EP1769103B1 - Procédé electrochimique pour la préparation de cyclopropylbenzylamines - Google Patents

Procédé electrochimique pour la préparation de cyclopropylbenzylamines Download PDF

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Publication number
EP1769103B1
EP1769103B1 EP05760066A EP05760066A EP1769103B1 EP 1769103 B1 EP1769103 B1 EP 1769103B1 EP 05760066 A EP05760066 A EP 05760066A EP 05760066 A EP05760066 A EP 05760066A EP 1769103 B1 EP1769103 B1 EP 1769103B1
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EP
European Patent Office
Prior art keywords
oxime
catholyte
process according
anolyte
amine
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Expired - Lifetime
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EP05760066A
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German (de)
English (en)
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EP1769103A1 (fr
Inventor
Ulrich Griesbach
Harald Winsel
Hermann Pütter
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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
    • C25B3/25—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
    • 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
    • C25B3/09—Nitrogen containing compounds

Definitions

  • the present invention relates to a process for the preparation of primary amines having a primary amino group bonded to an aliphatic or cycloaliphatic carbon atom and a cyclopropyl moiety.
  • BM PRASAD ET AL. in "Etectrochemica! Reduction of Ketoximes of some Cycloalkanones and 1,2-Diones" J INDIAN CHEM SOC, 1991, pages 95-97 , XP090057046 and N. AYYASWAMI, V. KRISHNAN in "Behavior of iximes at a nickel black cathode” JOURNAL OF APPLIED ELECTROCHEMISTRY, Vol. 14, No. 4, 1984, pages 557-559 , XPO09057148 disclose a process for the preparation of primary amines by electrochemical reduction of amines. Both BM PRASAD ET AL. but N. AYYASWAMI, V. KRISHNAN work at much lower temperatures and other amines A and oximes O, respectively.
  • amine A which comprises oximes having a cyclopropyl moiety or oxime derivatives in which the hydrogen atom in the oxime group is replaced by an alkyl or acyl group (oxime O) in a divided electrolytic cell at a temperature of 50 to 100 ° C at the cathode, the water content in the catholyte and anolyte is less than 2% by weight and the amines A are compounds the general formula la in which the phenyl ring is optionally substituted by halogen atoms or C 1 - to C 4 -alkoxy groups and the oximes O are compounds the general (formula IIa) acts, in which the phenyl ring is optionally substituted by halogen atoms or C 1 - to C 4 alkoxy groups.
  • the catholyte contains a solvent in addition to an amine formed in the course of the reaction A and an oxime.
  • a solvent in addition to an amine formed in the course of the reaction A and an oxime.
  • these are the inert solvents generally used in organic chemistry, such as dimethyl carbonate, propylene carbonate, tetrahydrofuran, dimethoxyethane, acetonitrile or dimethylformamide.
  • the solvent used is preferably a C 1 -C 4 -alkyl alcohol.
  • C 5 - to C 7 hydrocarbons such as hexane as a solvent.
  • For the preparation of the conductivity of the catholyte generally contains a mineral acid, preferably sulfuric acid or an alkali (C 1 to C 4 ) -alkylalkoholat, preferably sodium methoxide.
  • a mineral acid preferably sulfuric acid or an alkali (C 1 to C 4 ) -alkylalkoholat, preferably sodium methoxide.
  • an electrolyte salt is added to the anolyte and optionally also to the catholyte (in addition to one of the above-mentioned conductivity-producing agents).
  • These are generally alkali metal, tetra (C 1 -C 6 -alkyl) ammonium, preferably tri (C 1 -C 6 -alkyl-methylammonium salts.
  • the counterions used are sulfate, hydrogensulfate, alkyl sulfates, aryl sulfates, halides, phosphates, Carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate, hexafluorophosphate or perchlorate into consideration.
  • MTBS methyltributylammonium methylsulfates
  • methyltriethylammonium methylsulfate methyltri-propylmethylammonium methylsulfates.
  • the water content in the catholyte and anolyte is generally less than 2, preferably less than 1 wt.%, Particularly preferably less than 0.5 wt.%. It should be noted that in the reduction of the oxime O to the amine A water is formed in stoichiometric amounts. If the batchwise reaction of the process is carried out with sufficiently high dilution of the starting product and the catholyte and anolyte have a water content of less than 0.1% by weight at the beginning of the reaction, the water formed during the reaction is generally unnecessary to remove the electrolyte. Otherwise, the water content of the electrolyte can be determined by conventional methods, e.g. be lowered by distillation.
  • the process according to the invention can be carried out in all customary divided types of electrolysis cell in order to be able to exclude within the scope of the process according to the invention that reactants such as products undergo chemical side reactions by the cathodic process.
  • reactants such as products undergo chemical side reactions by the cathodic process.
  • one works continuously in divided flow cells.
  • Divided cells with plane-parallel electrode arrangement are preferably used.
  • separation media can ion exchange membranes, microporous membranes, diaphragms, filter fabric of non-electron-conducting materials, glass frits, and porous ceramics are used.
  • ion exchange membranes in particular cation exchange membranes are used.
  • These conductive membranes are commercially available, e.g. available under the tradename Nafion® (E.T. DuPont de Nemours and Company) and Gore Select® (W.L. Gore & Associates, Inc.).
  • cathodes it is preferable to use those in which the cathode surface is formed of a high hydrogen overvoltage material, e.g. of lead, zinc, tin, nickel, mercury, cadmium, copper or alloys of these metals or glassy cabon, graphite or diamond.
  • a high hydrogen overvoltage material e.g. of lead, zinc, tin, nickel, mercury, cadmium, copper or alloys of these metals or glassy cabon, graphite or diamond.
  • diamond electrodes such as in the EP-A-1036863 are described.
  • anodes preferably those which are also referred to as cathode materials.
  • acidic anolyte preference is given to using platinum, diamond, glassy carbon or graphite anodes or the dimensionally stable anodes (DSA) known to the person skilled in the art. If the anolyte is basic, preferably stainless steel is used.
  • the anodic reaction can be chosen freely, preferably the C 1 - to C 4 -alcohol used as solvent is oxidized there.
  • methanol methyl formate, formaldehyde dimethyl acetal or dimethyl carbonate are formed.
  • a sulfuric acid solution diluted with a C 1 -C 4 -alcohol is used for this purpose.
  • the current densities at which the process is carried out are generally 1 to 1000, preferably 10 to 100 mA / cm 2 .
  • working at atmospheric pressure In general, working at atmospheric pressure. Higher pressures are preferably used when operating at higher temperatures to avoid boiling of the starting compounds or solvents.
  • the electrolyte solution is worked up by general separation methods.
  • the catholyte 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 or by chromatography.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (6)

  1. Procédé pour la préparation d'amines primaires comportant un groupe amino primaire lié à un atome de carbone aliphatique ou cycloaliphatique, et une unité cyclopropyle (amine A), par réduction d'oximes comportant une unité cyclopropyle ou des dérivés d'oximes, dans lesquels l'atome d'hydrogène dans le groupe oxime est remplacé par un groupe alkyle ou acyle (oxime O), à la cathode dans une cellule électrolytique à une température de 50 à 100 °C, la teneur en eau du catholyte et de l'anolyte étant inférieure à 2 % en poids et les amines A consistant en des composés de formule générale Ia,
    Figure imgb0008
     dans laquelle le cycle phényle est éventuellement substitué par des atomes d'halogène ou des groupes alcoxy en C1-C4 et
    les oximes O consistant en des composés de formule générale IIa,
    Figure imgb0009
     dans laquelle le cycle phényle est éventuellement substitué par des atomes d'halogène ou des groupes alcoxy en C1-C4.
  2. Procédé selon la revendication 1, dans lequel le catholyte contient, outre une amine A et une oxime O, en tant que solvant un alcanol en C1-C4.
  3. Procédé selon la revendication 1 ou 2, dans lequel le catholyte contient un acide minéral ou un alcanolate en C1-C4 de métal alcalin.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel la surface de la cathode est constituée d'un matériau à haute surtension d'hydrogène.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel la surface de la cathode est constituée de plomb, zinc, étain, nickel, mercure, cadmium, cuivre ou des alliages de ceux-ci, ou de Glassy Carbon (carbone vitreux), graphite ou diamant.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel la teneur en eau du catholyte est inférieure à 2 % en poids.
EP05760066A 2004-07-13 2005-07-08 Procédé electrochimique pour la préparation de cyclopropylbenzylamines Expired - Lifetime EP1769103B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004033718A DE102004033718A1 (de) 2004-07-13 2004-07-13 Verfahren zur Herstellung von primären Aminen mit einer an ein aliphatisches oder cycloaliphatisches C-Atom gebunden primären Aminogruppe und einer Cyclopropyl-Einheit
PCT/EP2005/007400 WO2006005531A1 (fr) 2004-07-13 2005-07-08 Procede de production d'amines primaires comprenant un groupe amino primaire fixe sur un atome de carbone aliphatique ou cycloaliphatique, et une unite cyclopropyle

Publications (2)

Publication Number Publication Date
EP1769103A1 EP1769103A1 (fr) 2007-04-04
EP1769103B1 true EP1769103B1 (fr) 2010-05-05

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EP05760066A Expired - Lifetime EP1769103B1 (fr) 2004-07-13 2005-07-08 Procédé electrochimique pour la préparation de cyclopropylbenzylamines

Country Status (7)

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US (1) US7411094B2 (fr)
EP (1) EP1769103B1 (fr)
JP (1) JP4587329B2 (fr)
CN (1) CN1985024B (fr)
AT (1) ATE466972T1 (fr)
DE (2) DE102004033718A1 (fr)
WO (1) WO2006005531A1 (fr)

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KR101374491B1 (ko) * 2006-07-04 2014-03-14 바스프 에스이 입체 장애 아민의 전기화학적 제조
WO2013030316A2 (fr) 2011-09-01 2013-03-07 Johannes Gutenberg-Universität Mainz Procédé de désoxygénation cathodique d'amides et d'esters
CN110683957B (zh) * 2019-10-25 2022-10-28 湖南比德生化科技股份有限公司 一种二氨基萘的合成与分离提纯方法

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DE19620861A1 (de) * 1996-05-23 1997-11-27 Basf Ag Verfahren zur elektrochemischen Reduktion organischer Verbindungen
JP3568394B2 (ja) 1998-07-07 2004-09-22 独立行政法人 科学技術振興機構 低抵抗ｎ型ダイヤモンドの合成法

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JP4587329B2 (ja) 2010-11-24
CN1985024B (zh) 2010-12-29
CN1985024A (zh) 2007-06-20
WO2006005531A1 (fr) 2006-01-19
US7411094B2 (en) 2008-08-12
JP2008505953A (ja) 2008-02-28
ATE466972T1 (de) 2010-05-15
EP1769103A1 (fr) 2007-04-04
US20080064901A1 (en) 2008-03-13
DE502005009531D1 (de) 2010-06-17
DE102004033718A1 (de) 2006-02-16

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