Method for producing fluorine-containing cyclic compound, and fluorine-containing cyclic compound

Abstract

A method for producing a fluorine-containing cyclic compound, wherein a fluorine-containing cyclic compound is obtained by reacting a fluorine-containing acyl fluoride compound having two acyl fluoride groups at a temperature of 250 DEG C or higher.

Description

Technical Field

[0001] The present disclosure relates to a method for producing a fluorinated cyclic compound and a fluorinated cyclic compound. Background Art

[0002] Among fluorine-containing compounds, there are many industrially useful compounds, and various production methods have been developed in the past. For example, Patent Document 1 describes a method for producing a fluorine-containing compound. Patent Document 2 describes a method for producing an unsaturated compound based on a thermal decomposition reaction.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: International Publication No. 2000 / 056694

[0006] Patent Document 2: International Publication No. 2001 / 094285 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] However, there are cases where a method for selectively obtaining a fluorinated cyclic compound is required.

[0009] An object of one embodiment of the present invention is to provide a method for producing a fluorinated cyclic compound with a higher selectivity than existing production methods.

[0010] Solutions to the Problems

[0011] The present disclosure includes the following aspects.

[0012] <1>

[0013] A method for producing a fluorinated cyclic compound, which reacts a fluorinated acyl fluoride compound having two acyl fluoride groups at a temperature of 250 °C or higher to obtain a fluorinated cyclic compound.

[0014] <2>

[0015] The method for producing a fluorinated cyclic compound according to <1>, wherein the fluorinated acyl fluoride compound is represented by the following formula (1),

[0016] The fluorinated cyclic compound is represented by the following formula (2),

[0017] F-(O=)C-R AF -C(=O)F…(1)

[0018]

[0019] In formulas (1) to (2), R AF is a fluoroalkylene group having 3 to 20 carbon atoms or a fluoroalkylene group having 2 to 20 carbon atoms and having an etheric oxygen atom.

[0020] <3>

[0021] The method for producing a fluorinated cyclic compound according to <2>, wherein in formulas (1) to (2), R AF is represented by the following formula (3),

[0022] -CFR 1 -O-R BF -…(3)

[0023] In formula (3), R 1 is a fluorine atom or a trifluoromethyl group,

[0024] R BF is a fluoroalkylene group, and the number of carbon atoms contained in the main chain of R BF is 3 to 7.

[0025] <4>

[0026] The method for producing a fluorinated cyclic compound according to any one of <1> to <3>, wherein the reaction is carried out in the gas phase, and the concentration of the fluorine-containing acyl fluoride compound in the gas phase is 5 to 25 mol%.

[0027] <5>

[0028] The method for producing a fluorinated cyclic compound according to any one of <1> to <4>, wherein the reaction temperature is 350 °C or lower.

[0029] <6>

[0030] The method for producing a fluorinated cyclic compound according to any one of <1> to <5>, wherein the reaction time is 5 to 60 seconds.

[0031] <7>

[0032] The method for producing a fluorinated cyclic compound according to any one of <1> to <6>, wherein the reaction is carried out in the presence of glass beads.

[0033] <8>

[0034] A fluorinated cyclic compound represented by the following formula (4),

[0035]

[0036] Effects of the Invention

[0037] According to the present disclosure, there is provided a method for producing a fluorinated cyclic compound that can produce a fluorinated cyclic compound with a higher selectivity compared to existing production methods. Detailed Description

[0038] 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.

[0039] 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. Additionally, 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.

[0040] In the present disclosure, the combination of two or more preferred modes is a more preferred mode.

[0041] 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.

[0042] In the present disclosure, the compound represented by formula (1) is denoted as compound 1. The same applies to compounds, groups, etc. represented by other formulas.

[0043] [Method for Producing Fluorinated Cyclic Compound]

[0044] In the method for producing a fluorinated cyclic compound of the present disclosure, a fluorinated acyl fluoride compound having two acyl fluoride groups is reacted at a temperature of 250 °C or higher to obtain a fluorinated cyclic compound.

[0045] Conventionally, in the reaction using a fluorinated acyl fluoride compound having two acyl fluoride groups, multiple compounds are generated, and it is difficult to obtain a fluorinated cyclic compound with a high selectivity.

[0046] Hereinafter, the method for producing a fluorinated cyclic compound of the present disclosure will be described in detail.

[0047] <Fluorinated Acyl Fluoride Compound>

[0048] The fluorinated acyl fluoride compound used in the method for producing a fluorinated cyclic compound of the present disclosure is not particularly limited as long as it is a compound having two acyl fluoride groups (-C(=O)F).

[0049] Preferably, the fluorinated acyl fluoride compound is represented by the following formula (1), and the fluorinated cyclic compound is represented by the following formula (2).

[0050] F-(O=)C-R AF -C(=O)F…(1)

[0051]

[0052] In formulas (1) and (2), R AF is a fluoroalkylene group having 3 to 20 carbon atoms or a fluoroalkylene group having 2 to 20 carbon atoms and having an etheric oxygen atom.

[0053] 〔R AF 〕

[0054] R AF The fluoroalkylene group represented by can be a linear fluoroalkylene group or a branched fluoroalkylene group.

[0055] In the present disclosure, "fluoroalkylene group" means a group in which one or more hydrogen atoms present in the alkylene group are substituted by fluorine atoms. The fluoroalkylene group can be a partial fluoroalkylene group or a perfluoroalkylene group.

[0056] In the present disclosure, "perfluoroalkylene group" means a group in which all hydrogen atoms present in the alkylene group are substituted by fluorine atoms.

[0057] R AF The fluoroalkylene group represented by is preferably a perfluoroalkylene group.

[0058] R AF The number of carbon atoms of the fluoroalkylene group represented by is preferably 3 to 17, more preferably 3 to 15, and particularly preferably 3 to 10.

[0059] R AF The fluoroalkylene group having an etheric oxygen atom represented by can be a linear fluoroalkylene group having an etheric oxygen atom or a branched fluoroalkylene group having an etheric oxygen atom.

[0060] R AF The fluoroalkylene group having an etheric oxygen atom represented by is preferably a perfluoroalkylene group having an etheric oxygen atom.

[0061] R AF The number of carbon atoms of the fluoroalkylene group having an etheric oxygen atom represented by is preferably 3 to 17, more preferably 3 to 15, and particularly preferably 3 to 10.

[0062] From the aspect of excellent selectivity of the target product, R AF preferably contains an etheric oxygen atom.

[0063] In addition, in the fluorinated cyclic compound represented by formula (2), the number of atoms constituting the ring is preferably 6 to 10, more preferably 6 or 7. That is, in formulas (1) to (2), the number of atoms contained in the main chain in R AF is preferably 5 to 9, more preferably 5 or 6.

[0064] Here, "the main chain in R AF " means the linear part without branches.

[0065] R AF Preferably contains an etheric oxygen atom in the main chain, and more preferably the main chain is composed of etheric oxygen atoms and carbon atoms.

[0066] R AF Preferably contains 1 etheric oxygen atom in the main chain, and the number of carbon atoms contained in the main chain is preferably 4 to 8, more preferably 4 or 5.

[0067] Among them, R AF Is preferably represented by the following formula (3).

[0068] -CFR 1 -O-R BF -…(3)

[0069] In formula (3), R 1 Is a fluorine atom or a trifluoromethyl group, R BF Is a fluoroalkylene group, R BF The number of carbon atoms contained in the main chain of is 3 to 7.

[0070] Here, "the main chain of R BF " refers to the straight-chain part without branches.

[0071] From the viewpoint of excellent chemical stability, R 1 Is preferably a trifluoromethyl group.

[0072] R BF The fluoroalkylene group represented by can be a straight-chain fluoroalkylene group or a branched-chain fluoroalkylene group, but preferably a straight-chain fluoroalkylene group.

[0073] R BF The fluoroalkylene group represented by is preferably a perfluoroalkylene group.

[0074] R BF The number of carbon atoms of the fluoroalkylene group represented by is preferably 2 to 16, more preferably 3 to 14.

[0075] R BF The number of carbon atoms contained in the main chain of is preferably 3 or 4.

[0076] Specific examples of the fluorine-containing acyl fluoride compound represented by formula (1) are as follows.

[0077]

[0078] For example, when the above-mentioned fluorine-containing acyl fluoride compound A1 is reacted at a temperature of 250 °C or higher, the following fluorine-containing cyclic compound B1 can be obtained.

[0079]

[0080] In addition, when the above-mentioned fluorine-containing acyl fluoride compound A1 is reacted at a temperature of 250 °C or higher, in addition to the fluorine-containing cyclic compound B1, the following fluorine-containing compounds can also be obtained. According to the method for producing a fluorine-containing cyclic compound of the present disclosure, among the various products produced, the fluorine-containing cyclic compound B1 can be obtained with a high selectivity.

[0081]

[0082] For example, when the above-mentioned fluorine-containing acyl fluoride compound A2 is reacted at a temperature of 250 °C or higher, the following fluorine-containing cyclic compound B2 can be obtained.

[0083]

[0084] In addition, when the above-mentioned fluorine-containing acyl fluoride compound A2 is reacted at a temperature of 250 °C or higher, in addition to the fluorine-containing cyclic compound B2, the following fluorine-containing compounds can also be obtained. According to the method for producing a fluorine-containing cyclic compound of the present disclosure, among the various products produced, the fluorine-containing cyclic compound B2 can be obtained with a high selectivity.

[0085]

[0086] <Reaction conditions>

[0087] In the method for producing a fluorine-containing cyclic compound of the present disclosure, the fluorine-containing acyl fluoride compound is reacted at a temperature of 250 °C or higher. By carrying out the reaction at a temperature of 250 °C or higher, an intramolecular cyclization reaction occurs, and a fluorine-containing cyclic compound can be obtained with a high selectivity.

[0088] On the other hand, from the viewpoint of suppressing excessive reaction, the temperature during the reaction (hereinafter also referred to as "reaction temperature") is preferably 350 °C or lower. From the above viewpoint, in the method for producing a fluorine-containing cyclic compound of the present disclosure, the reaction temperature of the fluorine-containing acyl fluoride compound is preferably 250 to 350 °C.

[0089] The reaction is carried out in the gas phase, and the concentration of the fluorine-containing acyl fluoride compound in the gas phase is preferably 5 to 25 mol%, more preferably 5 to 20 mol%, still more preferably 5 to 15 mol%, and particularly preferably 7 to 15 mol%. From the viewpoint of production, if the concentration is 5 mol% or more, the productivity is excellent. On the other hand, if the concentration is 25 mol% or less, the intermolecular reaction is suppressed, and the selectivity of the fluorine-containing cyclic compound is increased.

[0090] The gas contained in the gas phase is preferably an inert gas. Examples of the inert gas include nitrogen, argon, and helium.

[0091] In the method for producing a fluorine-containing cyclic compound of the present disclosure, the reaction is preferably carried out in the presence of glass beads. Specifically, for the packing of glass beads, it is preferably brought into contact with a fluorine-containing acyl fluoride compound in a state heated to the reaction temperature.

[0092] Glass beads refer to granular glass.

[0093] As the glass, a known composition mainly composed of SiO2 can be used. The glass may contain at least one selected from the group consisting of Li2O, Na2O, K2O, MgO, CaO, and BaO in an amount of 0.01 to 20% by mass as a specific element.

[0094] Examples of specific compositions include soda-lime glass mainly composed of SiO2, Na2O, and CaO; potash crystal glass mainly composed of SiO2, Na2O, K2O, and CaO; aluminosilicate glass mainly composed of SiO2, Al2O3, Na2O, and K2O; lead glass mainly composed of SiO2, K2O, and PbO; borosilicate glass mainly composed of SiO2, B2O3, Na2O, and K2O; and aluminoborosilicate glass mainly composed of SiO2, Na2O, K2O, Al2O3, and B2O3.

[0095] The glass beads can be used in a fixed-bed process or a fluidized-bed process.

[0096] The reaction time (hereinafter also referred to as "reaction time") is preferably 5 to 60 seconds, more preferably 5 to 45 seconds, still more preferably 5 to 30 seconds, and particularly preferably 10 to 30 seconds.

[0097] Here, in the case of carrying out the reaction in the presence of the above glass beads, the reaction time refers to the contact time between the glass beads and the fluorine-containing acyl fluoride compound. For example, when using a tubular reactor, the contact time can be calculated based on the amount of gas containing the fluorine-containing acyl fluoride compound introduced into the tubular reactor and the packed volume of the glass beads in the tubular reactor.

[0098] [Fluorine-containing cyclic compound]

[0099] The fluorine-containing cyclic compound of the present disclosure is represented by the following formula (4).

[0100]

[0101] The fluorine-containing cyclic compound represented by formula (4) is expected to be used as a solvent, a heat medium, a surface treatment agent, an emulsifier, a synthesis intermediate for perfluoroelastomers, etc.

[0102] Examples

[0103] 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 6 are examples, and Example 7 is a comparative example.

[0104] Hereinafter, the analysis using gas chromatography (GC) was carried out by setting “Rtx-200” (inner diameter 0.25 mm, length 60 m, film thickness 1.00 μm) manufactured by Restek as a capillary column 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 / sec, and a column temperature of 40 °C, after holding for 10 minutes, the temperature was raised to 240 °C at a rate of 10 °C / minute and held for 20 minutes. A flame ionization detector (FID) was used as the detector. Quantitative analysis was carried out using a standard curve with CF3CH2OCF2CF2H (product name “Asahiklin AE-3000”, manufactured by AGC Inc.) as the internal standard.

[0105] [Example 1]

[0106] Using the method described in Example 12-2 of International Publication No. 2015 / 029839, the following fluorine-containing acyl fluoride compound A1 was obtained.

[0107]

[0108] In a U-shaped reaction tube made of stainless steel (SUS316) with an inner diameter of 21.4 mm, a fluidized bed reactor filled with sodium glass beads was placed in a salt bath and heated to 280 °C while introducing nitrogen. A mixed gas of nitrogen and fluorine-containing acyl fluoride compound A1 (nitrogen / fluorine-containing acyl fluoride compound A1 = 90 / 10 molar ratio) was introduced at a reaction temperature of 280 °C and a contact time of 20 seconds. A dry ice / ethanol collector was set at the reactor outlet to recover the product. Thus, the following fluorine-containing cyclic compound B1 was obtained as one of the products. The fluorine-containing cyclic compound B1 was analyzed by GC, GC-MS, and 19 F-NMR, and as a result, the selectivity of the fluorine-containing cyclic compound B1 was 41%.

[0109]

[0110] [Examples 2 to 4, 7 to 8]

[0111] Except that the concentration, reaction temperature, and contact time of the fluorine-containing acyl fluoride compound A1 were changed to the values shown in Table 1 below, the fluorine-containing cyclic compound B1 was obtained in the same manner as in Example 1.

[0112] [Example 5]

[0113] Using the method described in Example 14-2 of International Publication No. 2015 / 029839, the following fluorine-containing acyl fluoride compound A2 was obtained.

[0114]

[0115] In a U-shaped reaction tube made of stainless steel (SUS316) with an inner diameter of 21.4 mm, a fluidized bed reactor filled with sodium glass beads was placed in a salt bath and heated to 250 °C while passing nitrogen gas. A mixed gas of nitrogen and fluorine-containing acyl fluoride compound A2 (nitrogen / fluorine-containing acyl fluoride compound A1 = 95 / 5 molar ratio) was introduced at a reaction temperature of 250 °C and a contact time of 20 seconds. A dry ice / ethanol collector was set at the reactor outlet to recover the product. Thus, the following fluorine-containing cyclic compound B2 was obtained as one of the products. The fluorine-containing cyclic compound B2 was analyzed by GC, GC-MS, and NMR, and as a result, the selectivity of the fluorine-containing cyclic compound B2 was 81%.

[0116]

[0117] [Example 6]

[0118] Except that the concentration, reaction temperature, and contact time of the fluorine-containing acyl fluoride compound A2 were changed to the values shown in Table 1 below, the fluorine-containing cyclic compound B2 was obtained in the same manner as in Example 5.

[0119] The selectivity of the fluorine-containing cyclic compound is shown in Table 1.

[0120] [Table 1]

[0121]

[0122] As shown in Table 1, in Examples 1 to 6, since the fluorine-containing acyl fluoride compound having two acyl fluoride groups was reacted at a temperature of 250 °C or higher, the fluorine-containing cyclic compound could be obtained with a high selectivity.

[0123] Industrial Applicability

[0124] The method for producing the fluorine-containing cyclic compound of the present disclosure can produce the fluorine-containing cyclic compound with a higher selectivity than in the past. The obtained fluorine-containing cyclic 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 cyclic compound and fluorine-containing compound can be used as surface treatment agents, emulsifiers, rubbers, surfactants, solvents, heat media, pharmaceuticals, pesticides, lubricating oils, and their intermediates.

[0125] The entire disclosure of Japanese Patent Application No. 2022-185952, 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 fluorinated cyclic compound, which comprises reacting a fluorinated acyl fluoride compound having two acyl fluoride groups at a temperature of 250 °C or higher to obtain a fluorinated cyclic compound.

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

3. The method for producing a fluorine-containing cyclic compound according to claim 2, wherein, In formulas (1) to (2), R AF is represented by the following formula (3): -CFR 1 -O-R BF -…(3) In formula (3), R 1 is a fluorine atom or a trifluoromethyl group, R BF is a fluoroalkylene group, and the number of carbon atoms contained in the main chain of R BF is 3 to 7.

4. The method for producing a fluorine-containing cyclic compound according to claim 1 or 2, wherein, The reaction is carried out in the gas phase, and the concentration of the fluorinated acyl fluoride compound in the gas phase is 5 to 25 mol%.

5. The method for producing a fluorine-containing cyclic compound according to claim 1 or 2, wherein, The temperature of the reaction is 350 °C or lower.

6. The method for producing a fluorinated cyclic compound according to claim 1 or 2, wherein, The reaction time is 5 to 60 seconds.

7. The method for producing a fluorinated cyclic compound according to claim 1 or 2, wherein, The reaction is carried out in the presence of glass beads.

8. A fluorinated cyclic compound represented by the following formula (4),

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