WO2024111486A1 - Procédé de production d'un composé de fluorure d'acyle contenant du fluor - Google Patents

Procédé de production d'un composé de fluorure d'acyle contenant du fluor Download PDF

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WO2024111486A1
WO2024111486A1 PCT/JP2023/041151 JP2023041151W WO2024111486A1 WO 2024111486 A1 WO2024111486 A1 WO 2024111486A1 JP 2023041151 W JP2023041151 W JP 2023041151W WO 2024111486 A1 WO2024111486 A1 WO 2024111486A1
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fluorine
carbon atoms
group
acyl fluoride
ester compound
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PCT/JP2023/041151
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English (en)
Japanese (ja)
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貴史 川上
元志 青山
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Ａｇｃ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/38—Acyl halides
    • C07C53/46—Acyl halides containing halogen outside the carbonyl halide group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/38—Acyl halides
    • C07C53/46—Acyl halides containing halogen outside the carbonyl halide group
    • C07C53/50—Acyl halides containing halogen outside the carbonyl halide group of acids containing three or more carbon atoms

Definitions

  • This disclosure relates to a method for producing a fluorine-containing acyl fluoride compound.
  • Fluorine-containing acyl fluoride compounds are particularly useful because various fluorine-containing compounds can be produced by converting the acyl fluoride group into other functional groups.
  • Patent Document 1 describes a method for obtaining a fluorine-containing acyl fluoride compound by reacting a fluorine-containing ester compound with a nucleophile or electrophile in a liquid phase to decompose the compound.
  • the objective of one embodiment of the present invention is to provide a method for producing a fluorine-containing acyl fluoride compound that produces the compound in a higher yield than conventional production methods.
  • a method for producing a fluorine-containing acyl fluoride compound comprising the step of reacting a fluorine-containing ester compound with an alkali metal fluoride having a specific surface area of 0.3 m 2 /g or more to obtain a fluorine-containing acyl fluoride compound.
  • the fluorine-containing ester compound is represented by the following formula (1):
  • R AF is a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having an etheric oxygen atom and having 1 to 2,000 carbon atoms
  • R 3 BF is a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2,000 carbon atoms and having an etheric oxygen atom.
  • the fluorine-containing ester compound is represented by the following formula (3):
  • R CF is a fluoroalkylene group having 1 to 20 carbon atoms or a fluoroalkylene group having 2 to 2,000 carbon atoms and having an etheric oxygen atom
  • R DF and REF each independently represent a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2,000 carbon atoms and an etheric oxygen atom
  • One of R 51 and R 52 is a fluorine atom, and the other is a fluorine atom or a fluoroalkyl group having 1 to 20 carbon atoms.
  • R CF is a perfluoroalkylene group having 1 to 20 carbon atoms or a perfluoroalkylene group having 2 to 2,000 carbon atoms and having an etheric oxygen atom;
  • R DF and REF are each independently a perfluoroalkyl group having 1 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 2,000 carbon atoms and an etheric oxygen atom.
  • ⁇ 7> The method for producing a fluorine-containing acyl fluoride compound according to any one of ⁇ 1> to ⁇ 6>, further comprising a step of fluorinating an ester compound in a liquid phase to obtain a fluorine-containing ester compound.
  • the present disclosure provides a method for producing fluorine-containing acyl fluoride compounds that produces fluorine-containing acyl fluoride compounds in a higher yield than conventional production methods.
  • a numerical range indicated using “to” means a range that includes the numerical values before and after “to” as the minimum and maximum values, respectively.
  • the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in the present disclosure.
  • the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.
  • combinations of two or more preferred aspects are more preferred aspects.
  • the amount of each component means the total amount of multiple substances, unless otherwise specified.
  • the compound represented by the formula (X) may be referred to as compound X.
  • the compound when the compound is a fluorine-containing ester compound, it may also be referred to as fluorine-containing ester compound X.
  • the method for producing a fluorine-containing acyl fluoride compound of the present disclosure includes a step of reacting a fluorine-containing ester compound with an alkali metal fluoride having a specific surface area of 0.3 m 2 /g or more to obtain a fluorine-containing acyl fluoride compound.
  • the alkali metal fluoride used in the reaction is preferably used in the form of particles.
  • the shape of the particles is not particularly limited, and examples thereof include spherical, spindle-shaped, prismatic, cylindrical, flat, and irregular shapes.
  • the specific surface area of the alkali metal fluoride is 0.3 m 2 /g or more. It is considered that the specific surface area of 0.3 m 2 /g or more improves the contact frequency with the fluorine-containing ester compound in the reaction system, and therefore the fluorine-containing acyl fluoride compound can be obtained in high yield.
  • the reaction can be carried out with a smaller amount than before, which is advantageous in terms of the ease of purification treatment and cost.
  • the specific surface area of the alkali metal fluoride is preferably 0.6 m 2 /g or more, and more preferably 1.0 m 2 /g or more.
  • the upper limit of the specific surface area of the alkali metal fluoride is not particularly limited, but from the viewpoint of filterability in the purification step, it is preferably 3.0 m 2 /g.
  • the specific surface area of the alkali metal fluoride is preferably 0.3 to 3.0 m 2 /g, more preferably 0.6 to 3.0 m 2 /g, and even more preferably 1.0 to 3.0 m 2 /g.
  • the specific surface area of alkali metal fluorides can be determined by analyzing the results of measurements taken using a device that uses nitrogen gas as the measurement principle for gas adsorption (for example, Micrometric's "3Flex” or "Flowsorb III") using the BET method.
  • the average particle size of the alkali metal fluoride is preferably 0.005 to 2 mm, and more preferably 0.01 to 1 mm.
  • the average particle size of alkali metal fluorides can be determined by analyzing the particle size distribution measured using an instrument that uses the laser diffraction/scattering method as its measurement principle (e.g., Microtrac MT3300EX II manufactured by Microtrac Corporation).
  • alkali metal fluorides examples include sodium fluoride (NaF), potassium fluoride (KF), and lithium fluoride (LiF).
  • NaF sodium fluoride
  • KF potassium fluoride
  • LiF lithium fluoride
  • the alkali metal fluoride is KF.
  • the method for obtaining an alkali metal fluoride having a specific surface area of 0.3 m 2 /g or more is not particularly limited, but from the viewpoint of obtaining uniform particles, it is preferable to use a spray drying method.
  • the spray drying method is a method in which a solution containing an alkali metal fluoride is sprayed together with hot air into a spray dryer and then dried.
  • the temperature of the hot air is, for example, 300 to 500°C.
  • the amount of alkali metal fluoride used is preferably 5 to 30 mol %, more preferably 10 to 25 mol %, relative to the amount of the fluorine-containing ester compound used.
  • the amount of alkali metal fluoride used is 5 mol % or more, the frequency of contact with the fluorine-containing ester compound in the reaction system is improved, and the fluorine-containing acyl fluoride compound can be obtained in high yield.
  • the amount of alkali metal fluoride used is 30 mol % or less, the viscosity of the reaction system does not become too high, fluidity is maintained, and the frequency of contact with the fluorine-containing ester compound in the reaction system is improved, and the fluorine-containing acyl fluoride compound can be obtained in high yield.
  • the fluorine-containing ester compound used in the reaction is not particularly limited as long as it is an ester compound having a fluorine atom.
  • the number of fluorine atoms contained in the fluorine-containing ester compound is not particularly limited as long as it is one or more.
  • the fluorine-containing ester compound is preferably represented by the following formula (1)
  • the fluorine-containing acyl fluoride compound is preferably represented by the following formula (2).
  • R AF -CF 2 -OC( ⁇ O) -RBF ...
  • R AF is a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 2,000 carbon atoms and an etheric oxygen atom.
  • R BF is a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 2,000 carbon atoms and an etheric oxygen atom.
  • R AF is a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having an etheric oxygen atom and having 1 to 2,000 carbon atoms.
  • the fluoroalkyl group represented by R AF may be a straight-chain fluoroalkyl group, a branched-chain fluoroalkyl group, or a fluoroalkyl group having a ring structure.
  • fluoroalkyl group refers to a group in which one or more hydrogen atoms present in an alkyl group are substituted with a fluorine atom.
  • the fluoroalkyl group may be a partial fluoroalkyl group or a perfluoroalkyl group.
  • partially fluoroalkyl group refers to a group in which some of the hydrogen atoms present in an alkyl group have been substituted with fluorine atoms.
  • perfluoroalkyl group refers to an alkyl group in which all of the hydrogen atoms have been substituted with fluorine atoms.
  • the fluoroalkyl group represented by R AF is preferably a perfluoroalkyl group.
  • the fluoroalkyl group represented by R AF preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms.
  • the fluoroalkyl group having an etheric oxygen atom represented by R AF , is preferably represented by the following formula (X1).
  • R 11 is an alkyl group which may have a fluorine atom
  • R 12 are each independently an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom
  • R 13 is an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom
  • m1 is an integer from 0 to 500
  • at least one of R 11 , R 12 , and R 13 has at least one fluorine atom.
  • examples of R 11 include an alkyl group and a fluoroalkyl group.
  • the number of carbon atoms in R 11 is preferably 1 to 10 from the viewpoint of excellent availability.
  • the alkyl group represented by R 11 may be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.
  • the fluoroalkyl group represented by R 11 may be a straight-chain fluoroalkyl group, a branched-chain fluoroalkyl group, or a fluoroalkyl group having a ring structure.
  • R 11 is preferably a fluoroalkyl group, more preferably a perfluoroalkyl group, still more preferably a linear perfluoroalkyl group, and particularly preferably a linear perfluoroalkyl group having 1 to 6 carbon atoms.
  • m1 is preferably an integer from 0 to 300, more preferably an integer from 0 to 200, even more preferably an integer from 0 to 150, and particularly preferably an integer from 0 to 100.
  • —(R 12 O) m1 — is preferably represented by the following formula (X2). -[(R f1 O) k1 (R f2 O) k2 (R f3 O) k3 (R f4 O) k4 (R f5 O) k5 (R f6 O) k6 ]- ...
  • R f1 is a fluoroalkylene group having 1 carbon atom
  • R f2 is a fluoroalkylene group having 2 carbon atoms
  • R f3 is a fluoroalkylene group having 3 carbon atoms
  • R f4 is a fluoroalkylene group having 4 carbon atoms
  • R f5 is a fluoroalkylene group having 5 carbon atoms
  • R f6 is a fluoroalkylene group having 6 carbon atoms.
  • k1, k2, k3, k4, k5, and k6 each independently represent an integer of 0 or 1 or more
  • k1+k2+k3+k4+k5+k6 is an integer of 0 to 500.
  • k1+k2+k3+k4+k5+k6 is preferably an integer from 0 to 500, more preferably an integer from 0 to 300, even more preferably an integer from 0 to 200, and particularly preferably an integer from 0 to 150.
  • the bonding order of (R f1 O) to (R f6 O) in formula (X2) is arbitrary.
  • k1 to k6 respectively represent the number of (R f1 O) to (R f6 O), and do not represent the arrangement.
  • (R f5 O) k5 represents that the number of (R f5 O) is k5, and does not represent a block arrangement structure of (R f5 O) k5 .
  • the description order of (R f1 O) to (R f6 O) does not represent the bonding order of each unit.
  • the fluoroalkylene group may be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group having a ring structure.
  • R f1 include --CF 2 -- and --CHF--.
  • R f2 examples include -CF 2 CF 2 -, -CF 2 CHF-, -CHFCF 2 -, -CHFCHF-, -CH 2 CF 2 -, and -CH 2 CHF-.
  • R f3 include -CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 -, -CF 2 CH 2 CF 2 -, -CHFCF 2 CF 2 -, -CHFCHFCF 2 -, -CHFCHFCHF-, -CHFCH 2 CF 2 -, -CH 2 CF 2 CF 2 -, -CH 2 CHFCF 2 -, -CH 2 CH 2 CF 2 -, -CH 2 CF 2 CHF-, -CH 2 CHFCHF-, -CH 2 CH 2 CHF- , -CF (CF 3 )-CF 2 -, -CF(CHF 2 )-CF 2 -, -CF(CH 2 F)-CF 2 -, -CF( CH3 ) -CF2- , -CF(CF3)-CHF-, -CF( CHF2 )-CHF-, -CF( CH2F )-CHF- , -CF(CF3)
  • R f4 include -CF 2 CF 2 CF 2 - , -CF 2 CF 2 CHF-, -CF 2 CF 2 CF 2 CH 2 - , -CF 2 CHFCF 2 CF 2 -, -CHFCHFCF 2 CF 2 -, -CH 2 CHFCF 2 CF 2 -, -CF 2 CH 2 CF 2 CF 2 -, -CHFCH 2 CF 2 CF 2 -, -CH 2 CH 2 CF 2 CF 2 -, -CHFCF 2 CHFCF 2 -, -CH 2 CF 2 CHFCF 2 -, -CF 2 CHFCFCF 2 - , and -CF 2 CHFCFCF 2 -, -CHFCHFCHFCF 2 -, -CH 2 CHFCHFCF 2 -, -CF 2 CH 2 CHFCF 2 -, -CHFCH 2 CHFCF 2 -, -CH 2 CH 2 CHFCF 2 -, -CH 2 CHFC
  • R f5 examples include -CF 2 CF 2 CF 2 CF 2 CF 2 -, -CHFCF 2 CF 2 CF 2 -, -CH 2 CHFCF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 CF 2 -, -CHFCHFCF 2 CF 2 CF 2 -, -CF 2 CH 2 CF 2 CF 2 -, -CHFCH 2 CF 2 CF 2 CF 2 -, -CH 2 CH 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CHFCF 2 CF 2 -, -CHFCF 2 CHFCF 2 Examples include -CF 2 -, -CH 2 CF 2 CHFCF 2 CF 2 -, -CH 2 CF 2 CF 2 CF 2 CH 2 -, and -cycloC 5 F 8 -.
  • R f6 include -CF 2 CF 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CHFCHFCF 2 CF 2 -, -CHFCF 2 CF 2 CF 2 CF 2 CF 2 -, -CHFCHFCHFCHFCHFCHF-, -CHFCF 2 CF 2 CF 2 CH 2 - , -CH 2 CF 2 CF 2 CF 2 CH 2 - , and -cycloC 6 F 10 -.
  • -cycloC 4 F 6 - means a perfluorocyclobutanediyl group, a specific example of which is a perfluorocyclobutane-1,2-diyl group
  • -cycloC 5 F 8 - means a perfluorocyclopentanediyl group, a specific example of which is a perfluorocyclopentane-1,3-diyl group
  • -cycloC 6 F 10 - means a perfluorocyclohexanediyl group, a specific example of which is a perfluorocyclohexane-1,4-diyl group.
  • the fluoroalkylene group is preferably a perfluoroalkylene group, and more preferably a linear perfluoroalkylene group.
  • —(R 12 O) m1 — preferably contains —(R f2 O) k2 —, and more preferably contains —(C 2 F 4 O) k2 —.
  • k2 is preferably an integer of 1 to 10, and more preferably 1 to 4.
  • examples of R 13 include the same as R f1 to R f6 above.
  • R 13 is preferably a fluoroalkylene group having 1 to 3 carbon atoms, and more preferably a perfluoroalkylene group having 1 to 3 carbon atoms.
  • the fluoroalkyl group having an etheric oxygen atom is preferably a perfluoroalkyl group having an etheric oxygen atom.
  • R AF include the following structures: In the structural formula, a is preferably 1 to 500, for example, 7. b is preferably 1 to 30, for example, 13. * represents a bonding site with -CF 2 -.
  • R 3 BF is a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2,000 carbon atoms and having an etheric oxygen atom.
  • the fluoroalkyl group represented by R 3 BF is preferably a perfluoroalkyl group, more preferably a branched perfluoroalkyl group.
  • the fluoroalkyl group represented by R 3 BF preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.
  • R 3 BF is preferably a fluoroalkyl group having 1 to 2,000 carbon atoms and having an etheric oxygen atom, and is more preferably represented by the following formula (Y1).
  • R 21 is an alkyl group which may have a fluorine atom
  • R 22 are each independently an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom
  • R 23 is an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom
  • m2 is an integer of 0 to 20
  • at least one of R 21 , R 22 , and R 23 has at least one fluorine atom.
  • examples of R 21 include an alkyl group and a fluoroalkyl group.
  • R 21 preferably has 1 to 50 carbon atoms, more preferably has 1 to 10 carbon atoms, and further preferably has 1 to 6 carbon atoms.
  • the alkyl group represented by R21 may be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.
  • the fluoroalkyl group represented by R 21 may be a straight-chain fluoroalkyl group, a branched-chain fluoroalkyl group, or a fluoroalkyl group having a ring structure.
  • R 21 is preferably a fluoroalkyl group, more preferably a linear fluoroalkyl group, still more preferably a linear fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a linear perfluoroalkyl group having 1 to 6 carbon atoms.
  • m2 is preferably an integer from 0 to 15, more preferably an integer from 0 to 10, even more preferably an integer from 0 to 4, and particularly preferably an integer from 0 to 2.
  • —(R 22 O) m2 — preferably contains —(R f3 O) k3 —, and more preferably contains —(CF 2 —CF(CF 3 )) k3 —.
  • k3 is preferably an integer of 1 to 10, and more preferably 1 to 4.
  • examples of R 23 include the same as R f1 to R f6 above.
  • R 23 is preferably a fluoroalkylene group having 1 to 3 carbon atoms, and more preferably a perfluoroalkylene group having 1 to 3 carbon atoms.
  • At least one of R AF and R BF (preferably R BF ) in formula (1) is a fluoroalkyl group having an etheric oxygen atom, preferably a perfluoroalkyl group having 1 to 2,000 carbon atoms, more preferably a perfluoroalkyl group having 1 to 1,000 carbon atoms.
  • R AF and R BF each independently represent a fluoroalkyl group having 1 to 2,000 carbon atoms, preferably a perfluoroalkyl group having 1 to 2,000 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 1,000 carbon atoms, having an etheric oxygen atom.
  • fluorine-containing ester compounds represented by formula (1) are as follows:
  • the fluorine-containing ester compound is preferably represented by the following formula (3)
  • the fluorine-containing acyl fluoride compound is preferably represented by the following formula (4).
  • formulas (3) to (4)
  • R CF is a fluoroalkylene group having 1 to 20 carbon atoms or a fluoroalkylene group having 2 to 2,000 carbon atoms and containing an etheric oxygen atom.
  • R DF and REF each independently represent a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having an etheric oxygen atom and having 1 to 2,000 carbon atoms.
  • One of R 51 and R 52 is a fluorine atom, and the other is a fluorine atom or a fluoroalkyl group having 1 to 20 carbon atoms.
  • RCF is a fluoroalkylene group having 1 to 20 carbon atoms or a fluoroalkylene group having 2 to 2,000 carbon atoms and containing an etheric oxygen atom.
  • the fluoroalkylene group represented by R CF may be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group having a ring structure.
  • the fluoroalkylene group represented by R CF is preferably a perfluoroalkylene group, and more preferably a linear perfluoroalkylene group.
  • the fluoroalkylene group represented by R 3 CF preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms.
  • the fluoroalkylene group having an etheric oxygen atom represented by R CF is preferably represented by the following formula (C1). -(R 31 O) m3 -R 32 - ... (C1)
  • R 31 and R 32 each independently represent an alkyl group which may have a fluorine atom
  • m3 represents an integer of 1 to 500
  • at least one of R 31 and R 32 has at least one fluorine atom.
  • m3 is preferably 1 to 300, more preferably 1 to 200, and even more preferably 1 to 150.
  • examples of R 32 include the same as R f1 to R f6 above.
  • R CF is preferably a perfluoroalkylene group, and more preferably a linear perfluoroalkylene group.
  • R CF include the following structures: * represents a bonding site with —CF 2 —.
  • c is preferably 1-20, and d is preferably 1-30.
  • R D is the same as a preferred embodiment of R BF .
  • R DF and REF may be the same or different from each other, but are preferably the same from the viewpoint of ease of production of the fluorine-containing ester compound.
  • R 51 and R 52 are a fluorine atom, and the other is a fluorine atom or a fluoroalkyl group having 1 to 20 carbon atoms.
  • the fluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. From the viewpoint of obtaining a compound having two acyl fluoride groups, it is preferable that both R 51 and R 52 are a fluorine atom.
  • fluorine-containing ester compounds represented by formula (3) are as follows:
  • R CF is a perfluoroalkylene group having 1 to 20 carbon atoms, or a perfluoroalkylene group having 2 to 2,000 carbon atoms and having an etheric oxygen atom
  • R DF and REF are each independently a perfluoroalkyl group having 1 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 2,000 carbon atoms and having an etheric oxygen atom.
  • R CF , R DF and R EF is preferably a fluoroalkyl group having 1 to 2,000 carbon atoms and an etheric oxygen atom, more preferably a perfluoroalkyl group having 1 to 2,000 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 1,000 carbon atoms.
  • the reaction temperature in the reaction between the fluorine-containing ester compound and the alkali metal fluoride is not particularly limited, and is, for example, from -20 to 200°C.
  • the reaction time is not particularly limited, and is, for example, from 1 to 12 hours.
  • the method for producing a fluorinated acyl fluoride disclosed herein preferably further includes a step of fluorinating an ester compound in a liquid phase to obtain a fluorinated ester compound (hereinafter also referred to as a "fluorination step").
  • the ester compound used in the fluorination step is not particularly limited as long as it is an ester compound that has an atom that can be fluorinated.
  • Methods for fluorinating an ester compound in a liquid phase include, for example, the ECF method, the cobalt fluorination method, and a method of reacting with fluorine.
  • the method of reacting with fluorine in a liquid phase is preferred, as it is possible to favorably proceed with the fluorination of an ester compound.
  • fluorine gas may be used as is, or fluorine gas diluted with an inert gas may be used.
  • inert gas nitrogen or helium is preferred, and nitrogen is more preferred.
  • the content of fluorine gas is preferably 10% by volume or more, and more preferably 20% by volume or more, from the viewpoint of fluorination efficiency.
  • the content of fluorine is preferably 60% by volume or less, more preferably 50% by volume or less, and even more preferably 40% by volume or less, from the viewpoint of safety. From the above viewpoints, the content of fluorine gas in the mixed gas is preferably 10 to 60% by volume, more preferably 15 to 50% by volume, and even more preferably 20 to 40% by volume.
  • the raw material ester compound is brought into contact with fluorine gas, and the contact time is preferably 0.1 to 1.5 seconds, more preferably 0.3 to 1.5 seconds, and even more preferably 0.8 to 1.2 seconds.
  • the contact time between the ester compound and the fluorine gas can be adjusted, for example, by changing the length of the reaction tube in which the ester compound reacts with the fluorine.
  • the fluorination process is carried out in the liquid phase.
  • the solvent used in the liquid phase so long as it is capable of dissolving the ester compound.
  • the liquid phase preferably contains at least one of a chlorine-containing solvent and a fluorine-containing solvent, and more preferably contains a chlorine-containing solvent.
  • the chlorine-containing solvent is a solvent that contains chlorine atoms.
  • the chlorine-containing solvent preferably contains fluorine atoms in addition to chlorine atoms.
  • chlorine-containing solvents examples include CClF 2 CClFCF 2 OCF 2 CClF 2 (CFE-419), CH 2 ClCHClCH 2 OCF 2 CHFCl (HCFE-473), CF 2 ClCFClCHFOCF 2 CF 2 Cl (HCFE-428a, b), CFHClCFClCF 2 OCF 2 CF 2 Cl (HCFE-428c, d), CF 2 ClCHClCF 2 OCF 2 CF 2 Cl (HCFE-428e), 1,2,3,4-tetrachloroperfluorobutane (R-113), CF 2 Cl-CFCl-CFCl-O-CF 2 -CF 2 Cl (CFE-418), CClHFCClFCHFOCF 2 CClF 2 (HCFE-437a, b), CClF 2 CClHCHFOCF 2 CClF 2 (HCFE-437c), CClHFCClFCH 2 OCF 2 CClF 2 (HCFE-446a), CF
  • fluorine-containing solvents besides chlorine-containing solvents include perfluoroalkanes (FC-72, etc.), perfluoroethers (FC-75, FC-77, etc.), perfluoropolyethers (trade names: Krytox, Fomblin, Galden, Demnum, etc.), inert fluids (trade name: Fluorinert), and perfluorocarboxylic acid fluorides.
  • the liquid phase may contain other additives as necessary.
  • the other additives include assistants that promote the fluorination of the raw material compounds.
  • the assistants include C-H bond-containing compounds and carbon-carbon double bond-containing compounds other than the raw material compounds.
  • C--H bond-containing compounds include benzene, toluene, and the like.
  • Examples of the carbon-carbon double bond-containing compound include hexafluoropropylene and hexafluorobutadiene.
  • the content of the ester compound in the liquid phase is preferably 10 to 70 mass%, more preferably 30 to 50 mass%.
  • Examples 1 to 5 are examples
  • Examples 6 and 7 are comparative examples.
  • GC gas chromatography
  • Example 1 The following fluorine-containing ester compound A1 was obtained using the methods described in Example 1 (step 1-1) and (step 1-2) of JP-A No. 2006-321797.
  • a KF powder with a specific surface area of 1.21 m 2 /g was produced by a spray drying method.
  • 200 g of fluorine-containing ester compound A1 was charged into a 500 mL stainless steel autoclave, and the KF powder was charged in an amount of 5 mol% relative to the fluorine-containing ester compound A1, and heated at 80°C for 6 hours while stirring.
  • the generated gas was continuously extracted through a stainless steel jacketed column heated to 70°C and attached to the top of the reactor, and captured with a dry ice trap.
  • distillation purification was performed to obtain the following fluorine-containing acyl fluoride compound B1 as a product.
  • the yield of fluorine-containing acyl fluoride compound B1 was 95% based on the collected mass and GC analysis.
  • Example 2 and 3 A fluorine-containing acyl fluoride compound B1 was obtained in the same manner as in Example 1, except that the amount of KF powder was changed to the value shown in Table 1.
  • Example 4 A KF powder with a specific surface area of 0.72 m 2 /g was produced by a spray drying method.
  • a fluorine-containing acyl fluoride compound B1 was obtained in the same manner as in Example 2, except for using this KF powder.
  • Example 5 Using the method described in Example 1 of WO 2015/029839, the following fluorine-containing ester compound A2 was obtained.
  • fluorine-containing acyl fluoride compound B2 was obtained in the same manner as in Example 4, except that fluorine-containing ester compound A1 was changed to fluorine-containing ester compound A2.
  • Example 6 The following fluorine - containing ester compound A3 was obtained using the same methods as in (Step 1-1 ) and (Step 1-2 ) of Example 1 of JP-A No. 2006-321797, except that the raw materials were changed to CH 3 (CH 2 ) 7 OH and CF 3 CF 2 CF 2 OCF(CF 3 )COF.
  • fluorine-containing acyl fluoride compound B3 was obtained in the same manner as in Example 2, except that fluorine-containing ester compound A1 was replaced with fluorine-containing ester compound A3 and the reaction temperature was changed to 90°C.
  • Example 7 NaF powder with a specific surface area of 1.17 m 2 /g was produced by a spray drying method. Using this NaF powder, a fluorine-containing acyl fluoride compound B1 was obtained in the same manner as in Example 1, except that the amount of NaF powder was changed to 30 mol % relative to the fluorine-containing ester compound A1 and the reaction temperature was changed to 130°C.
  • Example 8 KF pellets with a specific surface area of 0.23 m 2 /g were prepared.
  • a fluorine-containing acyl fluoride compound B1 was obtained in the same manner as in Example 2, except that KF pellets were used.
  • Example 9 NaF pellets with a specific surface area of 0.21 m 2 /g were prepared.
  • a fluorine-containing acyl fluoride compound B1 was obtained in the same manner as in Example 7, except that NaF pellets were used.
  • Examples 1 to 7 include a step of reacting a fluorine-containing ester compound with an alkali metal fluoride having a specific surface area of 0.3 m 2 /g or more to obtain a fluorine-containing acyl fluoride compound, and it was found that the fluorine-containing acyl fluoride compound could be produced in a higher yield than in Examples 8 and 9.
  • the yield was higher in Example 2 than in Example 1, and higher in Example 3 than in Example 2. It was confirmed that the yield was higher as the amount of alkali metal fluoride used was larger. Comparing Examples 2 and 4, it was confirmed that the yield was higher in Example 2, which had a larger specific surface area.
  • the method for producing a fluorine-containing acyl fluoride compound disclosed herein can produce a fluorine-containing acyl fluoride compound in a higher yield than conventional methods.
  • the obtained fluorine-containing acyl fluoride compound can be derived into a fluorine-containing compound having various functional groups (e.g., a hydroxyl group, an ethylenically unsaturated group, an epoxy group, a carboxy group, etc.).
  • the obtained fluorine-containing ester compound and fluorine-containing compound can be used as a surface treatment agent, an emulsifier, rubber, a surfactant, a solvent, a heat transfer medium, a pharmaceutical, an agricultural chemical, a lubricant, an intermediate thereof, etc.

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Abstract

L'invention concerne un procédé de production d'un composé de fluorure d'acyle contenant du fluor, ledit procédé comprenant une étape consistant à faire réagir un composé d'ester contenant du fluor avec un fluorure de métal alcalin ayant une surface spécifique d'au moins 0,3 m2/g pour obtenir un composé de fluorure d'acyle contenant du fluor.
PCT/JP2023/041151 2022-11-21 2023-11-15 Procédé de production d'un composé de fluorure d'acyle contenant du fluor WO2024111486A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5865226A (ja) * 1981-10-14 1983-04-18 Morita Kagaku Kogyo Kk 有機化合物のフッ素化方法
JPS62103038A (ja) * 1985-10-30 1987-05-13 Asahi Chem Ind Co Ltd ４，４′−ジフルオロフタロフエノン類の製造方法
JPS6310737A (ja) * 1986-07-01 1988-01-18 Seimi Chem Kk 有機化合物のフツ素化方法
JPS6389417A (ja) * 1986-10-01 1988-04-20 Hashimoto Kasei Kogyo Kk 無水フツ化カリウムの製造方法
JPH02111624A (ja) * 1988-10-21 1990-04-24 Ihara Chem Ind Co Ltd フッ素化用凍結乾燥フッ化カリウム
JP2006321797A (ja) * 2005-04-22 2006-11-30 Asahi Glass Co Ltd ペルフルオロカルボン酸塩の新規製造方法
WO2015029839A1 (fr) * 2013-08-26 2015-03-05 旭硝子株式会社 Procédé de production d'un composé fluoré

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5865226A (ja) * 1981-10-14 1983-04-18 Morita Kagaku Kogyo Kk 有機化合物のフッ素化方法
JPS62103038A (ja) * 1985-10-30 1987-05-13 Asahi Chem Ind Co Ltd ４，４′−ジフルオロフタロフエノン類の製造方法
JPS6310737A (ja) * 1986-07-01 1988-01-18 Seimi Chem Kk 有機化合物のフツ素化方法
JPS6389417A (ja) * 1986-10-01 1988-04-20 Hashimoto Kasei Kogyo Kk 無水フツ化カリウムの製造方法
JPH02111624A (ja) * 1988-10-21 1990-04-24 Ihara Chem Ind Co Ltd フッ素化用凍結乾燥フッ化カリウム
JP2006321797A (ja) * 2005-04-22 2006-11-30 Asahi Glass Co Ltd ペルフルオロカルボン酸塩の新規製造方法
WO2015029839A1 (fr) * 2013-08-26 2015-03-05 旭硝子株式会社 Procédé de production d'un composé fluoré

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