EP2318569B1 - Verfahren zur anodischen dehydrodimerisierung von substituierten phenolen - Google Patents

Verfahren zur anodischen dehydrodimerisierung von substituierten phenolen Download PDF

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Publication number
EP2318569B1
EP2318569B1 EP09782303A EP09782303A EP2318569B1 EP 2318569 B1 EP2318569 B1 EP 2318569B1 EP 09782303 A EP09782303 A EP 09782303A EP 09782303 A EP09782303 A EP 09782303A EP 2318569 B1 EP2318569 B1 EP 2318569B1
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EP
European Patent Office
Prior art keywords
process according
alcohols
electrolysis
group
phenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
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EP09782303A
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German (de)
English (en)
French (fr)
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EP2318569A1 (de
Inventor
Andreas Fischer
Itamar Michael Malkowsky
Florian Stecker
Siegfried Waldvogel
Axel Kirste
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BASF SE
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BASF SE
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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
    • C25B3/23—Oxidation
    • 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 biaryl alcohols, which is carried out by anodic dehydrodimerization of substituted phenols in the presence of partially and / or perfluorinated mediators and a conductive salt on a graphite electrode.
  • the method according to the invention makes it possible to use very inexpensive electrode materials, undivided cell structures and solvent-free methods.
  • mediators e.g. 1,1,1,3,3,3-hexafluoroisopropanol or the much cheaper trifluoroacetic acid are used.
  • Biaryls are known as such and are industrially produced and used. Compounds of this class of compounds are i.a. as backbones for ligands of great interest for stereoselective transformations.
  • One possible approach to this class of substances is the electrochemical oxidative dimerization of phenols, which, however, is nonselective in electrolytes known to those skilled in the art.
  • iron (III) salts or other strong oxidizing agents are used as an alternative to the electrochemical dimerization of phenols.
  • BDD boron-doped diamond electrodes
  • the object of the present invention is to provide a method with which the selective and efficient oxidative coupling of substituted phenols takes place without having to work in the presence of expensive electrode material.
  • the coupling of substituted phenols should take place in the ortho position.
  • the process according to the invention is advantageous if the substituted aryl alcohols used are identical.
  • the process according to the invention is advantageous if the substituted aryl alcohols used can be mononuclear or polynuclear.
  • the process according to the invention is advantageous if the dimerization takes place ortho to the alcohol group of the substituted aryl alcohols.
  • 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 or trifluoroacetic acid is used as mediators.
  • the process according to the invention is advantageous if the conductive salts used are those selected from the group consisting of alkali, alkaline earth metal, tetra (C 1 -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 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 60 ° C. and normal pressure.
  • the process according to the invention is advantageous if 2,4-dimethylphenol is used as 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) or binuclear (naphthol derivatives), in particular mononuclear.
  • the aryl alcohols may also carry further substituents.
  • substituents are independently selected from the group of C 1 -C 10 -alkyl groups, halogens, C 1 -C 10 -alkoxy groups, interrupted by oxygen or sulfur alkylene or arylene radicals, C 1 -C 10 -alkoxycarboxyl, nitrile, nitro and C 1 -C 10 -alkoxycarbamoyl, particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, trifluoromethyl, fluorine, chlorine, bromine, iodine, methoxy, ethoxy, methylene, ethylene, propylene, isopropylene, benzylidene, nitrile, Nitro, most preferably methyl, methoxy, methylene, ethylene, trifluoromethyl, fluorine and bromine.
  • aryl alcohols can be used.
  • electron-rich arenes such as mono- or polysubstituted phenols and naphthol ( ⁇ - and ⁇ -) and substituted derivatives thereof, very particularly preferred are 4-alkyl and 2,4-dialkyl-substituted phenols.
  • Suitable substrates for the electrodimerization according to the present invention are in principle all aryl alcohols, provided that they are capable of dimerization due to their spatial structure and steric requirements.
  • the aryl alcohols may be mononuclear, dinuclear, trinuclear or higher nuclear. Preferably, they are mononuclear or dinuclear, in particular mononuclear.
  • the aryl alcohols preferably have an OH function.
  • the electrolyte solution is worked up by general separation methods.
  • 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.
  • the preparation of the biaryl alcohol is carried out electrolytically, 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 biaryl alcohols are produced selectively and in high yield by the method according to the invention using mediators. Furthermore, it has been found that very inexpensive electrode materials, undivided cell structures and solvent-free methods can be used by the method according to the invention.
  • the electrolyte solution is worked up by general separation methods.
  • 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.
  • 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.
  • 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.
  • 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, 1999 electronic release, Sixth Edition, VCH-Weinheim, Volumne and in Electrochemistry, Chapter 3.5 , special cell designs as well 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 60 ° 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.
  • 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. Preference is given to graphite or carbon electrodes. According to the invention, a graphite electrode is used as the anode.
  • the cathode material for example, iron, steel, stainless steel, nickel or precious metals such as platinum and graphite or carbon materials and diamond electrodes come into consideration.
  • the system is preferably graphite as the anode and cathode, graphite as the anode and nickel, stainless steel or steel as the cathode and platinum as the anode and cathode.
  • the aryl alcohol compound is dissolved in a suitable solvent.
  • a suitable solvent 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 examples include nitriles, amides, carbonates, ethers, ureas, chlorinated hydrocarbons.
  • polar aprotic solvents examples include Actonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate and dichloromethane.
  • polar protic solvents examples include alcohols, carboxylic acids and amides.
  • polar protic solvents examples include methanol, ethanol, propanol, butanol, pentanol and hexanol. These may also be partially or completely halogenated, e.g. 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 sulfate, bisulfate, 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
  • Phenol [g] 20.02 g phenol / 1 g MTES / 9 mL HFIP 30 14 0.77 10 54 24 36 13.25 20.02 g phenol / 1 g MTES / 9 mL TFA 30 22 0.77 10 73 51 76 9.08 Phenol: 2-bromo-4-methylphenol; a: N, N-dimethylpyrrolidinium methylsulfate; b: yield considering the recovered phenol; c: isolation by crystallization from toluene and chromatographic; d: Isolation by crystallization from i PrOH: water and chromatographic.

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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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP09782303A 2008-09-01 2009-08-28 Verfahren zur anodischen dehydrodimerisierung von substituierten phenolen Not-in-force EP2318569B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09782303A EP2318569B1 (de) 2008-09-01 2009-08-28 Verfahren zur anodischen dehydrodimerisierung von substituierten phenolen

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08163356 2008-09-01
EP09782303A EP2318569B1 (de) 2008-09-01 2009-08-28 Verfahren zur anodischen dehydrodimerisierung von substituierten phenolen
PCT/EP2009/061101 WO2010023258A1 (de) 2008-09-01 2009-08-28 Verfahren zur anodischen dehydrodimerisierung von substituierten arylalkoholen

Publications (2)

Publication Number Publication Date
EP2318569A1 EP2318569A1 (de) 2011-05-11
EP2318569B1 true EP2318569B1 (de) 2012-03-28

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EP09782303A Not-in-force EP2318569B1 (de) 2008-09-01 2009-08-28 Verfahren zur anodischen dehydrodimerisierung von substituierten phenolen

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US (1) US8449755B2 (enExample)
EP (1) EP2318569B1 (enExample)
JP (1) JP5535215B2 (enExample)
AT (1) ATE551445T1 (enExample)
WO (1) WO2010023258A1 (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105111048A (zh) * 2014-05-26 2015-12-02 赢创德固赛有限公司 使用二氧化硒制备2,2’-联苯酚的方法
CN105272826A (zh) * 2014-05-26 2016-01-27 赢创德固赛有限公司 使用二氧化硒和卤代溶剂制备2,2’-联苯酚的方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102459706B (zh) 2009-06-05 2015-02-11 巴斯夫欧洲公司 芳烃的阳极交叉脱氢二聚方法
WO2010139687A1 (de) * 2009-06-05 2010-12-09 Basf Se Verfahren zur herstellung von unsymmetrischen biarylalkoholen
DE102013203866A1 (de) * 2013-03-07 2014-09-11 Evonik Industries Ag Elektrochemische Kupplung eines Phenols mit einem Naphthol
DE102013211744A1 (de) 2013-06-21 2014-12-24 Evonik Industries Ag Elektrochemisches Verfahren zur Herstellung von symmetrischen Biphenolen unter Verwendung einer Glaskohlenstoffanode
DE102013211745A1 (de) 2013-06-21 2014-12-24 Evonik Industries Ag Elektrochemisches Verfahren zur Herstellung von symmetrischen Biphenolen unter Verwendung von Essigsäure als Elektrolyt
SG10201601501QA (en) 2015-03-05 2016-10-28 Evonik Degussa Gmbh Preparation of 2,2`-biaryls in the presence of molybdenum(v) chloride
EP3095776A1 (de) 2015-05-20 2016-11-23 Evonik Degussa GmbH Kupplung von einem Phenol und einem Aren unter Verwendung von Selendioxid

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101391A (en) * 1976-01-05 1978-07-18 Monsanto Company Electrolytic oxidative methyl-methyl coupling of cresol salts
JPH0243388A (ja) * 1988-08-03 1990-02-13 Mitsubishi Kasei Corp ４，４’−ジヒドロキシビフェニル類の製造法
DE102004005508A1 (de) * 2004-02-04 2005-08-25 Basf Ag Anodische Dimerisierung substituierter Benzole
DE102005003012A1 (de) * 2005-01-21 2006-07-27 Basf Ag Anodische Dimerisierung von Hydroxy-substituierten Aromaten

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105111048A (zh) * 2014-05-26 2015-12-02 赢创德固赛有限公司 使用二氧化硒制备2,2’-联苯酚的方法
CN105272826A (zh) * 2014-05-26 2016-01-27 赢创德固赛有限公司 使用二氧化硒和卤代溶剂制备2,2’-联苯酚的方法

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Publication number Publication date
JP2012501383A (ja) 2012-01-19
ATE551445T1 (de) 2012-04-15
WO2010023258A8 (de) 2010-04-22
WO2010023258A1 (de) 2010-03-04
JP5535215B2 (ja) 2014-07-02
EP2318569A1 (de) 2011-05-11
US8449755B2 (en) 2013-05-28
US20110147228A1 (en) 2011-06-23

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