Method for producing fluorine-containing acyl fluoride compound

Abstract

A method for producing a fluorine-containing acyl fluoride compound, which comprises a step for obtaining a fluorine-containing acyl fluoride compound by reacting a fluorine-containing ester compound with an alkali metal fluoride having a specific surface area of 0.3 m2 / g or more.

Description

Technical Field

[0001] The present disclosure relates to a method for producing a fluorine-containing acyl fluoride compound. Background Art

[0002] There are many industrially useful compounds among fluorine-containing compounds, and various production methods have been developed in the past. In particular, fluorine-containing acyl fluoride compounds are useful because various fluorine-containing compounds can be produced by converting the acyl fluoride group into other functional groups.

[0003] For example, Patent Document 1 describes a method in which a fluorine-containing ester compound is decomposed by reacting with a nucleophilic reagent or an electrophilic reagent in a liquid phase to obtain a fluorine-containing acyl fluoride compound.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: International Publication No. 2000 / 056694 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] However, in the production of fluorine-containing acyl fluoride compounds, there are cases where the yield needs to be further improved.

[0009] The subject of one embodiment of the present invention is to provide a method for producing a fluorine-containing acyl fluoride compound that produces a fluorine-containing acyl fluoride compound with a better yield compared to conventional production methods.

[0010] Solutions to the Problems

[0011] The present disclosure includes the following aspects.

[0012] <1>

[0013] A method for producing a fluorine-containing acyl fluoride compound, comprising 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.

[0014] <2>

[0015] The method for producing a fluorine-containing acyl fluoride compound according to <1>, wherein the amount of the alkali metal fluoride used is 5 to 30 mol% relative to the amount of the fluorine-containing ester compound used.

[0016] <3>

[0017] The method for producing a fluorine-containing acyl fluoride compound according to <1> or <2>, wherein the fluorine-containing ester compound is represented by the following formula (1),

[0018] The fluorine-containing acyl fluoride compound is represented by the following formula (2),

[0019] R AF -CF2-OC(=O)-R BF …(1)

[0020] R AF -C(=O)F…(2)

[0021] In formulas (1) to (2),

[0022] R AF is a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom,

[0023] R BF is a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom.

[0024] <4>

[0025] According to the method for producing a fluorine-containing acyl fluoride compound described in <3>, wherein, in formulas (1) to (2),

[0026] R AF and R BF are each independently a perfluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom.

[0027] <5>

[0028] According to the method for producing a fluorine-containing acyl fluoride compound according to any one of <1> to <4>, wherein the fluorine-containing ester compound is represented by the following formula (3),

[0029] The fluorine-containing acyl fluoride compound is represented by the following formula (4),

[0030] R DF -(O=)C-O-CFR 51 -R CF -CFR 52 -OC(=O)-R EF …(3)

[0031] R 51 -(O=)C-R CF -C(=O)R 52 …(4)

[0032] In formulas (3) to (4),

[0033] R CF is a fluoroalkylene group having 1 to 20 carbon atoms or a fluoroalkylene group having 2 to 2000 carbon atoms and having an etheric oxygen atom,

[0034] R DF and R EF each independently represents a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom,

[0035] R 51 and R 52 one of them is a fluorine atom and the other is a fluorine atom or a fluoroalkyl group having 1 to 20 carbon atoms.

[0036] <6>

[0037] The method for producing a fluorine-containing acyl fluoride compound according to <5>, wherein in formulas (3) to (4),

[0038] R CF is a perfluoroalkylene group having 1 to 20 carbon atoms or a perfluoroalkylene group having 2 to 2000 carbon atoms and having an etheric oxygen atom,

[0039] R DF and R EF each independently represents a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom.

[0040] <7>

[0041] 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.

[0042] Effects of the Invention

[0043] According to the present disclosure, there is provided a method for producing a fluorine-containing acyl fluoride compound, which produces a fluorine-containing acyl fluoride compound with a better yield as compared with the conventional production methods. Detailed Description of Embodiments

[0044] In the present disclosure, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively.

[0045] In the numerical ranges gradually described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the upper limit value or the lower limit value of the numerical range described in other stages. In addition, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the value shown in the examples.

[0046] In the present disclosure, the combination of two or more preferred modes is a more preferred mode.

[0047] In the present disclosure, when there are multiple substances corresponding to each component, unless otherwise specified, the amount of each component refers to the total amount of the multiple substances.

[0048] In the present disclosure, when a compound is represented by a specific formula (X), the compound represented by the formula (X) is sometimes denoted as compound (X). It should be noted that when the compound is a fluorinated ester compound, it is sometimes also denoted as fluorinated ester compound X.

[0049] [Method for producing fluorinated acyl fluoride compound]

[0050] In the method for producing a fluorinated acyl fluoride compound of the present disclosure, it includes a step of reacting a fluorinated ester compound with an alkali metal fluoride having a specific surface area of 0.3 m 2 / g or more to obtain a fluorinated acyl fluoride compound.

[0051] Conventionally, in the method for producing a fluorinated acyl fluoride compound, a method using a fluoride anion as a nucleophile is known, and an alkali metal fluoride is known as a supply source of the fluoride anion. However, the specific form of the alkali metal fluoride has not been studied.

[0052] Hereinafter, the method for producing a fluorinated acyl fluoride compound of the present disclosure will be described in detail.

[0053] (Alkali metal fluoride)

[0054] In the method for producing a fluorinated acyl fluoride compound of the present disclosure, 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 plate-shaped, and irregular shapes.

[0055] The specific surface area of the alkali metal fluoride is 0.3 m 2 / g or more. It is considered that by having a specific surface area of 0.3 m 2 / g or more, the contact frequency with the fluorinated ester compound in the reaction system is increased, so that a fluorinated acyl fluoride compound can be obtained in a high yield. In addition, by using an alkali metal fluoride having a specific surface area of 0.3 m 2 / g or more, the reaction can be carried out in a smaller amount than in the past, which is advantageous in terms of the simplicity of the purification process and cost.

[0056] From the viewpoint of further improving the yield, the specific surface area of the alkali metal fluoride is preferably 0.6 m 2 / g or more, more preferably 1.0 m 2 / g or more. The upper limit value of the specific surface area of the alkali metal fluoride is not particularly limited, and from the viewpoint of the filterability in the purification process, it is preferably 3.0 m 2 / g. From the above viewpoints, 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, further preferably 1.0 to 3.0 m 2 / g.

[0057] The specific surface area of the alkali metal fluoride can be determined by analyzing the results obtained by measuring with a device (e.g., Micrometrics, Inc. "3Flex", "FlowSorb III") using the gas adsorption method with nitrogen as the measurement principle according to the BET method.

[0058] From the viewpoint of further improving the yield, the average particle size of the alkali metal fluoride is preferably 0.005 to 2 mm, more preferably 0.01 to 1 mm.

[0059] The average particle size of the alkali metal fluoride can be determined by analyzing the particle size distribution measured using a device (e.g., "Microtrac MT3300EX II" manufactured by Microtrac) based on the laser diffraction / scattering method.

[0060] Examples of the alkali metal fluoride include sodium fluoride (NaF), potassium fluoride (KF), and lithium fluoride (LiF). Among them, from the viewpoint of further improving the yield, the alkali metal fluoride is preferably KF.

[0061] 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. From the viewpoint of obtaining uniform particles, the spray drying method is preferably used.

[0062] The spray drying method is, for example, a method in which a solution containing an alkali metal fluoride is sprayed into a spray dryer together with hot air and then dried. The temperature of the hot air is, for example, 300 to 500 °C.

[0063] In the method for producing a fluorine-containing acyl fluoride compound of the present disclosure, the amount of the 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. When the amount of the alkali metal fluoride used is 5 mol% or more, the contact frequency with the fluorine-containing ester compound in the reaction system increases, so that a fluorine-containing acyl fluoride compound can be obtained in a high yield. On the other hand, when the amount of the alkali metal fluoride used is 30 mol% or less, the viscosity of the reaction system does not become too high, maintaining fluidity, and the contact frequency with the fluorine-containing ester compound in the reaction system increases, so that a fluorine-containing acyl fluoride compound can be obtained in a high yield.

[0064] (fluorine-containing ester compound)

[0065] 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 1 or more. In addition, the number of ester bonds (-OC(=O)-) contained in the fluorine-containing ester compound may be only one or two or more, but from the viewpoint of easy availability, 1 or 2 is preferred.

[0066] Among them, it is preferred that the fluorine-containing ester compound is represented by the following formula (1), and the fluorine-containing acyl fluoride compound is represented by the following formula (2).

[0067] R AF -CF2-OC(=O)-R BF …(1)

[0068] R AF -C(=O)F…(2)

[0069] In formulas (1) to (2), R AF is a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom. R BF is a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom.

[0070] 〔R AF 〕

[0071] R AF is a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom.

[0072] R AF The fluoroalkyl group represented by R

[0073] may be a linear fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0074] In the present disclosure, "fluoroalkyl group" means a group in which one or more hydrogen atoms present in an alkyl group are replaced by fluorine atoms. The fluoroalkyl group may be a partially fluorinated alkyl group or a perfluoroalkyl group.

[0075] In the present disclosure, "partially fluorinated alkyl group" means a group in which some of the hydrogen atoms present in an alkyl group are replaced by fluorine atoms.

[0076] R AF The fluoroalkyl group represented by R

[0077] R AF The fluoroalkyl group represented by R

[0078] RAF The fluoroalkyl group having an etheric oxygen atom shown is preferably represented by the following formula (X1).

[0079] R 11 O-(R 12 O) m1 -R 13 -…(X1)

[0080] In formula (X1), R 11 is an alkyl group optionally having a fluorine atom, and each R 12 is independently an alkylene group having 1 to 6 carbon atoms and optionally having a fluorine atom, R 13 is an alkylene group having 1 to 6 carbon atoms and optionally having a fluorine atom, m1 is an integer of 0 to 500, and at least one of R 11 , R 12 and R 13 has at least one fluorine atom.

[0081] In formula (X1), examples of R 11 include an alkyl group and a fluoroalkyl group.

[0082] From the viewpoint of excellent availability, the number of carbon atoms of R 11 is preferably 1 to 10.

[0083] The alkyl group represented by R 11 can be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0084] The fluoroalkyl group represented by R 11 can be a linear fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0085] Among them, 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.

[0086] In formula (X1), m1 is preferably an integer of 0 to 300, more preferably an integer of 0 to 200, still more preferably an integer of 0 to 150, and particularly preferably an integer of 0 to 100.

[0087] In formula (X1), -(R 12 O) m1 - is preferably represented by the following formula (X2).

[0088] -[(R f1 O) k1 (R f2 O) k2 (R f3 O) k3 (Rf4 O) k4 (R f5 O) k5 (R f6 O) k6 -…(X2)

[0089] Among them,

[0090] R f1 is a fluoroalkylene group having 1 carbon atom,

[0091] R f2 is a fluoroalkylene group having 2 carbon atoms,

[0092] R f3 is a fluoroalkylene group having 3 carbon atoms,

[0093] R f4 is a fluoroalkylene group having 4 carbon atoms,

[0094] R f5 is a fluoroalkylene group having 5 carbon atoms,

[0095] R f6 is a fluoroalkylene group having 6 carbon atoms.

[0096] k1, k2, k3, k4, k5 and k6 each independently represent an integer of 0 or more, and k1 + k2 + k3 + k4 + k5 + k6 is an integer of 0 to 500.

[0097] From the viewpoint of excellent fluidity of the reaction solution, k1 + k2 + k3 + k4 + k5 + k6 is preferably an integer of 0 to 500, more preferably an integer of 0 to 300, still more preferably an integer of 0 to 200, and particularly preferably an integer of 0 to 150.

[0098] It should be noted that the bonding order of (R f1 O) to (R f6 O) in the formula (X2) is arbitrary. k1 to k6 in the formula (G1-1) respectively represent the number of (R f1 O) to (R f6 O), and do not represent the configuration. For example, (R f5 O) k5 represents that the number of (R f5 O) is k5, and does not represent the block configuration structure of (R f5 O) k5 . Similarly, the recording order of (R f1 O) to (R f6 O) does not represent the bonding order of each unit.

[0099] R f3 ~R f6Among them, the fluoroalkylene group can be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group having a ring structure.

[0100] As a specific example of R f1 , -CF2- and -CHF- can be cited.

[0101] As a specific example of R f2 , -CF2CF2-, -CF2CHF-, -CHFCF2-, -CHFCHF-, -CH2CF2- and -CH2CHF- can be cited.

[0102] As a specific example of R f3 , -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)-CHF-, -CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH2F)-CF2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2- and -CH(CH2F)-CH2- can be cited.

[0103] As a specific example of R f4Specific examples include -CF2CF2CF2CF2-, -CF2CF2CF2CHF-, -CF2CF2CF2CH2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -CF2CHFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF- and -cycloC4F6-.

[0104] As R f5 Specific examples include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2- and -cycloC5F8-.

[0105] As R f6 Specific examples include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2- and -cycloC6F 10 -.

[0106] Here, -cycloC4F6- refers to perfluorocyclobutane diyl, and specific examples thereof include perfluorocyclobutane-1,2-diyl. -cycloC5F8- refers to perfluorocyclopentane diyl, and specific examples thereof include perfluorocyclopentane-1,3-diyl. -cycloC6F 10- refers to perfluorocyclohexanediyl, and as a specific example thereof, perfluorocyclohexane-1,4-diyl can be cited.

[0107] Among them, R f1 ~R f6 in, the fluoroalkylene group is preferably a perfluoroalkylene group, more preferably a linear perfluoroalkylene group.

[0108] In addition, -(R 12 O) m1 - preferably contains -(R f2 O) k2 -, more preferably contains -(C2F4O) k2 -. k2 is preferably 1 to 10, more preferably 1 to 4.

[0109] In the formula (X1), as R 13 , substances the same as the above-mentioned R f1 ~R f6 can be cited.

[0110] Among them, R 13 is preferably a fluoroalkylene group having 1 to 3 carbon atoms, more preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0111] That is, the fluoroalkyl group having an etheric oxygen atom represented by R AF is preferably a perfluoroalkyl group having an etheric oxygen atom.

[0112] As a specific example of R AF , for example, the following structures can be cited. In the structural formula, a is preferably 1 to 500, for example, 7. b is preferably 1 to 30, for example, 13. * represents the bonding site with -CF2-.

[0113]

[0114] 〔R BF 〕

[0115] R BF is a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having an etheric oxygen atom and 1 to 2000 carbon atoms.

[0116] The fluoroalkyl group represented by R BF is preferably a perfluoroalkyl group, more preferably a branched perfluoroalkyl group.

[0117] The carbon number of the fluoroalkyl group represented by R BF is preferably 1 to 10, more preferably 1 to 6.

[0118] Among them, from the viewpoint of excellent availability of raw materials, R BF is preferably a fluoroalkyl group having an etheric oxygen atom and 1 to 2000 carbon atoms, more preferably represented by the following formula (Y1).

[0119] R 21 O-(R 22 O) m2 -R 23 -…(Y1)

[0120] In formula (Y1), R 21 is an optionally fluorine atom-containing alkyl group, and each R 22 is independently an optionally fluorine atom-containing alkylene group having 1 to 6 carbon atoms, R 23 is an optionally fluorine atom-containing alkylene group having 1 to 6 carbon atoms, m2 is an integer of 0 to 20, and at least one of R 21 , R 22 and R 23 has at least one fluorine atom.

[0121] In formula (Y1), examples of R 21 include alkyl groups and fluoroalkyl groups.

[0122] R 21 preferably has 1 to 50 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.

[0123] The alkyl group represented by R 21 can be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0124] The fluoroalkyl group represented by R 21 can be a linear fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0125] Among them, 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.

[0126] In formula (Y1), -(R 22 O) m2 - is preferably represented by the above formula (X2).

[0127] In formula (Y1), m2 is preferably an integer of 0 to 15, more preferably an integer of 0 to 10, still more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2.

[0128] In addition, -(R 22 O) m2 - preferably contains -(R f3 O) k3 -, more preferably contains -(CF2-CF(CF3)) k3 -. k3 is preferably 1 to 10, more preferably 1 to 4.

[0129] In formula (Y1), as R 23 , substances the same as the above R f1 to R f6 can be cited.

[0130] Among them, R 23 is preferably a fluoroalkylene group having 1 to 3 carbon atoms, more preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0131] As a specific example of R BF , for example, the following structures can be cited. * indicates the bonding site with -O-(C=O)-.

[0132]

[0133] As a preferred embodiment of the fluorinated ester compound represented by formula (1), in formula (1), at least one of R AF and R BF (preferably R BF ) is preferably a fluoroalkyl group having 1 to 2000 carbon atoms having an etheric oxygen atom, preferably a perfluoroalkyl group having 1 to 2000 carbon atoms, more preferably a perfluoroalkyl group having 1 to 1000 carbon atoms.

[0134] In addition, in formula (1), R AF and R BF are each independently preferably a fluoroalkyl group having 1 to 2000 carbon atoms having an etheric oxygen atom, preferably a perfluoroalkyl group having 1 to 2000 carbon atoms, more preferably a perfluoroalkyl group having 1 to 1000 carbon atoms.

[0135] Specific examples of the fluorinated ester compound represented by formula (1) are as follows.

[0136]

[0137] In addition, it is preferred that the fluorinated ester compound is represented by the following formula (3), and the fluorinated acyl fluoride compound is represented by the following formula (4).

[0138] R DF -(O=)C-O-CFR 51 -R CF -CFR 52 -OC(=O)-R EF …(3)

[0139] R 51 -(O=)C-R CF -C(=O)R 52 …(4)

[0140] In formulas (3) to (4),

[0141] In formulas (3) to (4),

[0142] R CF is a fluoroalkylene group having 1 to 20 carbon atoms or a fluoroalkylene group having 2 to 2000 carbon atoms with an etheric oxygen atom.

[0143] R DF and R EF are each independently a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2000 carbon atoms with an etheric oxygen atom.

[0144] R 51 and R 52 One of them is a fluorine atom, and the other is a fluorine atom or a fluoroalkyl group having 1 to 20 carbon atoms.

[0145] 〔R CF 〕

[0146] R CF is a fluoroalkylene group having 1 to 20 carbon atoms or a fluoroalkylene group having 2 to 2000 carbon atoms with an etheric oxygen atom.

[0147] R CF The fluoroalkylene group represented by R CF can be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group having a ring structure. Among them, the fluoroalkylene group represented by R

[0148] R CF is preferably a perfluoroalkylene group, more preferably a linear perfluoroalkylene group.

[0149] R CF The fluoroalkylene group having an etheric oxygen atom represented by R

[0150] -(R 31 O) m3 -R 32 -…(C1)

[0151] In formula (C1), R 31 and R 32 are each independently an alkyl group optionally having a fluorine atom, m3 is an integer of 1 to 500, and at least one of R 31 and R 32 has at least one fluorine atom.

[0152] In formula (C1), -(R 31 O) m3 - is preferably represented by the above formula (X2).

[0153] In formula (C1), m3 is preferably 1 to 300, more preferably 1 to 200, and further preferably 1 to 150.

[0154] In formula (Y1), as R 32 , substances the same as the above-mentioned R f1 ~R f6 can be enumerated.

[0155] Among them, R CF is preferably a perfluoroalkylene group, more preferably a linear perfluoroalkylene group.

[0156] As a specific example of R CF , for example, the following structures can be enumerated. * indicates the bonding site with -CF2-.

[0157] In the structural formula, c is preferably 1 to 20, and d is preferably 1 to 30.

[0158]

[0159] 〔R DF , R EF 〕

[0160] The preferred form of R D is the same as that of R BF . R DF and R EF are optionally the same or different from each other, but are preferably the same from the viewpoint of ease of manufacturing the fluorinated ester compound.

[0161] 〔R 51 , R 52 〕

[0162] 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. When the other is a fluoroalkyl group, the number of carbon atoms of the fluoroalkyl group is preferably 1 to 6, more preferably 1 to 4.

[0163] From the viewpoint of obtaining a compound having two acyl fluoride groups, it is preferable that both R 51 and R 52 are fluorine atoms.

[0164] Specific examples of the fluorinated ester compound represented by formula (3) are as follows.

[0165]

[0166] As a preferred form of the fluorinated ester compound represented by formula (3), in formula (3), it is preferable that R CF is a perfluoroalkylene group having 1 to 20 carbon atoms or a perfluoroalkylene group having 2 to 2000 carbon atoms and having an etheric oxygen atom, and R DF and R EFEach independently represents a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom.

[0167] Particularly preferably, R CF , and, R DF and R EF at least one of them (preferably R DF and R EF ) is a fluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom, preferably a perfluoroalkyl group having 1 to 2000 carbon atoms, more preferably a perfluoroalkyl group having 1 to 1000 carbon atoms.

[0168] In the method for producing the fluorinated acyl fluoride compound of the present disclosure, the reaction temperature in the reaction of the fluorinated ester compound with the alkali metal fluoride is not particularly limited, and is, for example, -20 to 200 °C. The reaction time is not particularly limited, and is, for example, 1 to 12 hours.

[0169] In the method for producing the fluorinated acyl fluoride compound of the present disclosure, it preferably further includes a step of fluorinating the ester compound in the liquid phase to obtain a fluorinated ester compound (hereinafter also referred to as "fluorination step").

[0170] The ester compound used in the fluorination step may be any ester compound having a fluorinable atom, and is not particularly limited.

[0171] As a method for fluorinating the ester compound in the liquid phase, for example, the ECF method, the cobalt fluorination method, and the method of reacting with fluorine can be cited. Among them, the method of reacting with fluorine in the liquid phase, which can advantageously perform the fluorination of the ester compound, is preferred.

[0172] In the fluorination step, fluorine gas can be directly used, or fluorine gas diluted with an inert gas can be used. As the inert gas, nitrogen or helium is preferred, and nitrogen is more preferred. From the viewpoint of the efficiency of fluorination, in the mixed gas of the inert gas and fluorine, the content of fluorine gas is preferably 10% by volume or more, more preferably 20% by volume or more. In addition, from the viewpoint of safety, the content of fluorine is preferably 60% by volume or less, more preferably 50% by volume or less, and further preferably 40% by volume or less. 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 further preferably 20 to 40% by volume.

[0173] In the fluorination step, from the viewpoint of efficiently obtaining the fluorinated ester compound, it is preferred that the ester compound as a raw material is brought into contact with fluorine gas, and the contact time is set to 0.1 to 1.5 seconds, more preferably set to 0.3 to 1.5 seconds, and further preferably set to 0.8 to 1.2 seconds.

[0174] The contact time between the ester compound and fluorine gas can be adjusted, for example, by the length of the reaction tube in which the ester compound reacts with fluorine.

[0175] The fluorination process is carried out in the liquid phase. The solvent used in the liquid phase is not particularly limited as long as it can dissolve the ester compound.

[0176] From the viewpoint of the solubility of the ester compound and the fluorinated 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. A chlorine-containing solvent is a solvent containing a chlorine atom. The chlorine-containing solvent preferably contains a fluorine atom in addition to the chlorine atom.

[0177] Examples of the chlorine-containing solvent include CClF2CClFCF2OCF2CClF2 (CFE-419), CH2ClCHClCH2OCF2CHFCl (HCFE-473), CF2ClCFClCHFOCF2CF2Cl (HCFE-428a, b), CFHClCFClCF2OCF2CF2Cl (HCFE-428c, d), CF2ClCHClCF2OCF2CF2Cl (HCFE-428e), 1,2,3,4-tetrachloroperfluorobutane (R-113), CF2Cl-CFCl-CFCl-O-CF2-CF2Cl (CFE-418), CClHFCClFCHFOCF2CClF2 (HCFE-437a, b), CClF2CClHCHFOCF2CClF2 (HCFE-437c), CClHFCClFCH2OCF2CClF2 (HCFE-446a), CF2ClCCl2CF2OCF2CFHCl (HCFE-427a, b), CF2HCClFCF2OCF2CF2Cl (HCFE-429), etc.

[0178] Examples of the fluorine-containing solvent other than the chlorine-containing solvent include perfluoroalkanes (such as FC-72), perfluoroethers (such as FC-75, FC-77), perfluoropolyethers (trade names: Krytox, Fomblin, Galden, Demnum, etc.), inert fluids (trade name: Fluorinert), perfluorocarboxylic acid fluorides, etc.

[0179] The liquid phase may also contain other additives as needed. Examples of other additives include assistants that promote the fluorination of the raw material compound. Examples of assistants include compounds containing a C-H bond and compounds containing a carbon-carbon double bond other than the raw material compound.

[0180] Examples of the compound containing a C-H bond include benzene, toluene, etc.

[0181] Examples of the compound having a carbon-carbon double bond include hexafluoropropene, hexafluorobutadiene, etc.

[0182] In the fluorination process, from the viewpoint of efficiently obtaining a fluorinated ester compound, in the liquid phase, the content of the ester compound is preferably 10 to 70% by mass, more preferably 30 to 50% by mass.

[0183] Examples

[0184] Hereinafter, the present disclosure will be further specifically described by way of examples. However, the present disclosure is not limited to the following examples as long as it does not deviate from its gist. In this example, Examples 1 to 5 are examples, and Examples 6 to 7 are comparative examples.

[0185] Hereinafter, the analysis using gas chromatography (GC) was performed by setting “Rtx-200” (inner diameter 0.25 mm, length 60 m, film thickness 1.00 μm) manufactured by Restek Corporation in an “Agilent 6850 Gas Chromatograph”. Helium was used as the carrier gas. Under the conditions of an injection port temperature of 240 °C, a gas linear velocity of 22.6 cm / s, and a column temperature of 40 °C, after holding for 10 minutes, the temperature was raised to 240 °C at 10 °C / min and held for 20 minutes. A flame ionization detector (FID) was used as the detector. Quantitative analysis was performed using a standard curve with CF3CH2OCF2CF2H (product name “Asahiklin AE-3000”, manufactured by AGC Inc.) as the internal standard.

[0186] [Example 1]

[0187] Using the methods described in Examples 1 (Step 1-1) and (Step 1-2) of JP-A-2006-321797, the following fluorinated ester compound A1 was obtained.

[0188]

[0189] KF powder with a specific surface area of 1.21 m 2 / g was produced by the spray drying method.

[0190] 200 g of the fluorinated ester compound A1 was charged into a 500 mL stainless steel autoclave, and the above KF powder was charged in an amount of 5 mol% relative to the fluorinated ester compound A1. The mixture was 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 provided at the upper part of the reactor and captured by a dry ice collector. After the reaction was completed, distillation purification was performed to obtain the following fluorinated acyl fluoride compound B1 as the product. According to the recovered mass and the analysis using GC, the yield of the fluorinated acyl fluoride compound B1 was 95%.

[0191]

[0192] [Examples 2 and 3]

[0193] A fluorine-containing acyl fluoride compound B1 was obtained in the same manner as in Example 1, except that the amount of KF powder charged was changed to the value described in Table 1.

[0194] [Example 4]

[0195] KF powder with a specific surface area of 0.72 m 2 / g was produced by spray drying.

[0196] A fluorine-containing acyl fluoride compound B1 was obtained in the same manner as in Example 2, except that this KF powder was used.

[0197] [Example 5]

[0198] The following fluorine-containing ester compound A2 was obtained using the method described in Example 1 of International Publication No. 2015 / 029839.

[0199]

[0200] The following fluorine-containing acyl fluoride compound B2 was obtained in the same manner as in Example 4, except that the fluorine-containing ester compound A1 was changed to the fluorine-containing ester compound A2.

[0201]

[0202] [Example 6]

[0203] 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 Japanese Patent Application Laid-Open No. 2006-321797, except that the raw materials were changed to CH3(CH2)7OH and CF3CF2CF2OCF(CF3)COF.

[0204]

[0205] The following fluorine-containing acyl fluoride compound B3 was obtained in the same manner as in Example 2, except that the fluorine-containing ester compound A1 was changed to the fluorine-containing ester compound A3 and the reaction temperature was changed to 90°C.

[0206]

[0207] [Example 7]

[0208] NaF powder with a specific surface area of 1.17 m 2 / g was produced by spray drying.

[0209] Except for using the NaF powder and changing the amount of the NaF powder to 30 mol% relative to the fluorine-containing ester compound A1 and changing the reaction temperature to 130 °C, the fluorine-containing acyl fluoride compound B1 was obtained in the same manner as in Example 1.

[0210] [Example 8]

[0211] KF pellets with a specific surface area of 0.23 m 2 / g were prepared.

[0212] Except for changing to use the KF pellets, the fluorine-containing acyl fluoride compound B1 was obtained in the same manner as in Example 2.

[0213] [Example 9]

[0214] NaF pellets with a specific surface area of 0.21 m 2 / g were prepared.

[0215] Except for changing to use the NaF pellets, the fluorine-containing acyl fluoride compound B1 was obtained in the same manner as in Example 7.

[0216] The yields of the fluorine-containing acyl fluoride compounds are shown in Table 1.

[0217] [Table 1]

[0218]

[0219] As shown in Table 1, it can be seen that in Examples 1 to 7, there is 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 compared with Examples 8 to 9, the fluorine-containing acyl fluoride compound can be efficiently produced.

[0220] Comparing Examples 1 to 3, the yield of Example 2 is higher than that of Example 1, and the yield of Example 3 is higher than that of Example 2. It was confirmed that the higher the amount of the alkali metal fluoride used, the higher the yield. Comparing Example 2 with Example 4, it was confirmed that the yield of Example 2 with a larger specific surface area is higher.

[0221] Industrial Applicability

[0222] The method for producing the fluorine-containing acyl fluoride compound of the present disclosure can produce the fluorine-containing acyl fluoride compound at a higher yield than in the past. The obtained fluorine-containing acyl fluoride compound can be derivatized into fluorine-containing compounds having various functional groups (such as hydroxyl group, ethylenically unsaturated group, epoxy group, carboxyl group, etc.). In addition, the obtained fluorine-containing ester compound and fluorine-containing compound can be used as surface treatment agents, emulsifiers, rubbers, surfactants, solvents, heat media, pharmaceuticals, pesticides, lubricating oils, their intermediates, etc.

[0223] The entire disclosure of Japanese Patent Application No. 2022-185951, filed on November 21, 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually recited.

Claims

1. A method for producing a fluorine-containing acyl fluoride compound, which comprises 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.

2. The method for producing a fluorine-containing acyl fluoride compound according to claim 1, wherein, The amount of the alkali metal fluoride used is 5 to 30 mol% relative to the amount of the fluorinated ester compound.

3. The method for producing a fluorine-containing acyl fluoride compound according to claim 1 or 2, wherein, The fluorinated ester compound is represented by the following formula (1), The fluorinated acyl fluoride compound is represented by the following formula (2), R AF -CF2-OC(=O)-R BF …(1) R AF -C(=O)F…(2) In formulae (1) to (2), R AF is a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom, R BF is a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2000 carbon atoms and an etheric oxygen atom.

4. The method for producing a fluorine-containing acyl fluoride compound according to claim 3, wherein, In the said formulae (1) to (2), R AF and R BF each independently represents a perfluoroalkyl group having from 1 to 2000 carbon atoms and having an etheric oxygen atom.

5. The method for producing a fluorine-containing acyl fluoride compound according to claim 1 or 2, wherein, The fluorinated ester compound is represented by the following formula (3), The fluorinated acyl fluoride compound is represented by the following formula (4), R DF -(O=)C-O-CFR 51 -R CF -CFR 52 -OC(=O)-R EF …(3) R 51 -(O=)C-R CF -C(=O)R 52 …(4) In formulae (3) to (4), R CF is a fluoroalkylene group having 1 to 20 carbon atoms or a fluoroalkylene group having 2 to 2000 carbon atoms and having an etheric oxygen atom, R DF and R EF each independently represents a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom, R 51 and R 52 One of them is a fluorine atom, and the other is a fluorine atom or a fluoroalkyl group having 1 to 20 carbon atoms.

6. The method for producing a fluorine-containing acyl fluoride compound according to claim 5, wherein, In the said formulae (3) to (4), R CF is a perfluoroalkylene group having 1 to 20 carbon atoms or a perfluoroalkylene group having 2 to 2000 carbon atoms and containing an etheric oxygen atom, R DF and R EF each independently represents a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom.

7. The method for producing a fluorinated acyl fluoride compound according to claim 1 or 2, further comprising a step of fluorinating an ester compound in a liquid phase to obtain the fluorinated ester compound.

8. The method for producing a fluorinated acyl fluoride compound according to claim 1 or 2, further comprising a step of fluorinating an ester compound in a liquid phase to obtain the fluorinated ester compound, The fluorinated ester compound is represented by the following formula (1), The fluorinated acyl fluoride compound is represented by the following formula (2), R AF -CF2-OC(=O)-R BF …(1) R AF -C(=O)F…(2) In formulae (1) to (2), R AF is a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom, R BF is a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2000 carbon atoms and an etheric oxygen atom.

9. The method for producing a fluorinated acyl fluoride compound according to claim 1 or 2, further comprising a step of fluorinating an ester compound in a liquid phase to obtain the fluorinated ester compound. The fluorinated ester compound is represented by the following formula (3), The fluorinated acyl fluoride compound is represented by the following formula (4), R DF -(O=)C-O-CFR 51 -R CF -CFR 52 -OC(=O)-R EF …(3) R 51 -(O=)C-R CF -C(=O)R 52 …(4) In formulae (3) to (4), R CF is a fluoroalkylene group having 1 to 20 carbon atoms or a fluoroalkylene group having 2 to 2000 carbon atoms and an etheric oxygen atom, R DF and R EF each independently represents a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 2000 carbon atoms and having an etheric oxygen atom, R 51 and R 52 One of them is a fluorine atom, and the other is a fluorine atom or a fluoroalkyl group having 1 to 20 carbon atoms.

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