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WO2007020816A1 - Procédé de production d’un sel d'acide difluoroacétique - Google Patents

Procédé de production d’un sel d'acide difluoroacétique Download PDF

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Publication number
WO2007020816A1
WO2007020816A1 PCT/JP2006/315484 JP2006315484W WO2007020816A1 WO 2007020816 A1 WO2007020816 A1 WO 2007020816A1 JP 2006315484 W JP2006315484 W JP 2006315484W WO 2007020816 A1 WO2007020816 A1 WO 2007020816A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydroxide
potassium
metal
tetrafluoroethane
difluoroacetate
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/JP2006/315484
Other languages
English (en)
Japanese (ja)
Inventor
Satoru Okamoto
Satoshi Yoshikawa
Yasuo Hibino
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.)
Central Glass Co Ltd
Original Assignee
Central Glass Co 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 Central Glass Co Ltd filed Critical Central Glass Co Ltd
Publication of WO2007020816A1 publication Critical patent/WO2007020816A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion

Definitions

  • the present invention relates to a method for producing difluoroacetate useful as an intermediate for medical and agricultural chemicals and an intermediate for functional materials.
  • a method for producing acetate a method of reacting acetic acid with a metal hydroxide has been widely known.
  • difluoroacetic acid is conventionally known as in the case of an acetate without a fluorine atom.
  • it is produced by reacting a metal hydroxide with a metal hydroxide, and examples other than this method have been known.
  • a method for producing difluoroacetic acid for example, in Patent Document 1, dichloroacetic acid chloride is reacted with a secondary amine to form N, N disubstituted dichloroacetic acid amide, and the N, N disubstituted dichloroacetic acid is produced.
  • a method for producing difluoroacetic acid by reacting an amide with a fluorinating agent such as an alkyl metal fluoride to form an N, N disubstituted difluoroacetamide, and then hydrolyzing the N, N disubstituted difluoroacetamide. ing.
  • Patent Document 2 S-difluoro-2-troethane is hydrolyzed in water to obtain difluoroacetic acid S.
  • Non-Patent Document 1 dichloroacetic acid methyl ester is converted to a fluoride such as KF.
  • a method for producing difluoroacetic acid by hydrolyzing methyl fluoroacetate after fluorination with difluoroacetic acid methyl ester is disclosed.
  • Patent Document 3 and Non-Patent Documents are disclosed as conventional techniques related to the present invention using 1 alkoxy 1,1,2,2-tetrafluoroethane represented by the formula [1] which is a raw material of the present invention.
  • Reference 2 [This is a 1-no-recoxi 1, 1, 2, 2--Terrafnore old Roetan, Anolemina (AI O)
  • R is an alkyl group having 1 to 4 carbon atoms.
  • Patent Document 1 JP-A-6-228043
  • Patent Document 2 JP-A-60-041634
  • Patent Document 3 JP-A-8-92162
  • Non-patent literature l Rec. Trav. Chim., 65 ⁇ , 427, 1947
  • Non-Patent Document 2 Reports Res. Lab. Asahi Glass Co., ltd., Vol. 47, 69-79, 1997
  • the method power S of reacting the corresponding difluoroacetic acid and metal hydroxide is considered to be the most common, but at that time, it is the raw material.
  • Method power to obtain difluoroacetic acid was not always easy.
  • a fluorinating agent that is difficult to handle must be used, and in addition, a large amount of waste such as inorganic salts after the reaction is by-produced.
  • multiple steps were taken to obtain difluoroacetic acid this was not advantageous for large-scale production.
  • sulfuric acid is used for hydrolysis, there is a problem that a large amount of sulfuric acid waste liquid is generated.
  • the above production method for obtaining difluoroacetate is difficult to produce difluoroacetate as a raw material, and a method for producing difluoroacetate by a more advantageous and efficient method is required. It was.
  • HCF 2 CF 2 OR 1 (Wherein R 1 represents a linear or branched alkyl group having 1 to 20 carbon atoms) and a difluoroacetate salt by reacting with an alcohol having 1 to 20 carbon atoms and a metal hydroxide or metal alkoxide.
  • R 1 represents a linear or branched alkyl group having 1 to 20 carbon atoms
  • R 1 represents a linear or branched alkyl group having 1 to 20 carbon atoms
  • a difluoroacetate salt by reacting with an alcohol having 1 to 20 carbon atoms and a metal hydroxide or metal alkoxide.
  • 1-alkoxy-1, 1, 2, 2-tetrafluoroethane which is a raw material of the present invention, has a fluorine atom as a carbon atom. Due to the strong electron withdrawing property of the fluorine atom, the reactivity of the hydrogen atom bonded to the ⁇ -position carbon atom becomes more energetically unstable than that without the fluorine atom, and the alkoxyalkane has been conventionally used. Unlike the complex substrate, it was expected that it would be extremely difficult to produce the corresponding difluoroacetate salt, which has a greater tendency to induce side reactions.
  • the present invention does not require the production of difluoroacetic acid, and is one-step from 1alkoxy 1,1,2,2-tetrafluoroethane and also includes waste.
  • the target difluoroacetate can be produced with a low and high selectivity. This is a particularly useful method for implementation on an industrial scale.
  • 1 alkoxy 1, 1, 2, 2-tetrafluoroethane represented by the formula [1] is reacted with an alcohol having 1 to 20 carbon atoms and a metal hydroxide or metal alkoxide.
  • a method for producing a metal salt of difluoroacetic acid is provided.
  • R 1 in the 1 alkoxy 1, 1, 2, 2-tetrafluoroethane represented by the formula [1] used in this reaction represents a linear or branched alkyl group having 1 to 20 carbon atoms.
  • 1S the usefulness of the linear or branched alkyl group strength product having 1 to 10 carbon atoms and the effect of coexistence are particularly remarkable, more preferably 1 to 6 carbon atoms. Or a linear or branched alkyl group.
  • 1-methoxy 1, 1, 2, 2-tetrafluoroethanethane (HFE-254pc) which is relatively easy to produce, is preferred!
  • Examples of the alcohol having 1 to 20 carbon atoms used in the present invention include an alcohol represented by ROH, and R represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. (Wherein some or all of the hydrogen atoms may be replaced by halogen (fluorine, chlorine, bromine, iodine)) or aryl groups (where some or all of the hydrogen atoms are halogen (fluorine, Chlorine, bromine, iodine).
  • methanol, ethanol, n— Propanol, n-butanol Preferably methanol, ethanol, n— Propanol, n-butanol.
  • the metal hydroxide is not particularly limited as long as it is a metal hydroxide that allows the reaction to proceed efficiently.
  • Group power consisting of potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, and calcium hydroxide. At least one selected from the group is preferred. Particularly preferred.
  • the metal alkoxide is selected from the group consisting of sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium n-propoxide, potassium n-propoxide, sodium isopropoxide, potassium isopropoxide.
  • potassium methoxide is selected from the group consisting of sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium n-propoxide, potassium n-propoxide, sodium isopropoxide, potassium isopropoxide.
  • potassium methoxide is particularly preferred.
  • the reaction of the present invention comprises diphloor metal acetate by reacting 1-alkoxy 1, 1, 2, 2-tetrafluoroethane with an alcohol having 1 to 20 carbon atoms and a metal hydroxide. Although it is a manufacturing method of salt, if a preferable combination is shown, it will be represented by the following reaction formula.
  • one alkoxy 1,1,2,2-tetrafluoroethane has 1 mol of alcohol per 1 mol. Alcohol is charged excessively and the cost is high. It is industrially useful to adjust the consumption of 2,2-tetrafluoroethane to increase.
  • the molar ratio of 1 alkoxy 1,1,2,2-tetrafluoroethane and alcohol is 1: 0.5-1: 200, preferably 1: 1-1: 100, more preferably Can be added from 1: 1 to L: 20 and metal hydroxide and 1alkoxy 1,1,2,2-tetrafluoroethane consumed as the reaction proceeds.
  • alcohol is used as a reaction reagent, and since it can function as a solvent, it is not usually necessary to use another solvent.
  • a solvent The reaction rate can be increased by adding an aprotic polar solvent into the reaction system.
  • the aprotic polar solvent used in this reaction is not particularly limited, but dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), dimethylformamide (D MF), nitromethane, acetonitrile, hexamethylphosphoric triamide (HMPA), glyme, diglyme, jetyl ether, tetrahydrofuran (THF), 1,4 dioxane, etc.
  • DMSO dimethyl sulfoxide
  • DMAC dimethylacetamide
  • DMF dimethylformamide
  • HMPA hexamethylphosphoric triamide
  • glyme diglyme, jetyl ether, tetrahydrofuran (THF), 1,4 dioxane, etc.
  • the amount of the solvent used is usually 0.05 to 1 times mol, preferably 0.1 to 0.3 times mol for 1 mol of 1 alkoxy 1,1,2,2-tetrafluoroethane. It is appropriately selected from the range.
  • Metal hydroxide or metal alkoxide for example, in KOH stoichiometrically added to an excess of force to react 3 moles per mole of 1 alkoxy 1, 1, 2, 2-tetrafluoroethane. If the reaction system! Since there is an increased possibility that the metal salt of difluoroacetic acid that is produced and precipitated will be precipitated together with the metal hydroxide or metal alkoxide, it becomes difficult to purify it.
  • the reaction pressure is not particularly limited, the reaction pressure is 0.1 lMPa to l. OMPa (absolute pressure, hereinafter the same in the present specification), and preferably 0.1 lMPa to 0.6 MPa. It is.
  • the target metal salt of difluoroacetate can be produced even under a mild pressure condition of 0.1 MPa to 0.6 MPa.
  • reaction temperature is not particularly limited, it can be carried out under relatively mild temperature conditions, and is in the range of 0 ° C to 100 ° C, preferably 20 ° C to 80 ° C, more preferably 30 °. C ⁇ 70 ° C is good. If the reaction temperature is too low, the reaction does not proceed, and if it is too high, the probability of side reactions increases, which is not economically preferable.
  • This reaction is a semi-continuous method in which a liquid alcohol in which a metal hydroxide is saturated into 1 alkoxy 1, 1, 2, 2-tetrafluoroethane is continuously introduced, metal hydroxide.
  • a semi-continuous system in which 1 alkoxy 1, 1, 2, 2-tetrafluoroethane is continuously introduced into liquid alcohol saturated with the product, or a batch in which all raw materials are charged into the reactor at once. It does not specifically limit, such as performing by a formula. Also, it can be produced in a continuous system in which a metal hydroxide saturated alcohol and 1-alkoxy 1,1,2,2-tetrafluoroethane are introduced into the reactor and the product is continuously withdrawn. .
  • the reactor is a material having heat resistance and corrosion resistance to fluorine, hydrogen fluoride, hydrogen chloride, etc.
  • 1 alkoxy 1, 1, 2, 2-tetrafluoroethane represented by the formula [1] in this reaction has a low boiling point (50 ° C or less) under normal temperature and atmospheric pressure conditions, so the reaction temperature If it is high, it may vaporize.
  • a pressure-resistant reaction vessel is used, and the vessel can be sealed and the reaction can be carried out by the batch method described above under the conditions of the pressure described above.
  • the method for the purification treatment of difluoroacetic acid metal salt is not particularly limited.
  • the resulting difluoroacetate salt has a lower solubility in 1-alkoxy 1, 1, 2, 2-tetrafluoroethane represented by the formula [1].
  • the reaction solution it precipitates with KF as an insoluble solid mixture.
  • the solid mixture can be easily separated by combining ordinary filtration operations.
  • To isolate difluoroacetic acid metal salt from the solid mixture use the difference in solubility with KF and dissolve in a good solvent such as methanol or ethanol, and add a poor solvent such as ether or hexane. It can be analyzed and separated.
  • the difluoroacetate can also be converted to difluoroacetic acid by reaction with an acid such as hydrochloric acid or sulfuric acid.
  • the difluoroacetate is then converted into difluoroacetic acid and the mixture solution power is extracted with a solvent such as ether, and then It can be separated by a normal distillation operation.
  • 1alkoxy 1,1,2,2-tetrafluoroethane as a starting material of the present invention can be produced by a known method. For example, a predetermined amount of methanol and a metal hydroxide are added to a pressure reactor. 1) After introducing a certain amount of tetrafluoroethylene (TFE) to form 1 alkoxy 1, 1, 2, 2-tetrafluoroethane, the reaction proceeds with the method of the present invention. It is also possible to produce a difluoroacetic acid metal salt.
  • TFE tetrafluoroethylene
  • the difluoroacetic acid metal salt obtained by the present invention is a very useful compound used as an intermediate for medical and agricultural chemicals and an intermediate for functional materials.
  • the obtained difluoroacetic acid metal salt can be easily converted to difluoroacetic acid by an acid hydrolysis reaction such as hydrochloric acid or sulfuric acid.
  • Example 1 The power to specifically describe the present invention with reference to examples below. The present invention is not limited by these. Example 1

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production d’un difluoroacétate de métal, lequel comprend la réaction d’un 1-alcoxy-1,1,2,2-tétrafluoroéthane représenté par la formule [1] : [Formule chimique 4] HCF2CF2OR1 (1) (dans laquelle R1 représente un groupe alkyle linéaire ou ramifié en C1 à C20) avec un alcool en C1 à C20 et un hydroxyde de métal ou un alcoxyde de métal.
PCT/JP2006/315484 2005-08-12 2006-08-04 Procédé de production d’un sel d'acide difluoroacétique Ceased WO2007020816A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005235061 2005-08-12
JP2005-235061 2005-08-12

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WO2007020816A1 true WO2007020816A1 (fr) 2007-02-22

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06228043A (ja) * 1993-02-05 1994-08-16 Asahi Glass Co Ltd ジフルオロ酢酸の製造方法
JPH0892162A (ja) * 1994-07-28 1996-04-09 Asahi Glass Co Ltd ジフルオロ酢酸フルオリドおよびジフルオロ酢酸エステルの製造方法
JP2002532442A (ja) * 1998-12-11 2002-10-02 ロディア・シミ 選択的水素化脱ハロゲン化方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06228043A (ja) * 1993-02-05 1994-08-16 Asahi Glass Co Ltd ジフルオロ酢酸の製造方法
JPH0892162A (ja) * 1994-07-28 1996-04-09 Asahi Glass Co Ltd ジフルオロ酢酸フルオリドおよびジフルオロ酢酸エステルの製造方法
JP2002532442A (ja) * 1998-12-11 2002-10-02 ロディア・シミ 選択的水素化脱ハロゲン化方法

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