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WO1994008929A1 - Production d'ethers partiellement fluores - Google Patents

Production d'ethers partiellement fluores Download PDF

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Publication number
WO1994008929A1
WO1994008929A1 PCT/GB1993/002035 GB9302035W WO9408929A1 WO 1994008929 A1 WO1994008929 A1 WO 1994008929A1 GB 9302035 W GB9302035 W GB 9302035W WO 9408929 A1 WO9408929 A1 WO 9408929A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
hydrogen
fluoroalkyl group
partially fluorinated
transition metal
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.)
Ceased
Application number
PCT/GB1993/002035
Other languages
English (en)
Inventor
Laurent Garnier
James Burdon
Richard Llewellyn Powell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of WO1994008929A1 publication Critical patent/WO1994008929A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/12—Saturated ethers containing halogen
    • C07C43/123—Saturated ethers containing halogen both carbon chains are substituted by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms

Definitions

  • This invention relates to a process for the production of higher partially fluorinated ethers, in particular
  • 1-difluoromethoxy-1 ,2,2,2-tetrafluoroethane from s lower partially fluorinated ethers, that is a process for the fluorination of partially fluorinated ethers.
  • l-difluoromethoxy-l,2,2,2-tetrafluoroethane commonly known and hereafter referred to as "Desflurane” is known to have valuable anaesthetic properties but processes previously proposed for its production have suffered from various disadvantages relating to the availability and toxicity of starting materials with resulting scale-up problems for the production of commercial quantities.
  • 1-difluoromethoxy-2 ,2,2-trifluoroethane under relatively mild conditions in the vapour phase using a transition metal fluorinating agent, in particular cobalt trifluoride.
  • 1-difluoromethoxy-2 ,2,2-trifluoroethane is itself not readily prepared and the yields of Desflurane obtained by the process are not as high as may be desired, the main by-products being over-fluorinated materials which cannot therefore be further fluorinated to desflurane.
  • 1-difluoromethoxy-2, 2 , 2-trifluoroethane can be fluorinated using a transition metal fluorinating agent to give substantial yields of Desflurane and by-products which may be further fluorinated to Desflurane. Furthermore, such lower fluorinated ethers are much more readily prepared than is 1-difluoromethoxy-2 ,2,2-trifluoroethane.
  • R is a fluoroalkyl group having from 1 to 6 carbon atoms and R 1 is hydrogen, fluorine or a fluoroalkyl group having from 1 to 6 carbon atoms, provided that where R-*- is a fluoroalkyl group, R is not a trifluoromethyl group or a fluoroalkyl group having a difluoromethylene group at the ⁇ -position relative to the oxygen atom, which comprises contacting the fluorinated ether with a transition metal fluorinating agent.
  • the group R comprises a partially fluorinated alkyl group having no more than one fluorine atom attached to the carbon atom at the ⁇ -position relative to the oxygen atom, and more preferably the group R comprises a
  • R 1 is a hydrogen or fluorine atom or a trifluoromethyl group, particularly a hydrogen or fluorine atom.
  • Ve especially prefer that the group R 1 is a fluorine or hydrogen atom and the group R is a 2,2,2-trifluoroethyl or 1 , 2 , 2 , 2-tetrafluoroethyl group, since these compounds readily yield
  • a process for the production of 1-difluoromethoxy-1 ,2,2,2-tetrafluoroethane which comprises contacting a fluorinated ether having the formula
  • each R is independently fluorine or hydrogen, with a transition metal fluoride fluorinating agent.
  • the starting fluorinated ethers of the preferred embodiment of the invention are therefore (i) 1 , 1 , 1-trifluoro-2-methoxyethane , CF3CH2-O-CH3 (ii) 1,1, 1-trifluoro-2-fluoromethoxyethane , CF3CH2-O-CH2F, (iii) l,l,l,2-tetrafluoro-2-methoxyethane, CF3CHF-O-CH3 and
  • (i) may be prepared by the reaction of trifluoroethanol with dimethyl sulphate under basic conditions or by the reaction of methyl iodide with CF3CH2 ⁇ a and (ii) may be prepared by the liquid phase reaction of trifluoroethanol with a mixture of hydrogen fluoride and formaldehyde as described in our published International Patent Application No. WO 93/12057.
  • (iii) and (iv) may be prepared as described in GB Patent No. 1537861, and DT-OS 23 40 560 referred to therein, or by the liquid phase reaction of methanol and fluoral hydrate respectively with a mixture of hydrogen fluoride and formaldehyde, as described in our published International Patent Application No. WO 93/12057.
  • Cobalt trifluoride is the preferred transition metal fluoride fluorinating agent but other transition metal fluoride fluorinating agents which may be employed include, for example, the fluorides of manganese, silver and cerium or alkali metal complexes of the transition metal fluorides, for example potassium tetrafluorocobaltanate , potassium tetrafluoroargentate , and potassium hexafluoronickelate .
  • the temperature at which the process is effected will depend to some extent upon the fluorinating power of the particular fluorinating agent employed although usually the temperature will be in the range from about 150°C to about A50°C. Where the fluorinating agent is cobalt trifluoride, the temperature is preferably in the range from about 180°C to about 280°C, especially from about 200°C to about 260°C.
  • the process is conveniently operated at about atmospheric pressure, although superatmospheric or subatmospheric pressure may be employed if desired.
  • the process of the invention is preferably carried out in the vapour phase.
  • the ether is preferably vaporised over a bed of the transition metal fluorinating agent.
  • a carrier gas may be employed, for example nitrogen.
  • the product ether may be readily purified, for example by fractional distillation.
  • the reactor w s heated to a temperature of 250°C and 50g of 1 , 1 , 1-trifluoro-2-methoxyethane was passed over the catalyst in a stream of nitrogen with a flow rate of 5 litres per hour.
  • the reactor off gases were collected in a Drikold-cooled copper vessel and the organics were separated from hydrogen fluoride by treatment with water at 0°C. 25g of organic product was collected.
  • the organic product was sampled and analysed by gas chromatography.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de fluoration d'un éther partiellement fluoré ayant la formule R-O-CH2-R1 dans laquelle R représente un groupe fluoroalkyle ayant 1 à 6 atomes de carbone et R1 représente hydrogène, fluor ou un groupe fluoroalkyle ayant 1 à 6 atomes de carbone, à condition que lorsque R1 représente un groupe fluoroalkyle, R ne représente pas un groupe trifluorométhyl ou un groupe fluoroalkyle ayant un groupe difluorométhylène en position α par rapport à l'atome d'oxygène. Ce procédé consiste à mettre en contact l'éther partiellement fluoré avec un agent de fluoration à base d'un métal de transition, en particulier le trifluorure de cobalt. Le 1-difluorométhoxy-1,2,2,2-tétrafluoroéthane peut être produit lorsque l'éther fluoré à la formule CF¿3?-CHR-O-CH2R dans laquelle R représente indépendamment fluor ou hydrogène.
PCT/GB1993/002035 1992-10-16 1993-09-30 Production d'ethers partiellement fluores Ceased WO1994008929A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB929221743A GB9221743D0 (en) 1992-10-16 1992-10-16 Production of partially fluorinated ethers
GB9221743.9 1992-10-16

Publications (1)

Publication Number Publication Date
WO1994008929A1 true WO1994008929A1 (fr) 1994-04-28

Family

ID=10723552

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1993/002035 Ceased WO1994008929A1 (fr) 1992-10-16 1993-09-30 Production d'ethers partiellement fluores

Country Status (2)

Country Link
GB (1) GB9221743D0 (fr)
WO (1) WO1994008929A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5741950A (en) * 1996-12-16 1998-04-21 Minnesota Mining And Manufacturing Company Method of preparing nonafluoroisobutyl methyl ether
US6800786B1 (en) 2002-09-25 2004-10-05 Baxter International, Inc. Preparation of desflurane

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984002909A1 (fr) * 1983-01-20 1984-08-02 Electricity Council Ethers fluores
EP0482938A1 (fr) * 1990-10-26 1992-04-29 Rhone-Poulenc Chemicals Limited Synthèse d'éthers fluorés

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984002909A1 (fr) * 1983-01-20 1984-08-02 Electricity Council Ethers fluores
EP0482938A1 (fr) * 1990-10-26 1992-04-29 Rhone-Poulenc Chemicals Limited Synthèse d'éthers fluorés

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5741950A (en) * 1996-12-16 1998-04-21 Minnesota Mining And Manufacturing Company Method of preparing nonafluoroisobutyl methyl ether
US6800786B1 (en) 2002-09-25 2004-10-05 Baxter International, Inc. Preparation of desflurane

Also Published As

Publication number Publication date
GB9221743D0 (en) 1992-12-02

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