ou d'alpha-méthyl styrène.
9. Une procédé selon la revendication 5, dans lequel on soumet à l'électrocarboxylation une benzaniline (substituée) ou un composé bromé ou chloré comme le 1-bromo-2-méthyl pentane ou le chlorure de pivaloyle.
10. Un procédé selon l'une quelconque des revendications 5 à 9, dans lequel l'électrocar- boxylation est effectuée en présence d'anhydride carbonique n'ayant pas été produit électrochimiquement.
11. Un procédé selon l'une quelconque des revendications 1 à 4, qui comprend l'électro- réduction de sels de sulfonium, spécialement de sels aromatiques de sulfonium, de sulfon- amides ou de 1,2-dihalogéno-alcanes.
12. Un procédé selon la revendication 11, qui comprend l'électroréduction d'un sulfonamide bis(substitué) d'un polyéther macrocyclique (hétérocyclique), spécialement du 1,10-bis(p-toluène sulfonyl)-1,10-diaza-4,7,13,16-tétra- oxacyclooctadécane.
13. Un procédé selon la revendication 11, qui comprend l'électroréduction d'un 1,2-dihalogéno-alcane, spécialement du 1,2-dibromo-1,2- diphényl éthane.
14. Un procédé selon l'une quelconque des revendications précédentes, dans lequel l'électroréduction est effectuée en présence d'un solvant inerte.
15. Un procédé selon la revendication 14, dans lequel le solvant utilisé est un éther, un hydrocarbure chloré ou fluoré, un nitrile, du méthanol, de l'éthanol, un sulfolane alcoylé, un carbonate organique, du nitrométhane, de la N-méthyl pyrrolidone ou de l'hexaméthylphos- phortriamide.
16. Un procédé selon la revendication 15, dans lequel le solvant utilisé est de l'acéto- nitrile, du diméthylformamide ou du méthanol.
17. Un procédé selon l'une quelconque des revendications précédentes, dans lequel l'électroréduction est effectuée en présence d'un électrolyte de support supplémentaire, de préférence dans une proportion comprise entre 0,5% en poids et 15% en poids.
18. Un procédé selon l'une quelconque des revendications précédentes, dans lequel la réaction est conduite à une densité de courant comprise dans l'intervalle de 5 à 1000 mA/cm2, de préférence à une densité de courant d'au moins 25 mA/cm2.
19. Un procédé selon l'une quelconque des revendications précedentes, dans lequel l'électroréduction est effectuée dans une cellule à une seul compartiment du type à intervalles capillaires.
20. Un procédé selon l'une quelconque des revendications précédentes, dans lequel on effectue l'électroréduction et utilisant une anode de platine ou de carbone et une cathode de plomb ou de plomb mercuré.
21. Un procédé selon l'une quelconque des revendications précédentes, dans lequel l'électroréduction est effectuée à la température ambiante.
EP80200992A 1979-11-01 1980-10-20 Procédé pour la préparation électroréductrice de composés organiques Expired EP0028430B1 (fr)

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JP5580837B2 (ja) 2009-01-29 2014-08-27 プリンストン ユニバーシティー 二酸化炭素の有機生成物への変換
US8500987B2 (en) 2010-03-19 2013-08-06 Liquid Light, Inc. Purification of carbon dioxide from a mixture of gases
US8721866B2 (en) 2010-03-19 2014-05-13 Liquid Light, Inc. Electrochemical production of synthesis gas from carbon dioxide
US8845877B2 (en) 2010-03-19 2014-09-30 Liquid Light, Inc. Heterocycle catalyzed electrochemical process
US8845878B2 (en) 2010-07-29 2014-09-30 Liquid Light, Inc. Reducing carbon dioxide to products
US8961774B2 (en) 2010-11-30 2015-02-24 Liquid Light, Inc. Electrochemical production of butanol from carbon dioxide and water
US8568581B2 (en) 2010-11-30 2013-10-29 Liquid Light, Inc. Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide
US9090976B2 (en) 2010-12-30 2015-07-28 The Trustees Of Princeton University Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction
PL2607349T3 (pl) 2011-12-23 2014-12-31 Soc Es De Carburos Metalicos S A Synteza elektrokarboksylowania do otrzymywania związków pośrednich użytecznych do syntezy pochodnych SPAN
US9175407B2 (en) 2012-07-26 2015-11-03 Liquid Light, Inc. Integrated process for producing carboxylic acids from carbon dioxide
US10329676B2 (en) 2012-07-26 2019-06-25 Avantium Knowledge Centre B.V. Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode
US20140206896A1 (en) 2012-07-26 2014-07-24 Liquid Light, Inc. Method and System for Production of Oxalic Acid and Oxalic Acid Reduction Products
US8858777B2 (en) 2012-07-26 2014-10-14 Liquid Light, Inc. Process and high surface area electrodes for the electrochemical reduction of carbon dioxide
US8641885B2 (en) 2012-07-26 2014-02-04 Liquid Light, Inc. Multiphase electrochemical reduction of CO2
US8845875B2 (en) 2012-07-26 2014-09-30 Liquid Light, Inc. Electrochemical reduction of CO2 with co-oxidation of an alcohol
WO2014042783A1 (fr) * 2012-09-14 2014-03-20 Liquid Light, Inc. Réduction électrochimique multiphase du co2

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US3344045A (en) * 1964-10-23 1967-09-26 Sun Oil Co Electrolytic preparation of carboxylic acids
US4028201A (en) * 1972-11-13 1977-06-07 Monsanto Company Electrolytic monocarboxylation of activated olefins
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DE3066199D1 (en) 1984-02-23
EP0028430A1 (fr) 1981-05-13

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