EP2438214B1 - Procédé de déshydrodimérisation croisée anodique d'arènes - Google Patents

Procédé de déshydrodimérisation croisée anodique d'arènes Download PDF

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Publication number
EP2438214B1
EP2438214B1 EP10724436.0A EP10724436A EP2438214B1 EP 2438214 B1 EP2438214 B1 EP 2438214B1 EP 10724436 A EP10724436 A EP 10724436A EP 2438214 B1 EP2438214 B1 EP 2438214B1
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EP
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Prior art keywords
process according
group
arenes
electrolysis
mediators
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German (de)
English (en)
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EP2438214A1 (fr
Inventor
Andreas Fischer
Itamar Michael Malkowsky
Florian Stecker
Siegfried R. Waldvogel
Axel Kirste
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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
    • C25B3/29—Coupling reactions

Definitions

  • the invention relates to a process for the preparation of biaryls, which is carried out by anodic cross-dehydrodimerization of substituted phenols with arenes in the presence of partially and / or perfluorinated mediators and a conductive salt.
  • the oxidative cross-coupling of arenes is a highly topical field of research and is characterized by (a) LJ Goossen, G. Deng, Guojun, LM Levy, in Science 2006, 313, 662 ; by DR Stuart, K. Fagnou, in Science 2007, 316, 1172 ; by Jean, J. Cantat, D. Birard, D. Bouchu, S. Canesi, in Org. Lett. 2007, 9, 2553 ; by R. Li, L. Jiang, W. Lu, in Organometallics 2006, 25, 5973 ; by A. Timothy, NR Dwight, DC Dagmara, J. Ryan, D. Brenton, in Org. Lett. 2007, 9, 3137 and by KL Hull, MS Sanford, in J. Am. Chem. Soc. 2007, 129, 11904 been described.
  • electrochemical processes have not been described in this context, despite numerous potential advantages.
  • the general strategy of oxidative cross-coupling of arenes utilizes the reactivity of a reagent with a component (A) of the coupling partners (A and B) to form an intermediate (I).
  • the entry into the reaction cascade on the first component (A) either by special neighboring groups, which allows the insertion of a strong oxidizing metal ion such as Pd 2+ in a C-H bond.
  • the subsequent cross-coupling usually uses halogen-substituted reactant (B).
  • the specific reactivity of indoles and fluorinated arenes towards transition metals can also be used for such a transformation.
  • hypervalent iodine compounds such as PIFA (phenyliodine bis (trifluoroacetate) and derivatives, upon activation with a Lewis acid, can coordinate to a ⁇ system, thus initiating the reaction sequence by electron transfer T.
  • PIFA phenyliodine bis (trifluoroacetate) and derivatives
  • Oxidative cross-coupling reactions of phenols with anilines or other electron-rich aromatic moieties can, in a few cases, be achieved either by certain Lewis acid additives such as by G. Satori, R. Maggi, F. Bigi, A. Arienti, G. Casnati, in Tetrahedron, 1992, 43, 9483 is described or achieved by prior co-crystallization. In the latter example, there is a preorganization via hydrogen bonding as it is by M. Smrcina, S. Vyskocil, AB Abbott, P. Kocovsky, J. Org. Chem. 1994, 59, 2156 ; by K. Ding, Q. Xu, Y. Wang, J. Liu, Z. Yu, B.
  • the object of the present invention is to provide a process which enables the anodic cross-dehydrodimerization of substituted aryl alcohols with arenes without having to use expensive catalysts and compounds having specific leaving groups and without generating toxic waste products.
  • This object is achieved by a process for the preparation of biaryls, wherein substituted aryl alcohols in which the OH group of the imbedded aryl alcohols is bonded directly to the aromatic, in the presence of partially and / or perfluorinated mediators and at least one conductive salt with arenes anodically to form the cross-coupling products are dehydrodimerized.
  • the process according to the invention is advantageous if the substituted aryl alcohols used can be mono- or binuclear.
  • the process of the invention is advantageous if the substituted arenes used can be mononuclear or binuclear.
  • the process according to the invention is advantageous if the dimerization takes place ortho to the alcohol group of the aryl alcohol.
  • the process according to the invention is advantageous if the mediators used are partially and / or perfluorinated alcohols and / or acids.
  • the process according to the invention is advantageous if 1,1,1,3,3,3-hexafluoroisopropanol and / or trifluoroacetic acid are used as mediators.
  • the process according to the invention is advantageous if the conductive salts used are those which are selected from the group of alkali, alkaline earth metal, tetra (C 1 to C 6 alkyl) ammonium salts.
  • the counterions of the conducting salts are selected from the group consisting of sulfate, hydrogensulfate, alkyl sulfates, aryl sulfates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate, hexafluorophosphate and perchlorate.
  • the process according to the invention is advantageous if no further solvent is used for the electrolysis.
  • the inventive method wherein a diamond anode and a nickel cathode are used.
  • the method according to the invention is advantageous if the diamond electrode is a boron-doped diamond electrode.
  • the process according to the invention is advantageous if a flow cell is used for the electrolysis.
  • the process according to the invention is advantageous when current densities of 1 to 1000 mA / cm 2 are used.
  • the process according to the invention is advantageous if the electrolysis is carried out at temperatures in the range from -20 to 100 ° C. and atmospheric pressure.
  • the process according to the invention is advantageous if 4-methylguajacol is used as the aryl alcohol.
  • aryl alcohol is understood as meaning aromatic alcohols in which the hydroxyl group is bonded directly to the aromatic nucleus.
  • the aromatic which is based on the aryl alcohol, may be mononuclear or polynuclear.
  • the aromatic is preferably mononuclear (phenol derivatives) according to formula I or binuclear (naphthol derivatives) according to formula II of III, in particular mononuclear.
  • An sp 2 -hybridized ring carbon atom of the aromatic, which is the basis of the aryl alcohol, can also be replaced by a nitrogen atom (pyridine, quinoline or isoquinoline derivative).
  • the aryl alcohols may also carry further substituents R1 to R7.
  • substituents R 1 to R 7 are independently selected from the group of C 1 -C 10 -alkyl groups, halogens, hydroxy, C 1 -C 10 -alkoxy groups, alkylene or arylene radicals interrupted by oxygen or sulfur, C 1 -C 10 -alkoxycarboxyl , Amino, nitrile, nitro and C 1 -C 10 alkoxycarbamoyl.
  • the substituents R 1 to R 7 are preferably selected from the group of methyl, ethyl, n-propyl, isopropyl, n-butyl, trifluoromethyl, fluorine, chlorine, bromine, iodine, hydroxy, methoxy, ethoxy, methylene, ethylene, propylene, isopropylene, Benzylidene, amino, nitrile, nitro.
  • the substituents R1 to R7 are particularly preferably selected from the group of methyl, methoxy, methylene, ethylene, trifluoromethyl, fluorine and bromine. Very particular preference is given to 4-alkyl- and 2,4-dialkyl-substituted phenols.
  • Suitable substrates for the electrodimerization according to the present invention are in principle all arenes, provided that they are capable of cross-dehydrodimerization because of their spatial structure and steric requirements.
  • Arene in the context of the present invention is understood as meaning aromatic carbon compounds and heteroaromatics. Preference is given in this connection to carbon compounds and heteroaromatics of the general formula IV to VIII.
  • the aromate on which the arene is based can be mononuclear or polynuclear.
  • the aromatic is preferably mononuclear (benzene derivatives) or binuclear (naphthalene derivatives), in particular mononuclear.
  • the arenes can also carry further substituents.
  • Preferred arenes are those of the formula IV to VIII.
  • An sp 2 -hybridized ring carbon atom of the arenes Moreover, according to formulas IV and V, it may be replaced by a nitrogen atom (pyridine, quinoline or isoquinoline derivative
  • R8 to R 37 which are independently selected from the group of C 1 -C 10 alkyl groups, halogens, hydroxy, C 1 -C 10 alkoxy, interrupted by oxygen or sulfur alkylene or arylene radicals, C 1 -C 10- Alkoxycarboxyl-, amino, nitrile, nitro and C 1 -C 10 alkoxycarbamoyl radicals.
  • the substituents are preferably selected from the group of methyl, ethyl, n-propyl, isopropyl, n-butyl, trifluoromethyl, fluorine, chlorine, bromine, iodine, hydroxyl, methoxy, ethoxy, methylene, ethylene, propylene, isopropylene, benzylidene, amino , Nitrile, nitro.
  • the substituents are particularly preferably selected from the group of methyl, methoxy, methylene, ethylene, trifluoromethyl, fluorine and bromine.
  • the preparation of the biaryl is carried out electrochemically, wherein the corresponding aryl alcohol is anodized.
  • the process according to the invention is referred to below as electrodimerization. It has surprisingly been found that the biaryls are produced selectively and in high yield by the method according to the invention using mediators. It has furthermore been found that undivided cell structures and solvent-free methods can be used by the method according to the invention.
  • the processing and recovery of the desired biaryle is very simple.
  • the electrolyte solution is worked up by general separation methods. For this purpose, the electrolyte solution is generally 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.
  • a diamond electrode is used. These diamond electrodes are formed by applying one or more diamond layers to a substrate.
  • Possible support materials are niobium, silicon, tungsten, titanium, silicon carbide, tantalum, graphite or ceramic supports such as titanium suboxide.
  • a support of niobium, titanium or silicon is preferred for the process according to the invention, very particular preference is given to a support of niobium.
  • Electrodes selected from the group of iron, steel, stainless steel, nickel, noble metals such as platinum, graphite, carbon materials such as the diamond electrodes are used for the process according to the invention.
  • 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 and diamond electrodes.
  • a diamond electrode which is also doped with further elements is preferred. Boron and nitrogen are preferred as doping elements.
  • BDD electrode boron-doped diamond electrode
  • the cathode material is selected from the group of iron, steel, stainless steel, nickel, precious metals such as platinum, graphite, carbon, glassy carbon materials and diamond electrodes.
  • the cathode is selected from the group of nickel, steel and stainless steel.
  • the cathode is particularly preferably made of nickel.
  • Partially and / or perfluorinated alcohols and / or acids preferably perfluorinated alcohols and carboxylic acids, very particularly preferably 1,1,1,3,3,3-hexafluoroisopropanol or trifluoroacetic acid, are used as mediators in the process according to the invention.
  • the 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. Preferably, one works continuously in undivided flow cells or discontinuously in beaker cells.
  • Particularly suitable are bipolar switched capillary gap cells or plate stack cells, in which the electrodes are designed as plates and are arranged plane-parallel as in Ullmann's Encyclopaedia of Industrial Chemistry, Electrochemistry, 1999 electronic release, Sixth Edition, Wiley-VCH Weinheim (doi: 10.1002 / 14356007.a09_183.pub2) and in Electrochemistry, Chapter 3.5. special cell designs and Chapter 5, Organic Electrochemistry, Subchapter 5.4.3.2 Cell Design is described.
  • the current densities at which the process is carried out are generally 1 to 1000, preferably 5 to 100 mA / cm 2 .
  • the temperatures are usually -20 to 100 ° C, preferably 10 to 60 ° C. In general, working at atmospheric pressure. Higher pressures are preferably used when operating at higher temperatures to avoid boiling of the co-solvents or mediators.
  • the aryl alcohol compound and the arene are dissolved in a suitable solvent.
  • suitable solvents known to the person skilled in the art, preferably solvents from the group of polar protic and polar aprotic solvents, are suitable.
  • the aryl alcohol compound itself serves as a solvent and reagent.
  • polar aprotic solvents include nitriles, amides, carbonates, ethers, ureas, chlorinated hydrocarbons.
  • particularly preferred polar aprotic solvents include acetonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate and dichloromethane.
  • polar protic solvents include alcohols, carboxylic acids and amides.
  • particularly preferred polar protic solvents include methanol, ethanol, propanol, butanol, pentanol and hexanol. These may also be partially or completely halogenated, such as 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) or trifluoroacetic acid (TFA).
  • HFIP 1,1,1,3,3,3-hexafluoroisopropanol
  • TFA trifluoroacetic acid
  • the electrolysis solution is added to customary cosolvents.
  • these are the inert solvents customary in organic chemistry with a high oxidation potential. Examples include its dimethyl carbonate, propylene carbonate, tetrahydrofuran, dimethoxyethane, acetonitrile or dimethylformamide.
  • Conducting salts which are contained in the electrolysis solution are generally alkali metal, alkaline earth metal, tetra (C 1 - to C 6 -alkyl) ammonium, preferably tri (C 1 - to C 6 -alkyl) -methylammonium salts .
  • Suitable counterions are sulfates, hydrogen sulfates, alkyl sulfates, aryl sulfates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate, hexafluorophosphate or perchlorate.
  • the acids derived from the abovementioned anions are suitable as conductive salts.
  • MTBS methyltributylammonium methylsulfates
  • MTES methyltriethylammonium methylsulfate
  • TABF tetrabutylammonium, tetrafluoroborate
  • Example 1 Anodic oxidation of 4-methyl guaiacol and substituted benzenes at a BDD anode with hexafluoroisopropanol
  • an electrolysis cell attached via a flange to a BDD-coated silicon plate and connected as an anode, the electrolyte consisting of substituted benzene and 4-methyl guaiacol in a molar ratio of 10: 1 according to Table 1, 0.68 g Methyltriethylammoniummethylsulfat (MTES) and 30 mL hexafluoroisopropanol presented.
  • MTES Methyltriethylammoniummethylsulfat
  • the cathode used is a nickel mesh which is immersed in the electrolyte at a distance of 1 cm from the BDD anode.
  • the cell is heated in a sand bath (50 ° C).
  • the electrolysis is carried out under galvanostatic control and a current density of 4.7 mA / cm 2 .
  • the reaction is stopped after reaching the set charge limit (1 F per mole of 4-methylguajacol).
  • the cooled reaction mixture is transferred with about 20 mL of toluene in a flask from which toluene and the fluorinated solvent used are almost completely removed on a rotary evaporator. Excess starting materials can be recovered by short path distillation at reduced pressure. By column chromatographic purification of the distillation residue on silica gel 60 and subsequent washing with a little cold n-heptane, the product can be isolated as a colorless, crystalline solid.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Claims (15)

  1. Procédé pour la préparation de biarylène, dans lequel on déshydrodimérise des alcools aryliques substitués, dans lesquels le groupe OH est directement lié aux cycles aromatiques, en présence de médiateurs partiellement et/ou perfluorés et d'au moins un sel conducteur, avec des arènes par voie anodique, avec formation des produits de couplage croisé.
  2. Procédé selon la revendication 1, dans lequel les alcools aryliques substitués utilisés peuvent être mono- ou binucléaires.
  3. Procédé selon la revendication 1 ou 2, dans lequel les arènes substitués utilisés peuvent être mono- ou binucléaires.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel la dimérisation a lieu en position ortho par rapport au groupe alcool de l'alcool arylique.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel les médiateurs utilisés sont des alcools et/ou acides partiellement et/ou perfluorés.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel on utilise comme médiateurs le 1,1,1,3,3,3-hexafluoro-isopropanol et/ou l'acide trifluoroacétique.
  7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel on utilise comme sels conducteurs ceux qui son choisis dans le groupe des sels de métaux alcalins, de métaux alcalino-terreux, de tétra [alkyl(C1-C6)] ammonium.
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel les ions opposés des sels conducteurs sont choisis dans le groupe constitué par les ions sulfate, hydrogénosulfate, les alkylsulfates, arylsulfates, halogénures, phosphates, carbonates, alkylphosphates, alkylcarbonates, l'ion nitrate, les alcoolates, les ions tétrafluoroborate, hexafluorophosphate et perchlorate.
  9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel pour l'électrolyse on n'utilise aucun autre solvant.
  10. Procédé selon l'une quelconque des revendications 1 à 9, dans lequel on utilise une anode en diamant et une cathode en nickel.
  11. Procédé selon l'une quelconque des revendications 1 à 10, dans lequel l'électrode en diamant consiste en une électrode en diamant dopée au bore.
  12. Procédé selon l'une quelconque des revendications 1 à 11, dans lequel pour l'électrolyse on utilise une cellule à écoulement continu.
  13. Procédé selon l'une quelconque des revendications 1 à 12, dans lequel on utilise des densités de courant de 1 à 1 000 mA/cm2.
  14. Procédé selon l'une quelconque des revendications 1 à 13, dans lequel on effectue l'électrolyse à des températures dans la plage de -20 à 100 °C et sous la pression normale.
  15. Procédé selon l'une quelconque des revendications 1 à 14, dans lequel on utilise comme alcool arylique le 4-méthylguaïacol.
EP10724436.0A 2009-06-05 2010-06-01 Procédé de déshydrodimérisation croisée anodique d'arènes Not-in-force EP2438214B1 (fr)

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EP09162074 2009-06-05
EP10724436.0A EP2438214B1 (fr) 2009-06-05 2010-06-01 Procédé de déshydrodimérisation croisée anodique d'arènes
PCT/EP2010/057617 WO2010139685A1 (fr) 2009-06-05 2010-06-01 Procédé de déshydrodimérisation croisée anodique d'arènes

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EP2438214A1 EP2438214A1 (fr) 2012-04-11
EP2438214B1 true EP2438214B1 (fr) 2013-05-29

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US (1) US8747646B2 (fr)
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JP (1) JP5705216B2 (fr)
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WO (1) WO2010139685A1 (fr)

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CN102459707A (zh) * 2009-06-05 2012-05-16 巴斯夫欧洲公司 制备不对称联芳基醇的方法
US9340884B2 (en) 2010-12-15 2016-05-17 Basf Se Process for the electrochemical fluorination of organic compounds
DE102013203867A1 (de) * 2013-03-07 2014-09-11 Evonik Industries Ag Elektrochemische Kupplung von Anilinen
DE102013203865A1 (de) * 2013-03-07 2014-09-11 Evonik Industries Ag Elektrochemische Kupplung zweier Phenole, welche sich in ihrem Oxidationspotential unterscheiden
DE102013203866A1 (de) 2013-03-07 2014-09-11 Evonik Industries Ag Elektrochemische Kupplung eines Phenols mit einem Naphthol
DE102014202274B4 (de) * 2013-03-07 2016-11-10 Evonik Degussa Gmbh Elektrochemisches Verfahren zur Kupplung von Phenol mit Anilin
DE102013211745A1 (de) 2013-06-21 2014-12-24 Evonik Industries Ag Elektrochemisches Verfahren zur Herstellung von symmetrischen Biphenolen unter Verwendung von Essigsäure als Elektrolyt
CN107089895B (zh) * 2017-05-05 2020-02-18 乐山师范学院 一种卤代芳烃电离放电偶联制备偶联芳烃的方法
EP3489391A1 (fr) * 2017-11-27 2019-05-29 Evonik Degussa GmbH Procédé de couplage électrochimique de phénol avec du benzofurane dans la position 3 et de réarrangement consécutif à 3-phényl-benzofurane par échanges des substituants
EP3489392A1 (fr) * 2017-11-27 2019-05-29 Evonik Degussa GmbH Procédé de couplage électrochimique de phénol avec du benzofurane dans la position 2 et de réarrangement consécutif à 3-phényl-benzofurane par échanges des substituants
EP3489390A1 (fr) * 2017-11-27 2019-05-29 Evonik Degussa GmbH Procédé électrochimique de couplage o-c des phénols non protégés avec les arylamines optiquement pures

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Publication number Priority date Publication date Assignee Title
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JP5705216B2 (ja) 2015-04-22
US8747646B2 (en) 2014-06-10
EP2438214A1 (fr) 2012-04-11
CN102459706B (zh) 2015-02-11
JP2012528938A (ja) 2012-11-15
US20120080320A1 (en) 2012-04-05
WO2010139685A1 (fr) 2010-12-09

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