WO2001068578A1 - Trifluoroacetaldehyde trifluoroethyle hemi-acetal et son procede de preparation - Google Patents

Trifluoroacetaldehyde trifluoroethyle hemi-acetal et son procede de preparation Download PDF

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Publication number
WO2001068578A1
WO2001068578A1 PCT/JP2001/001934 JP0101934W WO0168578A1 WO 2001068578 A1 WO2001068578 A1 WO 2001068578A1 JP 0101934 W JP0101934 W JP 0101934W WO 0168578 A1 WO0168578 A1 WO 0168578A1
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WO
WIPO (PCT)
Prior art keywords
compound
hemiacetal
trifluoroacetaldehyde
trifluoroethyl
trifluoroethanol
Prior art date
Application number
PCT/JP2001/001934
Other languages
English (en)
Japanese (ja)
Inventor
Yoshihiro Matsumura
Osamu Onomura
Original Assignee
Daikin 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 Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Priority to JP2001567677A priority Critical patent/JP4830249B2/ja
Publication of WO2001068578A1 publication Critical patent/WO2001068578A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/313—Compounds having groups containing halogen
    • 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

Definitions

  • the present invention relates to trifluoroacetaldehyde trifluoroethyl hemiacetal and a method for producing the same.
  • Related technology trifluoroacetaldehyde trifluoroethyl hemiacetal and a method for producing the same.
  • Organic compounds containing fluorine atoms are widely used as medicines, agricultural chemicals, and functional materials (for example, liquid crystal materials) and are of great interest.
  • Various methods have already been pioneered as a method for introducing a fluorine atom.
  • trifluoroacetoaldehyde is a reagent capable of introducing a trifluoromethyl group while adding two carbon atoms. It is especially heavily used.
  • the synthesis of trifluoroacetoaldebi to date has been limited to the following methods.
  • Processes (1) and (2) give the desired trifluoroacetaldehyde hydrate in relatively high yields, but the excess lithium aluminum hydride / sodium borohydride is difficult to handle. is necessary. Some require severe reaction conditions (400-450 ° C) and are not suitable for large-scale synthesis.
  • the method (3) has a problem in obtaining nitrile as a raw material, and requires lithium aluminum hydride as in (1) and (2).
  • Method (4) requires nitric acid and severe reaction conditions (around 450 ° C).
  • Method (5) requires highly corrosive HF.
  • reaction products are obtained in the form of hydrates or ethanol adducts of trifluoroacetoaldehyde, and trifluoroacetoaldehydes are obtained from these hydrates or ethanol adducts. It is manufactured using an acid catalyst and heating. In this case, in order to synthesize more efficiently, a method of heating the hydrate in the presence of calcium chloride instead of an acid catalyst has been adopted.
  • One object of the present invention is to provide an organic fluorine compound useful in the fields of medicine, agricultural chemicals, and functional materials (for example, liquid crystal materials).
  • Another object of the present invention is to provide a process for producing such an organic fluorine compound which does not have the drawbacks of the conventional process.
  • the present inventors By electrooxidation of 2,2,2-trifluoroethanol, the present inventors have found that the 2,2,2-trifluoroethanol adduct of trifluoroacetic acid is obtained. It was found that the compound can be easily synthesized, and that the adduct has higher reactivity than the ethanol adduct of trifluoroacetoaldehyde.
  • the electrolytic oxidation method does not require any oxidizing agent, can be performed at normal temperature and normal pressure, and the adduct functions as an equivalent of trifnoroleoloacetaldehyde. It can be said to be a simple and easy synthesis method.
  • the present invention provides trifluoroacetaldehyde trifluoroethyl hemiacetals.
  • the present invention also provides a process for producing trifluoroacetal trifluoroacetyl hemiacetal which comprises electrolytically oxidizing trifluoroethanol.
  • FIG. 1 is a graph showing the relationship between the yield of the product and the reaction time for each of the case where compound 2 was used and the case where compound 3 was used. Detailed description of the invention
  • Trifluoroacetaldehyde trifluoroethyl hemiacetal is generally a 2,2,2-trifluoroethanol adduct of trifluoroacetoaldehyde (ie, Trifluoroacetaldehyde 2,2,2-trifluoroethyl hemiacetal).
  • the conditions of the electrolytic oxidation are as follows.
  • the anode is a material that can be normally used as an anode, for example, platinum, gold, carbon and the like.
  • the cathode is made of a material such as platinum, gold, carbon, zinc, copper, lead, and titanium.
  • the supporting electrolyte is an organic ammonium salt.
  • a tetraalkylammonium salt is preferable.
  • the alkyl has usually 1 to 30 carbon atoms, for example 1 to 12 carbon atoms. Examples of alkyl include methyl, ethyl, propyl, butyl, pentyl, benzyl, octyl, and the like.
  • the counter ion of the ammonium salt that is the supporting electrolyte may be a common base of an inorganic acid or an organic acid.
  • anti-ones are tetrafluoroborate, toluenesulfonate, benzenesnolefonate, methanesnolefonate, hexafnoleo Such as phosphate and park mouth rates.
  • the amount of current may usually be 0.5-2.0 FZmo1, for example 1.0-1.70 FZmo1.
  • the reaction temperature is between 50 ° C and 50 ° C, preferably between 20 ° C and 20 ° C.
  • trifluoroethanol particularly ethanol with 2,2,2-trifnoreo mouth
  • a reaction system consisting of a single solvent of trifluoroethanol may be used, but it is also possible to use a mixture of trifluoroethanol in a solvent such as acetonitrile or propionitrile which is inactive against the electrolytic oxidation reaction. good.
  • 2,2,2-trifluoro-1-phenylethanol (2,2,2-trifluoro-1-phenylethanol) was obtained at a yield of 60%.
  • FIG. 1 is a graph showing the relationship between the yield of the product (compound 5) and the reaction time when compound 2 was used and when compound 3 was used. This indicates that compound 2 has higher reactivity than compound 3.
  • the invention's effect is a graph showing the relationship between the yield of the product (compound 5) and the reaction time when compound 2 was used and when compound 3 was used. This indicates that compound 2 has higher reactivity than compound 3.
  • the trifluoroacetaldehyde trifluoroethyl hemiacetal of the present invention can be used as a drug, a pesticide, a functional material (for example, a liquid crystal material), or as a raw material thereof. According to the production method of the present invention, trifluoroacetaldehyde trifluoromethyl hemiacetal can be easily produced at normal temperature and normal pressure.

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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)

Abstract

L'invention concerne un trifluoroacétaldéhyde trifluoroéthyle hémi-acétal constituant un composé de fluor utilisé comme médicament, comme produit chimique agricole ou comme matière fonctionnelle (matière à cristaux liquides, par exemple). Ce composé s'obtient par oxydation électrolytique d'un trifluoroéthanol.
PCT/JP2001/001934 2000-03-14 2001-03-13 Trifluoroacetaldehyde trifluoroethyle hemi-acetal et son procede de preparation WO2001068578A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2001567677A JP4830249B2 (ja) 2000-03-14 2001-03-13 トリフルオロアセトアルデヒドトリフルオロエチルヘミアセタールの製法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000070232 2000-03-14
JP2000-70232 2000-03-14

Publications (1)

Publication Number Publication Date
WO2001068578A1 true WO2001068578A1 (fr) 2001-09-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2001/001934 WO2001068578A1 (fr) 2000-03-14 2001-03-13 Trifluoroacetaldehyde trifluoroethyle hemi-acetal et son procede de preparation

Country Status (2)

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JP (1) JP4830249B2 (fr)
WO (1) WO2001068578A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4647706A (en) * 1984-07-18 1987-03-03 Atochem Process for the synthesis of 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoroisopropanol
US4658070A (en) * 1985-04-23 1987-04-14 Atochem Process for the synthesis of 2,2,2-trifluoroethanol

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4647706A (en) * 1984-07-18 1987-03-03 Atochem Process for the synthesis of 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoroisopropanol
US4658070A (en) * 1985-04-23 1987-04-14 Atochem Process for the synthesis of 2,2,2-trifluoroethanol

Also Published As

Publication number Publication date
JP4830249B2 (ja) 2011-12-07

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