EP0100877A1 - Verfahren zur Herstellung von Arylessig- und Arylpropionsäure - Google Patents

Verfahren zur Herstellung von Arylessig- und Arylpropionsäure Download PDF

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Publication number
EP0100877A1
EP0100877A1 EP83106657A EP83106657A EP0100877A1 EP 0100877 A1 EP0100877 A1 EP 0100877A1 EP 83106657 A EP83106657 A EP 83106657A EP 83106657 A EP83106657 A EP 83106657A EP 0100877 A1 EP0100877 A1 EP 0100877A1
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Prior art keywords
ligand
anode
formula
metal
chosen
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EP83106657A
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English (en)
French (fr)
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EP0100877B1 (de
Inventor
Jean-François Fauvarque
Anny Jutand
Claude Chevrot
Fernando Pfluger
Michel Troupel
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Centre National de la Recherche Scientifique
Alcatel Lucent SAS
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Centre National de la Recherche Scientifique
Compagnie Generale dElectricite SA
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Priority to AT83106657T priority Critical patent/ATE20480T1/de
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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
    • C25B3/25—Reduction
    • 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
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds

Definitions

  • the invention relates to the preparation of arylacetic and arylpropionic acids from halides of the benzyl type, of formula Ar CH 2 X and Ar CH (CH 3 ) x or Ar denotes a substituted or unsubstituted aromatic group and X a halogen.
  • arylacetic and arylpropionic acids are of great importance, since they constitute an essential class of anti-inflammatory drugs, anesthetics and are also precursors in the preparation of penicillins.
  • triphenylphosphine P (C 6 H 5 ) 3 was used to form the organic nickel complexes.
  • the present invention makes it possible to remedy this drawback and to easily obtain arylacetic and arylpropionic acids by electrosynthesis.
  • It relates to a process for the preparation of arylacetic and arylpropionic acids, comprising an electrochemical reduction, under a carbon dioxide atmosphere, of benzyl halides of formula Ar CH 2 X or Ar CH (CH 3 ) X, characterized by fact that said reduction is carried out in the presence of a catalyst comprising at least one organo-metallic complex derived from a transition metal associated with a bidentate or tetradentate ligand.
  • bidentate ligand is meant a ligand which has two coordination sites on the metal used.
  • tetradentate ligand is meant a ligand which has four coordination sites on the metal used.
  • the transition metal is chosen so that it forms, with the preceding ligands, an electroreducible organometallic complex capable in its reduced form of reacting with the benzyl halide.
  • the metal is advantageously chosen from the group comprising nickel and cobalt.
  • the organometallic complex is chosen from the group formed on the one hand by nickel bis cyclooctadiene and on the other hand by metal ligated halides, of formula Ni Y 2 L, Y being a halogen, L bipyridyl or a diphosphine-type ligand of formula PR2 - ( CH2 ) n - PR 2 , in which P denotes the phosphorus which is a coordination site, R being a radical chosen from the group formed by the phenyl radical and the aliphatic radicals, n being an integer less than or equal to 4.
  • n can be equal to 2, 3 or 4.
  • diphenyl phosphinoethane of formula: P (C 6 H 5 ) 2 - ( CH 2 ) 2 - P (C 6 H 5 ) 2 is used as the ligand L.
  • diphenyl phosphino propane of formula P (C 6 H 5 ) 2 - (CH2) 3 - P (C6HS) 3 or dimethyl phosphino ethane (DMPE) of formula P (CH 3 ) 2 - ( CH 2 ) 2 -P (CH 3 ) 2 ⁇
  • the catalyst consists of a complex M 'salen where M' represents nickel or cobalt and "salen” represents the tetradentate bis salicylidene ethylene diamine ligand, the catalyst having the formula.
  • cobalt will be used which forms with the "salen” ligand a complex more easily electroreducible than the corresponding complex of nickel.
  • organometallic catalysts according to the invention can be used alone or as a mixture.
  • the second ligand L ' can be used as triphenyl phosphine (TPP) of formula P (C 6 H 5 ) 3 , tributyl phosphine P (C 4 H 9 ) 3 , tricyclohexyl phosphine P (C 6 H 11 ) 3 .
  • TPP triphenyl phosphine
  • the catalyst used comprises approximately four molar equivalents corresponding to the first complex MY 2 L for a molar equivalent corresponding to the second complex M 1 Y 2 L ' 2 .
  • the catalyst comprises at least one organometallic complex of the aforementioned type to which a monodentate or bidentate ligand of the aforementioned type is added, for example cyclooctadiene (COD) or bipyridyl.
  • COD cyclooctadiene
  • bipyridyl for example cyclooctadiene (COD) or bipyridyl.
  • the single figure very schematically represents an electrolysis cell usable for the implementation of the invention.
  • the cell is designated by the reference 1. It comprises two separate compartments, a cathode compartment 2 and an anode compartment 3.
  • the cathode 4 can be constituted by a felt, a fabric or a braid of carbon fibers or by a sheet of mercury , of surface about 20 cm 2 .
  • the cathode conductor constituted by a copper wire is designated by the reference 5.
  • the anode 6 can be of the alterable metal, lithium, copper, etc. type or of the unalterable type, carbon or metal, associated with an oxidizable electrolyte (oxalate for example).
  • the anode conductor, consisting of a copper wire, is designated by the reference 7.
  • the conductors 5 and 7 are connected to an appropriate generator.
  • the reference 8 designates a sintered glass separating the 2 compartments.
  • the reference 9 designates a magnetic bar used for agitating the medium.
  • the solvent of the electrolyte is formed by a mixture comprising by volume 2/3 of an aprotic solvent, such as tetrahydrofuran (THF), 1/3 of dipolar aprotic solvent such as hexamethylphosphorotriamide (HMPT) or N- methyl pyrrolidone, or tetramethylurea.
  • an aprotic solvent such as tetrahydrofuran (THF)
  • dipolar aprotic solvent such as hexamethylphosphorotriamide (HMPT) or N- methyl pyrrolidone, or tetramethylurea.
  • the electrolyte can be chosen identical or different in the anode 3 and cathode 2 compartments; it is used at a concentration of about 0.1 to 0.3 moles per liter.
  • the electrolyte 10 can be of the oxidizable type, advantageously a sodium or lithium oxalate, or non-oxidizable, associated with a soluble anode, for example lithium perchlorate (Li Cl 0 4 ), tetrafluoborate of tetrabutyl ammonium "C 4 Hg) 4 NB F 4 ).
  • a non-reducible electrolyte 11 Li C10 4 , tetrabutylammonium tetrafluoborate
  • the benzyl halide and the catalyst according to the invention are introduced.
  • a reference electrode 15 consisting of a silver wire immersed in an aprotic solvent solution containing silver perchlorate at a concentration of 0.1 mol / liter, makes it possible to identify the potential of the cathode.
  • the arrows 12 and 13 symbolize the introduction, if necessary, of an inert gas into the anode 3 and cathode 2 compartments. Furthermore, carbon dioxide can be introduced into the cathode electrolytic solution by the tube 1U at the atmospheric pressure or slightly higher.
  • This elimination can be done for example by adding a magnesium, such as C 2 H 5 MgX ', X' being a halogen, for example Br, in solution in ether or tetrahydrofuran.
  • a magnesium such as C 2 H 5 MgX ', X' being a halogen, for example Br, in solution in ether or tetrahydrofuran.
  • Carbon dioxide is then bubbled through the cathode compartment of the cell, at atmospheric pressure or slightly higher.
  • the reaction medium is maintained at ambient temperature or cooled by an external circulation of cold water.
  • the electrochemical reduction is then carried out at controlled potential.
  • the potential of the agitated mercury sheet compared to the Ag / AgClO 4 system , is maintained at approximately - 2.6 V.
  • the electrochemical reduction is carried out until the amount of current passed corresponds to a predetermined value, or until the current is zero.
  • the current density at the start of the reduction is approximately 35 mA / cm 2 .
  • the solution is then hydrolyzed in an acid medium and extracted with ether.
  • the ethereal phase is stirred with aqueous sodium hydroxide and then separated.
  • the basic aqueous phase is acidified, saturated with NaCl, then extracted with ether.
  • the ethereal phase is dried over MgSO 4 , then evaporated.
  • the phenylacetic acid formed is thus recovered, which is characterized by its IR and 1 H NMR spectra and its melting point.
  • This step is not necessary if a zerovalent nickel complex such as Ni (COD) 2 is used , but such complexes, which are very oxidizable in air, are less convenient to handle.
  • a zerovalent nickel complex such as Ni (COD) 2 is used , but such complexes, which are very oxidizable in air, are less convenient to handle.
  • Ni ° L complex is generally very reactive and not very stable. Its stability is increased by the presence of another bidentate ligand in the medium chosen so as to weakly complex Ni ° L, for example COD or bipyridyle, which are relatively weak ligands of zerovalent nickel and do little to hinder its subsequent reaction with the chloride. benzyl.
  • This complex can be reduced electrochemically according to:
  • the reaction medium contained 0.1 gram atom of nickel per 1 mole of C 6 H 5 CH 2 Cl, the pressure of C0 2 was 1 atmosphere, the potential was maintained at -2.6 V, unless otherwise stated;
  • the solvent of the electrolyte consisted of THF / HMPT (ratio 2/3, 1/3) for examples 1 to 12, (ratio 1/2, 1/2) for examples 13 and 14; for examples 1 to 9 the electrolyte was 0.1 M Li C104; for Examples 10 to 12, the cathode electrolyte was 0.3 M tetrabutylamonium tetrafluoborate, the anode electrolyte being 0.1 M lithium oxalate, with a carbon anode; for examples 13 and 14 the electrolyte was Li Cl0 4 0.2 M.
  • the first stage corresponding to the formation of the intermediate complex C 6 H 5 CH 2 Ni Cl L, operation carried out under neutral gas
  • the second to the reduction of this complex in the presence of CO 2 the biaryl derivative is preferably formed.
  • the reaction medium contained 0.1 gram atom of nickel per 1 mole of C 6 H 5 CH (CH 3 ) Cl, the pressure of C0 2 was 1 atmosphere, the temperature 0 °, the potential was maintained at approximately -2.4, -2.6 V relative to the Ag + / Ag reference electrode.
  • the catalytic species consisted of Co salen.
  • the cathode electrolyte is tetrabutylammonium tetrafluoborate 0.3 M, for example 21, Li Cl0 4 0.2 M.
  • the solvent of the electrolyte was THF - HMPT (ratio 2/3, 1/3).

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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)
  • Catalysts (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP83106657A 1982-07-13 1983-07-07 Verfahren zur Herstellung von Arylessig- und Arylpropionsäure Expired EP0100877B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83106657T ATE20480T1 (de) 1982-07-13 1983-07-07 Verfahren zur herstellung von arylessig- und arylpropionsaeure.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8212275A FR2530266B1 (fr) 1982-07-13 1982-07-13 Procede de preparation des acides arylacetiques et arylpropioniques
FR8212275 1982-07-13

Publications (2)

Publication Number Publication Date
EP0100877A1 true EP0100877A1 (de) 1984-02-22
EP0100877B1 EP0100877B1 (de) 1986-06-18

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EP83106657A Expired EP0100877B1 (de) 1982-07-13 1983-07-07 Verfahren zur Herstellung von Arylessig- und Arylpropionsäure

Country Status (6)

Country Link
US (1) US4517061A (de)
EP (1) EP0100877B1 (de)
JP (1) JPS5935688A (de)
AT (1) ATE20480T1 (de)
DE (1) DE3364177D1 (de)
FR (1) FR2530266B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0286944A3 (en) * 1987-04-16 1989-08-02 Enichem Synthesis S.P.A. New process for the preparation of 2-aryl-propionic acids
AT411504B (de) * 1998-12-17 2004-01-26 Fhp Motors Gmbh Schutzleiteranschluss an einem lamellierten ständerblechpaket eines elektromotors

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2566434B1 (fr) * 1984-06-21 1986-09-26 Poudres & Explosifs Ste Nale Procede d'electrosynthese d'acides carboxyliques
FR2579627B1 (fr) * 1985-03-29 1987-05-15 Poudres & Explosifs Ste Nale Procede d'electrosynthese d'alcools
JPS63295021A (ja) * 1987-05-28 1988-12-01 Nippon Steel Corp 溶接管における薄肉管成形法
GB0228018D0 (en) * 2002-11-30 2003-01-08 Lucite Int Uk Ltd Carbonylation of ester
WO2005003070A1 (en) * 2003-07-03 2005-01-13 Lucite International Uk Limited Process for the hydroformylation of ethylenically unsaturated compounds
GB0315536D0 (en) * 2003-07-03 2003-08-06 Lucite Int Uk Ltd Process for the hydroformylation of ethylenically unsaturated compounds
GB0403592D0 (en) * 2004-02-18 2004-03-24 Lucite Int Uk Ltd A catalyst system
WO2005082343A2 (en) 2004-02-25 2005-09-09 La Jolla Pharmaceutical Company Amines and amides for the treatment of diseases
GB0411951D0 (en) * 2004-05-28 2004-06-30 Lucite Int Uk Ltd Carbonylation of ester
GB0516556D0 (en) * 2005-08-12 2005-09-21 Lucite Int Uk Ltd Improved catalyst system
US9334227B2 (en) 2005-11-17 2016-05-10 Lucite International Uk Limited Carbonylation of ethylenically unsaturated compounds
GB0607494D0 (en) 2006-04-13 2006-05-24 Lucite Int Uk Ltd Metal complexes
BRPI0719344B1 (pt) * 2006-12-02 2017-05-02 Lucite Int Uk Ltd ligando bidentado, processo para a carbonilação de compostos etilenicamente insaturados, e, sistema de catalisador
GB0625518D0 (en) * 2006-12-21 2007-01-31 Lucite Int Uk Ltd Carbonylation of conjugated dienes
GB0812297D0 (en) * 2008-07-04 2008-08-13 Lucite Int Uk Ltd Novel carbonylation ligand sand thier use of in the carbonylation of ethylenically unsaturated compounds
GB201000078D0 (en) 2010-01-05 2010-02-17 Lucite Int Uk Ltd Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporatng such ligands
JP5842774B2 (ja) * 2012-09-20 2016-01-13 コニカミノルタ株式会社 光電変換素子および太陽電池
CN113136593A (zh) * 2021-04-14 2021-07-20 赤峰学院 一种布洛芬的合成方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3344045A (en) * 1964-10-23 1967-09-26 Sun Oil Co Electrolytic preparation of carboxylic acids
US3764492A (en) * 1972-01-10 1973-10-09 Monsanto Co Electrolytic preparation of esters from organo halides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3344045A (en) * 1964-10-23 1967-09-26 Sun Oil Co Electrolytic preparation of carboxylic acids
US3764492A (en) * 1972-01-10 1973-10-09 Monsanto Co Electrolytic preparation of esters from organo halides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF ORGANIC CHEMISTRY, vol. 37, no. 12, 1972, pages 1951-1957 *
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 111, janvier 1964, pages 74-78 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0286944A3 (en) * 1987-04-16 1989-08-02 Enichem Synthesis S.P.A. New process for the preparation of 2-aryl-propionic acids
AT411504B (de) * 1998-12-17 2004-01-26 Fhp Motors Gmbh Schutzleiteranschluss an einem lamellierten ständerblechpaket eines elektromotors

Also Published As

Publication number Publication date
DE3364177D1 (en) 1986-07-24
EP0100877B1 (de) 1986-06-18
JPH0229755B2 (de) 1990-07-02
ATE20480T1 (de) 1986-07-15
US4517061A (en) 1985-05-14
FR2530266A1 (fr) 1984-01-20
FR2530266B1 (fr) 1985-07-12
JPS5935688A (ja) 1984-02-27

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