WO1994029498A1 - Procede de production de 1,4-dihydroperfluorobutane - Google Patents

Procede de production de 1,4-dihydroperfluorobutane Download PDF

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Publication number
WO1994029498A1
WO1994029498A1 PCT/JP1994/000866 JP9400866W WO9429498A1 WO 1994029498 A1 WO1994029498 A1 WO 1994029498A1 JP 9400866 W JP9400866 W JP 9400866W WO 9429498 A1 WO9429498 A1 WO 9429498A1
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WO
WIPO (PCT)
Prior art keywords
reaction
acid
alkali metal
metal salt
dihydroperfluorobutane
Prior art date
Application number
PCT/JP1994/000866
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English (en)
Japanese (ja)
Inventor
Hirokazu Aoyama
Takashi Yasuhara
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.
Publication of WO1994029498A1 publication Critical patent/WO1994029498A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
    • C07C17/363—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms by elimination of carboxyl groups
    • 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

Definitions

  • the present invention relates to 1,4-dihydroperfluorobutane (hereinafter, referred to as HFC-338 pcc) which is an HFC compound which can be used as a substitute for a CFC compound or an H CFC compound which is widely used as a refrigerant, a generator, and a washing agent. )).
  • HFC-338 pcc 1,4-dihydroperfluorobutane
  • An object of the present invention is to produce 1,4-dihydroperfluorobutane (HFC-338 pcc) from easily available raw materials in good yield.
  • the present inventors have conducted intensive studies on an economical and industrial method for producing HFC-338 pcc.
  • the alkali metal salt of 2,2,3,3-tetrafluoropropionic acid was converted to water, alcohol, Oxidation in platinum acetonitrile or a mixed solvent of these with platinum positivity results in a decarboxylation dimerization reaction, which indicates that 1,4-dihydroperfluorobutane can be obtained in good yield.
  • platinum positivity results in a decarboxylation dimerization reaction, which indicates that 1,4-dihydroperfluorobutane can be obtained in good yield.
  • the first invention of the present invention was completed intensive studies on an economical and industrial method for producing HFC-338 pcc.
  • the first invention relates to a method of preparing a salt of 2,2,3,3-tetrafluoropropionic acid (particularly an alkali metal salt) in a solvent comprising at least one selected from water, alcohol and acetonitrile at an anode (
  • the present invention relates to the S ⁇ ⁇ t method of obtaining 1,4-dihydro ⁇ -p-fluorobutane through a decarboxylation dimerization reaction by electrolytic oxidation on a platinum anode.
  • the method of the first invention is based on the following reaction (Kolbe reaction), and can take the following embodiments.
  • platinum for the anode, and particularly preferable to use a platinum plate having a smooth surface.
  • platinum, carbon, lead, nickel, iron, copper, and the like can be used as the material of the cathode.
  • Alcohol Water, alcohol, acetonitrile, or a mixture thereof is used as a solvent for the reaction.
  • the alcohol include monohydric alcohols such as methanol, ethanol, propanol, and butanol, and divalent alcohols such as ethylene glycol and propylene glycol. Alcohol and the like, and methanol, ethanol and ethylene glycol are particularly preferable.
  • any method such as constant, constant current, and constant potential may be used.
  • the reaction of the first invention it is preferable to carry out the anodic oxidation reaction at a current density of 10 to 2000 mA / cm 2 in order to increase the yield of decarboxylation dimerization.
  • the raw materials used in the first invention include 2,2,3,3-tetrafluoro
  • the metal salt of propionic acid alone can be used as the raw material, or 2,2,3,3-tetrafluoropropionic acid can be used as the raw material and the metal salt can be used in the reaction system.
  • the reaction can be carried out while neutralizing.
  • the concentration of metal carboxylate to carboxylic acid is about 5 to 10 mol% to suppress two-electron oxidation which is a side reaction.
  • the alkali metal salt of 2,2,3,3-tetrafluoropropionic acid is used as a raw material. Even if the reaction is carried out in the state where it is used (that is, there is no carboxylic acid at all), it has the characteristic that the two-electron oxidation, which is a side reaction, hardly proceeds.
  • the alkali metal salt of 2,2,3,3-tetrafluoropropionic acid used in the first invention a sodium salt or a potassium salt is suitably used.
  • the concentration with respect to the solvent is preferably in the range of 2 to 80 wt%.
  • alkali such as NaOH, KOH, MeONa, EtONa, and the like are converted to 2,2,3,3-tetrafluoropropionic acid. It is necessary to add 2 to 15 mol% to lopropionic acid.
  • concentration of the raw material 2,2,3,3-tetrafluoropropionic acid in the solvent is preferably in the range of 2 to 80% by weight.
  • the ammonium salt of 2,2,3,3-tetrafluoropropionic acid ⁇ Amine salts such as pyridine can also be used as the raw material.
  • the mi-reaction of the first invention may be 0 to ⁇ , preferably
  • the solvent may be refluxed by the heat generated by the reaction, or the reaction may be performed while extracting the product from the reaction tank.
  • electrolytic cell used in the first invention a batch type or a flow type without a diaphragm is particularly used. It is also possible to use an electrolytic cell in which the anode and the cathode are separated by a diaphragm.
  • the raw material of the first invention 2,2,3,3-tetrafluorobution pionic acid and its metal salt, can be easily and industrially obtained by the reaction of tetrafluoroethylene with sodium hydrocyanate or potassium hydrocyanate.
  • sodium 2,2,3,3-tetrafluoropropionate which is commercially available as a herbicide, can be used as it is.
  • the second invention thermally decomposes an alkali metal salt of 2,2,3,3,4,5,5-pentagonal pentanoic acid in water, an alcohol, or a mixed solvent of both, After decarboxylation, 1,4-dihydroperful
  • the present invention relates to a production method for obtaining oroben.
  • 1,4-Dihydro ⁇ -perfluorobutane obtained by the method of the second invention can usually be easily purified by a known purification method such as rectification.
  • Examples of the reaction mode in the production method of the second invention include a batch-type reaction scheme and a metal salt of 2,2,3,3,4,4,5,5-octafluoropentanoic acid. It is possible to take a reaction system of the following formula, in which the product is continuously extracted while continuously charging the reactor.
  • the solvent used in the second invention water, alcohol or a mixture thereof is preferably used, and as the alcohol, glycols such as ethylene glycol, diethylene glycol and propylene glycol can be used in consideration of the reaction (1). preferable.
  • reaction of the second invention is usually 100-200 e C, rather preferably is 120 to: a range of 180.
  • the reaction temperature is lower than this range, the decarboxylation reaction does not substantially proceed, and when the reaction temperature is higher, the reaction progresses rapidly and control becomes difficult.
  • Examples of the alkali metal salt of 2,2,3,3,4,4,5,5-tactafluoropentanoic acid, which is a raw material of the second invention, include 2,2,3,3,4,4,5,5- 1,2,3,3,4,4,5,5-year-old sodium kutafluoropentanoate is used for potassium.
  • alkali metal salts the corresponding carboxylic acid, water, methanol, E evening Nord, ethylene glycol, in a solvent such as diethylene glycol, NaOH, KOH, eONa. MeOK , Et ONa, Et OK, N a 2 COs, K 2 C0 3, NaHCOs, by neutralization with KHCOs like, can be obtained.
  • a solvent such as ethylene glycol or diethylene glycol, which is a solvent for the decarboxylation reaction, This is advantageous because it allows subsequent transition to decarboxylation.
  • 2,2,3,3,4,4,5,5-octafluoropentanoic acid is obtained by the reaction of tetrafluoroethylene with methanol. It can be easily obtained by the oxidation of 4,5,5-octafluoropentanol with permanganic acid or chromic acid (Aliphatic Fluorine Compounds, page 205, einhokd Publishing Corporation) 0
  • the first invention of the present invention relates to a method of preparing a salt of 2,2,3,3-tetrafluorobionic pionic acid (particularly a metal salt of alkali metal) in a solvent comprising at least one selected from water, alcohol and acetonitrile. Since the decarboxylation dimerization reaction is carried out by oxidizing on the anode (particularly a platinum anode), 1, -dihydroperfluorobutane (HFC—338 pcc) can be obtained from easily available inexpensive raw materials in good yield. can do.
  • an alkali metal salt of 2,2,3,3,4,4,5,5-year-old ketafluoropentanoic acid is added to water, alcohol, or both of them. It is thermally decomposed in a mixed solvent and decarboxylated to give 1,4-dihydroperfluorobutane. Therefore, 1,4-dihydroperfluorobutane (HFC—338 pcc) is an easily available ⁇ Can be produced in good yield.
  • 1,4-dihydroperfluorobutane (HFC-338 pcc), an HFC compound that can be used as a substitute for CFC compounds and H CFC compounds, is produced with high yield from easily available ⁇ K raw materials. You can do what you can.
  • Example 4 f 200 ml of ethylene glycol and 246 g of HCF 2 CF 2 CF 2 COOH were charged into a 500 ml glass reaction vessel equipped with a distillation extractor equipped with a condenser cooled to 1 ° C. Then, while adjusting the internal temperature to 55 eC and stirring, 90 g of potassium carbonate was charged over 2 hours.
  • the amount of the organic substance extracted by distillation during the reaction was 195 g, and as a result of analysis by gas chromatography, it contained 98.5% of 1,4-dihydroperfluorobutane. The yield was 95%.
  • Example 4 an alkali metal salt (sodium salt) was prepared by using 41 g of sodium hydroxide instead of carbonic acid lime, and the other reactions were carried out in the same manner. As a result, the amount of organic matter was 193 g. It contains 97% of 1,4-dihydroperfluorobutane. The yield was 93%.
  • 1,4-dihydroperfluorobutane (HFC-338 pcc), which is an HFC compound that can be a substitute for the same compound (compound ⁇ 1 ⁇ 1 ⁇ ?), Is easily available. It can be seen that it can be produced with good yield from raw materials.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de production de 1,4-dihydroperfluorobutane grâce à une dimérisation décarboxylante d'un 2,2,3,3-tétrafluoropropionate métallique alcalin par oxydation électrolytique du sel sur une anode de platine dans un solvant renfermant au minimum de l'eau, de l'alcool et de l'acétonitrile. L'invention porte également sur un autre procédé d'obtention de 1,4-dihydroperfluorobutane, par l'intermédiaire d'une décarboxylation d'un 2,2,3,3,4,4,5,5-octafluoropentanoate métallique alcalin, par décomposition thermique du sel dans l'eau, l'alcool ou un mélange des deux. Ces procédés permettent d'obtenir du 1,4-dihydroperfluorobutane (HFC-338pcc) à partir d'une matière brute de départ peut coûteuse et largement disponible, avec un rendement élevé.
PCT/JP1994/000866 1993-06-10 1994-05-30 Procede de production de 1,4-dihydroperfluorobutane WO1994029498A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP5/165231 1993-06-10
JP16523193 1993-06-10
JP5/165232 1993-06-10
JP16523293 1993-06-10

Publications (1)

Publication Number Publication Date
WO1994029498A1 true WO1994029498A1 (fr) 1994-12-22

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009526131A (ja) * 2006-02-08 2009-07-16 ダイナミック フード イングリディエンツ コーポレーション エリスロースまたはエリスリトールの電解製造法
JP2009263729A (ja) * 2008-04-25 2009-11-12 Asahi Glass Co Ltd フルオロカーボンの製造方法および新規なフルオロカーボン
RU2739319C1 (ru) * 2020-07-02 2020-12-22 Общество С Ограниченной Ответственностью "Ника-Петротэк" Способ получения α,ω-дигидроперфторбутана

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5640616A (en) * 1979-09-11 1981-04-16 Sanabotsuto Kk Decarboxylation of carboxylic acids
JPS63183541A (ja) * 1986-10-01 1988-07-28 Shinakita Kasei Kk フッ素系不活性液体組成物の製造方法
JPH0261081A (ja) * 1988-08-25 1990-03-01 Hoechst Ag ペルフルオロカルボン酸またはその可溶性塩を電解的に脱カルボキシル化しそしてその際に生じた遊離基を次いで二量体化する方法
US5084146A (en) * 1990-04-09 1992-01-28 E. I. Du Pont De Nemours And Company Method for preparing perfluoropolyethers
JPH0544070A (ja) * 1991-08-08 1993-02-23 Sumitomo Seika Chem Co Ltd 長鎖脂肪族アルコール又はそのアルキルエステルの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5640616A (en) * 1979-09-11 1981-04-16 Sanabotsuto Kk Decarboxylation of carboxylic acids
JPS63183541A (ja) * 1986-10-01 1988-07-28 Shinakita Kasei Kk フッ素系不活性液体組成物の製造方法
JPH0261081A (ja) * 1988-08-25 1990-03-01 Hoechst Ag ペルフルオロカルボン酸またはその可溶性塩を電解的に脱カルボキシル化しそしてその際に生じた遊離基を次いで二量体化する方法
US5084146A (en) * 1990-04-09 1992-01-28 E. I. Du Pont De Nemours And Company Method for preparing perfluoropolyethers
JPH0544070A (ja) * 1991-08-08 1993-02-23 Sumitomo Seika Chem Co Ltd 長鎖脂肪族アルコール又はそのアルキルエステルの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF FLUORINE CHEMISTRY, Vol. 59, No. 1, (1992), HUDLICKY, TOMAS et al., "Practical Preparation of Some Potentially Anesthetic Fluoroalkanes: Regiocontrolled Introduction of Hydrogen Atoms", p. 9-14. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009526131A (ja) * 2006-02-08 2009-07-16 ダイナミック フード イングリディエンツ コーポレーション エリスロースまたはエリスリトールの電解製造法
JP2009263729A (ja) * 2008-04-25 2009-11-12 Asahi Glass Co Ltd フルオロカーボンの製造方法および新規なフルオロカーボン
RU2739319C1 (ru) * 2020-07-02 2020-12-22 Общество С Ограниченной Ответственностью "Ника-Петротэк" Способ получения α,ω-дигидроперфторбутана

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