EP2964810B1 - Procédé électrochimique de couplage de phénol à aniline - Google Patents

Procédé électrochimique de couplage de phénol à aniline Download PDF

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EP2964810B1
EP2964810B1 EP14705353.2A EP14705353A EP2964810B1 EP 2964810 B1 EP2964810 B1 EP 2964810B1 EP 14705353 A EP14705353 A EP 14705353A EP 2964810 B1 EP2964810 B1 EP 2964810B1
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Prior art keywords
alkyl
aryl
cycloalkyl
heteroaryl
aniline
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EP2964810A1 (fr
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Katrin Marie DYBALLA
Robert Franke
Dirk Fridag
Siegfried R. Waldvogel
Bernd Elsler
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Evonik Operations GmbH
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Evonik Degussa GmbH
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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
    • C25B3/29—Coupling reactions
    • 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 following invention relates to an electrochemical process for the coupling of phenol and aniline.
  • anilines and phenols are used in this application as a generic term and thus also includes substituted aminoaryls and substituted hydroxyaryls.
  • a major disadvantage of the above-mentioned methods of phenol-aniline cross-coupling is the frequent need for dry solvents and exclusion of air. Furthermore, often large amounts of partially toxic oxidizing agents are used. During the reaction often occur toxic by-products, which are consuming separated from the desired product and expensive must be disposed of. Dwindling raw materials (eg, boron and bromine in the case of transition-metal-catalyzed cross-coupling) and the increasing relevance of environmental protection are raising the price of such transformations. Especially when using multi-level sequences, a change of different solvents is necessary.
  • the object of the following invention was to provide an electrochemical process in which anilines and phenols can be coupled together, and can be dispensed with multi-stage syntheses using metallic reagents.
  • the object is achieved by a method according to the invention.
  • the method steps a ') to c') can be carried out in any order.
  • the method steps a ") to c") can be carried out in any order.
  • substituents R 1 to R 50 are independently selected from the group of hydrogen, hydroxyl, (C 1 -C 12 ) -alkyl, (C 1 -C 12 ) -Heteroalkyl, (C 4 -C 14 ) -aryl , (C 4 -C 14 ) -aryl (C 1 -C 12 ) -alkyl, (C 4 -C 14 ) -aryl-O- (C 1 -C 12 ) -alkyl, (C 3 -C 14 ) Heteroaryl, (C 3 -C 14 ) heteroaryl (C 1 -C 12 ) alkyl, (C 3 -C 12 ) cycloalkyl, (C 3 -C 12 ) cycloalkyl (C 1 -C 12 ) -Alkyl, (C 3 -C 12 ) -heterocycloalkyl, (C 3 -C 12 ) -heterocycloalkyl
  • Alkyl is a non-branched or branched aliphatic radical.
  • Aryl for aromatic (hydrocarbon) radicals preferably having up to 14 carbon atoms, for.
  • phenyl C 6 H 5 -
  • naphthyl C 10 H 7 -
  • anthryl C 14 H 9 -
  • phenyl preferably phenyl.
  • Cycloalkyl for saturated cyclic hydrocarbons containing exclusively carbon atoms in the ring is
  • Heteroalkyl for a non-branched or branched aliphatic radical which may contain one to four, preferably one or two, heteroatoms selected from the group consisting of N, O, S and substituted N.
  • Heteroaryl is an aryl radical in which one to four, preferably one or two, carbon atoms may be replaced by heteroatoms selected from the group consisting of N, O, S and substituted N, wherein the heteroaryl radical may also be part of a larger condensed ring structure.
  • Heterocycloalkyl for saturated cyclic hydrocarbons which may contain one to four, preferably one or two, heteroatoms selected from the group consisting of N, O, S and substituted N.
  • heteroaryl radical which may be part of a fused ring structure is preferably understood systems in which fused five- or six-membered rings are formed, e.g. Benzofuran, isobenzofuran, indole, isoindole, benzothiophene, benzo (c) thiophene, benzimidazole, purine, indazole, benzoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, acridine.
  • the abovementioned substituted N can be monosubstituted; the alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups can be monosubstituted or polysubstituted, particularly preferably monosubstituted, disubstituted or trisubstituted by radicals selected from the group consisting of selected from among hydrogen, (C 1 -C 14 ) -alkyl, (C 1 -C 14 ) -heteroalkyl, (C 4 -C 14 ) -aryl, (C 4 -C 14 ) -aryl (C 1 -C 14) Alkyl, (C 3 -C 14 ) -heteroaryl, (C 3 -C 14 ) -heteroaryl (C 1 -C 14) -alkyl, (C 3 -C 12 ) -cycloalkyl, (C 3 -C 12 ) -Cyclo
  • R 1 , R 2 , R 11 , R 12 , R 21 , R 22 , R 32 , R 33 , R 43 , R 44 are selected from: -H, and / or an in " Greene's Protective Groups in Organic Synthesis "by PGM Wuts and TW Greene, 4th edition, Wiley Interscience, 2007, pp. 696-926 protecting groups described for amino functions.
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 34 , R 35 , R 36 , R 37 , R 40 , R 41 , R 42 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 are selected from the group of hydrogen, hydroxyl, (C 1 -C 12 ) -alkyl, (C 1 -C 12 ) -Heteroalkyl, (C 4 -C 14 ) -aryl, (C 4 -C 14 ) -aryl (C 1 -C 12 ) -alkyl, O- (C 1 -C 12 ) -al
  • R 1 , R 2 , R 11 , R 12 , R 21 , R 22 , R 32 , R 33 , R 43 , R 44 are selected from: -H, (C 1 -C 12 ) acyl.
  • the process can be performed on different carbon (glassy carbon, boron-doped diamond, graphites, carbon fibers, nanotubes, etc.), metal oxide and metal electrodes. Current densities in the range of 1-50 mA / cm 2 are applied.
  • the workup and recovery of the biaryls is very simple and takes place after completion of the reaction according to common separation methods.
  • the electrolyte solution is first distilled and recovered the individual compounds in the form of different fractions separately. Further purification can be carried out, for example, by crystallization, distillation, sublimation or chromatographic.
  • electrolysis is carried out in the usual, known in the art electrolysis cells. Suitable electrolysis cells are known to the person skilled in the art.
  • One aspect of the invention is that the yield of the reaction on the difference of the oxidation potentials ( ⁇ E) can be controlled of the two substrates.
  • Another aspect of the invention is that the difference of the two oxidation potentials ( ⁇ E), influence on the used solvent or solvent mixtures can be.
  • the difference between the two oxidation potentials can ( ⁇ E) are moved to the desired range by appropriate choice of solvent / solvent mixture.
  • the aniline has the higher oxidation potential (not according to the invention)
  • the aniline is used at least twice the amount of phenol.
  • the ratio of phenol to aniline is in the range from 1: 2 to 1: 4.
  • the phenol in one variant of the process, is used at least twice as much as the aniline.
  • the ratio of aniline to phenol is in the range from 1: 2 to 1: 4.
  • the conductive salt is selected from the group of alkali metal, alkaline earth metal, tetra (C 1 -C 6 alkyl) ammonium, 1,3-di (C 1 -C 6 alkyl) imidazolium or tetra (C 1 -C 6 alkyl) phosphonium salts.
  • the counterions of the conducting salts are selected from the group consisting of sulfate, hydrogensulfate, alkylsulfates, arylsulfates, alkylsulfonates, arylsulfonates, halides, phosphates, carbonates, alkylphosphates, alkylcarbonates, nitrate, tetrafluoroborate, hexafluorophosphate, hexafluorosilicate, fluoride and perchlorate.
  • the conductive salt is selected from tetra (C 1 -C 6 -alkly) ammonium salts and the counterion selected from sulfate, alkyl sulfate, aryl sulfate.
  • reaction solution is free of fluorinated compounds.
  • reaction solution is free of transition metals.
  • the reaction solution is free of organic oxidizing agents.
  • the phenol and the aniline are selected from: Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb:
  • substituents R 1 to R 50 are independently selected from the group of hydrogen, hydroxyl, (C 1 -C 12 ) -alkyl, (C 1 -C 12 ) -Heteroalkyl, (C 4 -C 14 ) -aryl , (C 4 -C 14 ) -aryl (C 1 -C 12 ) -alkyl, (C 4 -C 14 ) -aryl-O- (C 1 -C 12 ) -alkyl, (C 3 -C 14 ) Heteroaryl, (C 3 -C 14 ) heteroaryl (C 1 -C 12 ) alkyl, (C 3 -C 12 ) cycloalkyl, (C 3 -C 12 ) cycloalkyl (C 1 -C 12 ) -Alkyl, (C 3 -C 12 ) -heterocycloalkyl, (C 3 -C 12 ) -heterocycloalkyl
  • Alkyl is a non-branched or branched aliphatic radical.
  • Aryl for aromatic (hydrocarbon) radicals preferably having up to 14 carbon atoms, for.
  • phenyl C 6 H 5 -
  • naphthyl C 10 H 7 -
  • anthryl C 14 H 9 -
  • phenyl preferably phenyl.
  • Cycloalkyl for saturated cyclic hydrocarbons containing exclusively carbon atoms in the ring is
  • Heteroalkyl for a non-branched or branched aliphatic radical which may contain one to four, preferably one or two, heteroatoms selected from the group consisting of N, O, S and substituted N.
  • Heteroaryl is an aryl radical in which one to four, preferably one or two, carbon atoms may be replaced by heteroatoms selected from the group consisting of N, O, S and substituted N, wherein the heteroaryl radical may also be part of a larger condensed ring structure.
  • Heterocycloalkyl for saturated cyclic hydrocarbons which may contain one to four, preferably one or two, heteroatoms selected from the group consisting of N, O, S and substituted N.
  • Heteroaryl radical which may be part of a fused ring structure, is preferably understood to mean systems in which fused five- or six-membered rings are formed, for example Benzofuran, isobenzofuran, indole, isoindole, benzothiophene, benzo (c) thiophene, benzimidazole, purine, indazole, benzoxazole, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, acridine.
  • the abovementioned substituted N can be monosubstituted; the alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups can be monosubstituted or polysubstituted, particularly preferably monosubstituted, disubstituted or trisubstituted by radicals selected from the group consisting of selected from among hydrogen, (C 1 -C 14 ) -alkyl, (C 1 -C 14 ) -heteroalkyl, (C 4 -C 14 ) -aryl, (C 4 -C 14 ) -aryl (C 1 -C 14) Alkyl, (C 3 -C 14 ) -heteroaryl, (C 3 -C 14 ) -heteroaryl (C 1 -C 14 ) -alkyl, (C 3 -C 12 ) -cycloalkyl, (C 3 -C 12 ) -Cy
  • R 1 , R 2 , R 11 , R 12 , R 21 , R 22 , R 32 , R 33 , R 43 , R 44 are selected from: -H, and / or an in " Greene's Protective Groups in Organic Synthesis "by PGM Wuts and TW Greene, 4th edition, Wiley Interscience, 2007, pp. 696-926 protecting groups described for amino functions.
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 34 , R 35 , R 36 , R 37 , R 40 , R 41 , R 42 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 are selected from the group of hydrogen, hydroxyl, (C 1 -C 12 ) -alkyl, (C 1 -C 12 ) -Heteroalkyl, (C 4 -C 14 ) -aryl, (C 4 -C 14 ) -aryl (C 1 -C 12 ) -alkyl, O- (C 1 -C 12 ) -al
  • R 1 , R 2 , R 11 , R 12 , R 21 , R 22 , R 32 , R 33 , R 43 , R 44 are selected from: -H and / or (C 1 -C 12 ) acyl ,
  • a VA stand Metrohm 663 VA equipped with a ⁇ Autolab type III potentiostat was used (Metrohm AG, Herisau, Switzerland).
  • WE glassy carbon electrode, 2 mm in diameter;
  • AE glass wool rod;
  • RE Ag / AgCl in saturated LiCl / EtOH.
  • Solvent HFIP + 0-25% v / v MeOH.
  • c (aniline derivative) 151 mM
  • conductive salt Et 3 NMe O 3 SOMe (MTES),
  • MTES 0.09M.
  • TLC thin-layer chromatography
  • PSC precast plates Kieselgel 60 F254 from Merck KGaA, Darmstadt were used. The Rf values are given as a function of the solvent mixture used.
  • a cerium-molybdophosphoric acid solution was used as the dipping reagent.
  • Cerium molybdophosphoric acid reagent 5.6 g molybdophosphoric acid, 2.2 g cerium (IV) sulfate tetrahydrate and 13.3 g concentrated sulfuric acid to 200 mL water.
  • GCMS Gas chromatographic mass spectra
  • gas chromatograph GC-2010 combined with the mass detector GCMS-QP2010 from Shimadzu, Japan. It is attached to a quartz capillary column HP-1 from Agilent Technologies, USA (length: 30 m, internal diameter: 0.25 mm, film thickness of the covalently bonded stationary phase: 0.25 ⁇ m, carrier gas: hydrogen, injector temperature: 250 ° C, detector temperature: 310 ° C
  • Melting points were measured using the melting point determination device SG 2000 from HW5, Mainz and are uncorrected.
  • the elemental analyzes were prepared in the analytical department of the Institute of Organic Chemistry of Johannes Gutenberg University Mainz on a Vario EL Cube of the company Foss- Heraeus, Haunau.
  • the NMR spectroscopic investigations were carried out on multicore resonance spectrometers of the type AC 300 or AV II 400 from Bruker, Analytical Messtechnik, Düsseldorf.
  • the solvent used was CDCl3.
  • the 1 H and 13 C spectra were calibrated according to the residual content of non-deuterated solvent according to the NMR Solvent Data Chart from Cambridge Isotopes Laboratories, USA.
  • the assignment of the 1 H and 3 C signals was carried out in part by means of H, H-COZY, H, H-NOESY, H, C-HSQC and H, C-HMBC spectra.
  • the chemical shifts are given as ⁇ values in ppm.
  • AAV1 Instructions for electrochemical cross-coupling
  • the electrolysis is carried out in accordance with AAV1 in an undivided glass beaker cell with glassy carbon electrodes.
  • AAV1 undivided glass beaker cell with glassy carbon electrodes.
  • the electrolysis is carried out in accordance with AAV1 in an undivided glass beaker cell with glassy carbon electrodes.
  • 0.43 g (2.15 mmol, 1.0 equiv.) Of 4-bromo-3-methoxyaniline and 0.89 g (6.45 mmol, 3.0 equiv.) Of 4-methyl guaiacol are dissolved in 25 mL HFIP, 0.77 g MTBS are added and the electrolyte is transferred to the electrolysis cell , The solvent and unreacted Eduktmengen be removed after the electrolysis under reduced pressure, the crude product on silica gel 60 as a "flash chromatography" in the eluent 9: 1 (CH: EE) and the product obtained as a brown oil.
  • the electrolysis is carried out in accordance with AAV1 in an undivided glass beaker cell with glassy carbon electrodes.
  • 0.52g (3.79 mmol, 1.0 equiv.) Of 4-methylguaiacol and 2.22 g (11:37 mmol, 3.0 equiv.) Of N - (3,4-dimethoxyphenyl) acetamide in 25 ml of HFIP dissolved 0.77 g MTBS added and the electrolyte in transferred the electrolysis cell.
  • the solvent and unreacted Eduktmengen be after electrolysis under reduced pressure
  • the crude product was purified on silica gel 60 as a "flash chromatography" in the eluent 2: 3 (CH: EE) + 1% AcOH and the product obtained as a viscous, light yellow oil.
  • the electrolysis is carried out in accordance with AAV1 in an undivided glass beaker cell with glassy carbon electrodes. To this is dissolved 0.75 g (5.00 mmol, 1.0 equiv.) Of 3-methyl-4- (methylethyl) phenol and 2.93 g (15.00 mmol, 3.0 equiv.) Of N - (3,4-dimethoxyphenyl) acetamide in 33 mL HFIP, 1.02 g MTBS added and the electrolyte transferred to the electrolysis cell.
  • the electrolysis is carried out in accordance with AAV1 in an undivided glass beaker cell with glassy carbon electrodes.
  • 0.60 g (3.79 mmol, 1.0 equiv.) Of 2-chloro-3-hydroxy-4-methylaniline and 1.57 g (11.36 mmol, 3.0 equiv.) Of 4-methylguajacol are dissolved in 25 mL HFIP, 0.77 g of MTBS are added and the electrolyte transferred to the electrolysis cell.
  • the FIG. 1 shows a reaction apparatus in which the coupling reaction described above can be carried out.
  • the apparatus comprises a nickel cathode (1) and an anode of boron-doped diamond (BDD) on silicon or another carrier material or another electrode material (5) known to the person skilled in the art.
  • BDD boron-doped diamond
  • the apparatus can be cooled by means of the cooling jacket (3).
  • the arrows indicate the flow direction of the cooling water.
  • the reaction space is closed with a Teflon stopper (2).
  • the Reaction mixture is mixed through a magnetic stir bar (7).
  • the apparatus is closed by screw clamps (4) and seals (6).
  • the FIG. 2 shows a reaction apparatus in which the coupling reaction described above can be carried out on a larger scale.
  • the apparatus comprises two glass flanges (5 '), on which are pressed by screw clamps (2') and seals electrodes (3 ') of boron-doped diamond (BDD) coated carrier materials or other, known in the art, electrode materials.
  • the reaction space can be provided with a reflux condenser via a glass sleeve (1 ').
  • the reaction mixture is mixed with the aid of a magnetic stirring bar (4 ').
  • FIGS. 4 to 10 each show the change in the oxidation potential (V) as a function of the proportion of methanol (MeOH), which was added to the solvent 1,1,1,3,3,3-hexafluoroisopropanol (HFIP).
  • V oxidation potential
  • MeOH methanol
  • HFIP 1,1,1,3,3,3-hexafluoroisopropanol

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Claims (6)

  1. Procédé électrochimique de couplage de phénol à de l'aniline, comprenant les étapes suivantes :
    a") introduction, dans un réacteur, d'un solvant ou d'un mélange de solvants, ainsi que d'un sel conducteur,
    b") introduction, dans le réacteur, d'une aniline ayant un potentiel d'oxydation EOX 1,
    c") introduction dans le réacteur d'un phénol ayant un potentiel d'oxydation EOX 2, où on a : E Ox 2 > E Ox 1 et E Ox 2 − E Ox 1 = ΔE ,
    Figure imgb0047
     le phénol étant ajouté en excès par rapport à l'aniline, et le solvant ou le mélange de solvants étant choisi de façon que ΔE soit compris dans la plage de 10 mV à 450 mV,
    d") mise en place de deux électrodes dans la solution réactionnelle,
    e") application d'une tension aux électrodes,
    f") couplage du phénol et de l'aniline,
    le phénol et l'aniline étant couplés par l'intermédiaire d'un couplage C,C.
  2. Procédé selon la revendication 1, dans lequel le phénol est utilisé en une quantité au moins double par rapport à celle de l'aniline.
  3. Procédé selon l'une des revendications 1 ou 2, dans lequel le rapport de l'aniline au phénol est compris dans la plage de 1:2 à 1:4.
  4. Procédé selon l'une des revendications 1 à 3, dans lequel le solvant ou le mélange de solvants est choisi de façon que ΔE soit compris dans la plage de 20 mV à 400 mV.
  5. Procédé selon l'une des revendications 1 à 4, dans lequel la solution réactionnelle est exempte d'oxydants organiques.
  6. Procédé selon l'une des revendications 1 à 5, dans lequel le phénol et l'aniline sont choisis parmi : Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb :
    Figure imgb0048
    Figure imgb0049
    Figure imgb0050
    Figure imgb0051
    Figure imgb0052
     où les substituants R1 à R50 sont choisis indépendamment les uns des autres dans le groupe consistant en l'hydrogène, les groupes hydroxyle, alkyle en C1-C12, hétéroalkyle en C1-C12, aryle en C4-C14, (aryle en C4-C14) - (alkyle en C1-C12), (aryle en C4-C14) -O- (alkyle en C1-C12), hétéroaryle en C3-C14, (hétéroaryle en C3-C14)-(alkyle en C1-C12), (cycloalkyle en C3-C12, (cycloalkyle en C3-C12) - (alkyle en C1-C12), hétérocycloalkyle en C3-C12, (hétérocycloalkyle en C3-C12) - (alkyle en C1-C12), 0-(alkyle en C1-C12), O-(hétéroalkyle en C1-C12), O-(aryle en C4-C14), O-(aryle en C4-C14) - (alkyle en C1-C14), O-(hétéroaryle en C3-C14), O-(hétéroaryle en C3-C14)-(alkyle en C1-C14), O- (cycloalkyle en C3-C12), O-(cycloalkyle en C3-C12) - (alkyle en C1-C12), 0-(hétérocycloalkyle en C3-C12), O-(hétérocycloalkyle en C3-C12) - (alkyle en C1-C12), halogéno, S- (alkyle en C1-C12), S- (hétéroalkyle en C1-C12), S- (aryle en C4-C14), S-(aryle en C4-C14) - (alkyle en C1-C14), S- (hétéroaryle en C3-C14), S-(hétéroaryle en C3-C14) - (alkyle en C1-C14), S-(cycloalkyle en C3-C12), S-(cycloalkyle en C3-C12)-(alkyle en C1-C12), S-(hétérocycloalkyle en C3-C12), acyle en C1-C12, aroyle en C4-C14, (aroyle en C4-C14)-(alkyle en C1-C14), hétéroaroyle en C3-C14, di (alkyle en C1-C14) phosphoryle, di (aryle en C4-C14) phosphoryle, alkylsulfonyle en C3-C12, cycloalkylsulfonyle en C3-C12, arylsulfonyle en C4-C12, (alkyle en C1-C12)-(arylsulfonyle en C4-C12), hétéroarylsulfonyle en C3-C12, (C=O)O-(alkyle en C1-C12), (C=O)O-(hétéroalkyle en C1-C12), (C=O)O-(aryle en C4-C14),
    où
    hétéroalkyle désigne un radical aliphatique qui contient un à quatre hétéroatomes choisis parmi N, 0, S et N substitué,
    hétéroaryle désigne un radical aryle dans lequel un à quatre atomes de carbone sont remplacés par des hétéroatomes choisis parmi N, 0, S et N substitué,
    hétérocycloalkyle désigne un radical cycloalkyle qui contient un à quatre hétéroatomes choisis parmi N, 0, S et N substitué,
    les N substitués peuvent être substitués une fois, les groupes alkyle, hétéroalkyle, cycloalkyle, hétérocycloalkyle, aryle et hétéroaryle peuvent être substitués une ou plusieurs fois, par des radicaux choisis parmi l'atome d'hydrogène, les groupes alkyle en C1-C14, hétéroalkyle en C1-C14, aryle en C4-C14, (aryle en C4-C14) - (alkyle en C1-C14), hétéroaryle en C3-C14, (hétéroaryle en C3-C14) - (alkyle en C1-C14), cycloalkyle en C3-C12, (cycloalkyle en C3-C12) - (alkyle en C1-C14), hétérocycloalkyle en C3-C12, (hétérocycloalkyle en C3-C12) - (alkyle en C1-C14), CF3, halogéno, halogènalkyle en C1-C10, hydroxy, alcoxy en C1-C14, aryloxy en C4-C14, 0-(alkyle en C1-C14) - (aryle en C4-C14), hétéroaryloxy en C3-C14, N (alkyle en C1-C14)2, N (aryle en C4-C14)2, N (alkyle en C1-C14) - (aryle en C4-C14), et
    les combinaisons suivantes étant possibles : Aniline Ia, IIa, IIIa, IVa, Va Phénol Ib, IIb, IIIb, IVb, Vb
EP14705353.2A 2013-03-07 2014-02-19 Procédé électrochimique de couplage de phénol à aniline Not-in-force EP2964810B1 (fr)

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DE102013203869 2013-03-07
DE102014202274.6A DE102014202274B4 (de) 2013-03-07 2014-02-07 Elektrochemisches Verfahren zur Kupplung von Phenol mit Anilin
PCT/EP2014/053231 WO2014135371A1 (fr) 2013-03-07 2014-02-19 Procédé électrochimique de couplage de phénol à aniline

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DE102014202274B4 (de) 2016-11-10
JP6113308B2 (ja) 2017-04-12
EP2964810A1 (fr) 2016-01-13
US20160017504A1 (en) 2016-01-21
AR095048A1 (es) 2015-09-16
MY175639A (en) 2020-07-03
TWI588299B (zh) 2017-06-21
KR20150126645A (ko) 2015-11-12
JP2016517467A (ja) 2016-06-16
US10422047B2 (en) 2019-09-24
TW201504478A (zh) 2015-02-01
WO2014135371A1 (fr) 2014-09-12
DE102014202274A1 (de) 2014-09-25
SG11201507145YA (en) 2015-10-29
ES2614989T3 (es) 2017-06-02

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