EP0203851B1 - Elektrochemisches Verfahren zur Herstellung von organischen trifluoro- (oder chlorodifluoro- oder dichlorofluoro) methylierten Verbindungen - Google Patents

Elektrochemisches Verfahren zur Herstellung von organischen trifluoro- (oder chlorodifluoro- oder dichlorofluoro) methylierten Verbindungen Download PDF

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Publication number
EP0203851B1
EP0203851B1 EP86401046A EP86401046A EP0203851B1 EP 0203851 B1 EP0203851 B1 EP 0203851B1 EP 86401046 A EP86401046 A EP 86401046A EP 86401046 A EP86401046 A EP 86401046A EP 0203851 B1 EP0203851 B1 EP 0203851B1
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EP
European Patent Office
Prior art keywords
process according
compound
formula
aprotic solvent
dichlorofluoro
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Expired
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EP86401046A
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English (en)
French (fr)
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EP0203851A1 (de
Inventor
Francis Leroux
Michel Jaccaud
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Arkema France SA
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Atochem SA
Elf Atochem SA
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Priority to AT86401046T priority Critical patent/ATE37048T1/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
    • C25B3/27—Halogenation
    • C25B3/28—Fluorination
    • 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
    • C25B3/25—Reduction

Definitions

  • the invention relates to a process for trifluoro (or chlorodifluoro or dichlorofluoro) methylation of non-electroactive electrophilic substrates.
  • the invention relates to the preparation of methyl trifluoro (or chlorodifluoro or dichlorofluoro) methyl derivatives, useful in particular as synthesis intermediates.
  • the trifluoromethylation reaction can be carried out by radical route starting from CF 3 1 by initiating the reaction by raising the temperature or by irradiation with UV rays (J. Chem. Soc. 1953, p, 1199; U.S. Patents 3,016,406 and 3,016,407); however; this method has not yet been industrialized since access to trifluoromethyl iodide from trifluoroacetyl fluoride according to the scheme: is difficult and expensive.
  • the olefin trifluoromethylation was moreover carried out by electrochemical oxidation of the trifluoroacetate anion according to a radical mechanism, as described by BROOKES et al. (J. Chem. Soc. Chem. Commun. 1974, 323) and RENAUD et al. (Can. J. Chem 53, 1975, 529).
  • ISHIKAWA Choemistry Letters 1984, 517-520
  • phosphines a generator of polluted effluents
  • the present invention therefore relates to a process for the preparation of trifluoro (or chlorodifluoro or dichlorofluoro) methylated organic derivatives, characterized in that a compound of formula (1) is reduced electrochemically in the presence of a non-electroactive electrophilic substrate and a support electrolyte in an aprotic solvent.
  • non-electroactive electrophilic substrate is understood here to mean any organic electron-attracting compound which under operating conditions has a reduction potential more negative than the potential at which the operation is carried out.
  • substrates mention may be made more particularly of carbon dioxide, aldehydes such as formaldehyde and acetaldehyde, ketones such as acetone and benzophenone, and activated olefins (i.e. comprising at least one electron-withdrawing group) such as allyl alcohol and methyl acrylate.
  • the support electrolyte whose role is to ensure the passage of the current can be chosen from all the mineral or organic salts known for this purpose (cf. for example, Organic Electrochemistry by MM BAIZER , 1973, pp. 227-230) and, more particularly, among the bromides, chlorides, perchlorates or arylsulfonates of alkali metals (preferably lithium) or of tetraalkylammonium (C 1 to C 4 alkyl radicals).
  • the amount of support electrolyte in the aprotic solvent can range from 0.01 mole / liter until saturation; preferably, the support electrolyte is used at a concentration of 0.1 to 1 mole per liter of aprotic solvent.
  • the reaction can be carried out in any aprotic solvent or mixture of such solvents provided that its cathode limit is less than the reduction potential of the compound (1).
  • amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP) or hexamethylphosphorotriamide (HMPT), sulfoxides such as dimethyl sulfoxide (DMSO), nitriles such as acetonitrile (ACN) and ethers such as tetrahydrofuran (THF).
  • aprotic solvents mention may be made of pyridine, nitromethane, nitrobenzene, propylene carbonate, 1,2-dimethoxyethane, methylene chloride, tetrahydrothiophene-dioxide.
  • the cathode which constitutes the working electrode can be a carbon, graphite, platinum, nickel, gold, lead or mercury electrode.
  • the anode can be identical to the working electrode, but can also be made of any usual electrode material insofar as it is inert under the reaction conditions.
  • the electrochemical reduction according to the present invention can be carried out in the various usual cell types. Although one can operate in a cell with a single compartment, it is preferred to conduct the operation in a cell with two compartments to avoid free circulation between the cathode and the anode; the separator is generally made of an inert material, for example porcelain, sintered glass or ion exchange membrane.
  • the operation can be carried out according to a potentiostatic or intensiostatic control and is preferably carried out at the reduction potential of the compound of formula (I) under the operating conditions, this potential being able to be determined in a manner known per se by polarography or by cyclic voltammetry.
  • the range of temperatures at which the electrochemical reduction according to the invention can be carried out can vary within wide limits depending on the nature of the substrates and solvents used. In general, one operates at a temperature which can range from ⁇ 15 ° C to the boiling point of the aprotic solvent or even at a higher temperature by operating under pressure (from 0 to 50 bars). However, it is preferred to operate at a temperature between 0 and 80 ° C.
  • the molar ratio: electrophilic substrate / compound of formula (I) can vary between 1 and 20 and is advantageously between 3 and 10.
  • the reaction medium is preferably carried out when the reaction medium is saturated with the compound of formula (1), this saturation possibly being able to be maintained during operation by continuous or discontinuous addition of compound (1).
  • the product formed can be isolated by any conventional method, in particular by liquid-liquid extraction and / or by distillation, etc.
  • anode compartment of the cell 40 ml of a 0.1 mol / liter solution of LiCl0 4 in DMF are introduced as anolyte.
  • cathode compartment 550 ml of a solution containing 0.055 mole of LiCl0 4 and 0.55 mole of acetaldehyde in DMF are introduced as catholyte.
  • the reactor is closed, the stirring is started and brought to 3 ° C. by circulation of a water-glycol mixture (2/1 weight ratio) in the double jacket of the reactor, then the catholyte is saturated with bromo-trifluoromethane.
  • the electrolysis potential is - 2.00 volts / DHW.
  • the reaction solution is hydrolyzed in an acid medium (HCl, pH 1), neutralized with sodium hydroxide and added sodium chloride until saturation. Then extracted with ethyl ether and dried over sodium sulfate. After evaporation of the ether and distillation, the trifluoro-1,1,1 propanol-2 (PEb. 78 ° C.) is obtained, the structure of which has been identified by NMR and by mass spectrography coupled to gas chromatography.
  • the current yield that is to say the ratio: mass of product identified by analysis / theoretical mass, is 35%.
  • Carbon dioxide is used as the electrophilic substrate and operates under the following conditions:
  • reaction solution is then hydrolyzed in an acid medium, then subjected to distillation.
  • the water-trifluoroacetic acid azeotrope changes to 105.5 ° C at atmospheric pressure.
  • Example 1 The following table summarizes seven operations carried out by operating as in Example 1 with other solvents, other electrolytes and / or other substrates.
  • the abbreviation TBAB stands for tetrabutylammonium bromide.
  • the other operating conditions are the same as at example 1.
  • the products were all identified by NMR.

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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)

Claims (11)

1. Verfahren zur Herstellung trifluormethylisierter (oder chlordifluormethylisierter oder dichlorfluormethylisierter), organischer Derivate, dadurch gekennzeichnet, daß auf elektrochemischem Weg eine Verbindung der Formel
Figure imgb0008
in der x gleich 0, 1 oder 2 ist, in Anwesenheit eines elektrophilen, beim Reduktionspotential der Verbindung (I) nicht elektrisch aktiven Substrats und eines Elektrolyten in einem aprotischen Lösungsmittel reduziert wird.
2. Verfahren nach Anspruch 1, in dem die Verbindung der Formel (I) Bromtrifluormethan ist.
3. Verfahren nach Anspruch 1 oder 2. in dem das elektrophile, nicht elektrisch aktive Substrat Kohlendioxid, ein Aldehyd, ein Keton oder ein aktiviertes Alken ist.
4. Verfahren nach einem der Ansprüche 1 bis 3, in dem der Elektrolyt ein Lithium- oder Tetraalkylammoniumsalz ist.
5. Verfahren nach einem der Ansprüche 1 bis 4, in dem das aprotische Lösungsmittel ein Amid, Sulfoxid, Nitril, Ether oder ein Gemisch aus derartigen ist.
6. Verfahren nach einem der Ansprüche 1 bis 5, in dem die Kathode aus Kohlenstoff, Graphit, Platin, Nickel, Gold, Blei oder Quecksilber besteht.
7. Verfahren nach einem der Ansprüche 1 bis 6, in dem die Kathode von der Anode durch eine ionenaustauschende Membran, Porzellan oder Sinterglas getrennt ist.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es bei einer Temperatur zwischen 0 und 80 °C durchgeführt wird.
9. Verfahren nach einem der Ansprüche 1 bis 8, in dem die Menge des Elektrolyten im aprotischen Lösungsmittel zwischen 0,01 Mol/Liter und Sättigung und vorzugsweise zwischen 0, 1 und 1 Mol/Liter liegt.
10. Verfahren nach einem der Ansprüche 1 bis 9, in dem das Molverhältnis des elektrophilen Substrates und der Verbindung der Formel (I) zwischen 1 und 20, vorzugsweise zwischen 3 und 10 liegt.
11. Verfahren nach einem der Ansprüche 1 bis 10, in dem das Reaktionsgemisch mit der Verbindung der Formel (I) gesättigt ist.
EP86401046A 1985-05-21 1986-05-15 Elektrochemisches Verfahren zur Herstellung von organischen trifluoro- (oder chlorodifluoro- oder dichlorofluoro) methylierten Verbindungen Expired EP0203851B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86401046T ATE37048T1 (de) 1985-05-21 1986-05-15 Elektrochemisches verfahren zur herstellung von organischen trifluoro- (oder chlorodifluorooder dichlorofluoro) methylierten verbindungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8507595A FR2582320B1 (fr) 1985-05-21 1985-05-21 Procede electrochimique de preparation de derives organiques trifluoro (ou chlorodifluoro ou dichlorofluoro) methyles
FR8507595 1985-05-21

Publications (2)

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EP0203851A1 EP0203851A1 (de) 1986-12-03
EP0203851B1 true EP0203851B1 (de) 1988-09-07

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US (1) US4654128A (de)
EP (1) EP0203851B1 (de)
JP (1) JPS61291987A (de)
AT (1) ATE37048T1 (de)
AU (1) AU594678B2 (de)
DE (1) DE3660684D1 (de)
ES (1) ES8703946A1 (de)
FR (1) FR2582320B1 (de)

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JPS63145581A (ja) * 1986-12-08 1988-06-17 Omron Tateisi Electronics Co Ｉｃカ−ドシステム
DE3718726A1 (de) * 1987-06-04 1988-12-22 Hoechst Ag Verfahren zur herstellung fluorierter vinylether
FR2623525B1 (fr) * 1987-11-19 1990-03-02 Poudres & Explosifs Ste Nale Procede d'electrosynthese de composes gem di ou tri halogenes
CN112195481B (zh) * 2020-11-02 2021-12-10 上海漫关越水处理有限公司 膜电解合成四甲氧基乙烷的方法
US11926911B2 (en) 2022-02-07 2024-03-12 United States Of America As Represented By The Secretary Of The Air Force Microfluidic process for the general electrochemical synthesis of geminal dipseudohalide or halide-pseudohalide compounds
CN115572210B (zh) * 2022-12-08 2023-03-21 暨南大学 一种(1,2,2,2-四氟乙基)芳烃衍生物及其制备方法和应用

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JPS5034552B2 (de) * 1972-06-01 1975-11-10
DE3034491A1 (de) * 1980-09-12 1982-04-29 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung von polyfluorcarbonylverbindungen sowie einige neue vertreter dieser verbindungsklasse
GB2135669A (en) * 1983-03-01 1984-09-05 Ici Plc Electrolytic production of tetrafluoroethylene

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ES555180A0 (es) 1987-03-01
FR2582320B1 (fr) 1987-06-26
JPS6221876B2 (de) 1987-05-14
JPS61291987A (ja) 1986-12-22
ES8703946A1 (es) 1987-03-01
US4654128A (en) 1987-03-31
ATE37048T1 (de) 1988-09-15
AU594678B2 (en) 1990-03-15
DE3660684D1 (en) 1988-10-13
AU5756386A (en) 1986-11-27
FR2582320A1 (fr) 1986-11-28
EP0203851A1 (de) 1986-12-03

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