Method for producing 1,4-dioxane derivatives, compositions containing 1,4-dioxane derivatives and 1,4-dioxane derivatives, and methods for producing (1,3-dioxolane)-2-carboxylic acid derivatives, compositions containing (1,3-dioxolane)-2-carboxylic acid derivatives and (1,3-dioxolane)-2-carboxylic acid derivatives.

Abstract

Provided is a method for producing a 1,4-dioxane derivative represented by formula (2) and / or formula (10), including reacting water, an inorganic base, and fluoroalkene oxide represented by formula (1). Provided is a method for producing a (1,3-dioxolane)-2-carboxylic acid derivative, including: producing a 1,4-dioxane derivative represented by formula (2) and / or formula (10) via the above method; and subjecting the 1,4-dioxane derivative represented by formula (2) and / or formula (10) to ring contraction under heating. In formula (1), R represents a fluorine atom or a fluoroalkyl group. In formula (2) and formula (10), R represents a fluorine atom or a fluoroalkyl group, the two Rs are identical to or different from each other, and М'+ represents a counter cation.

Description

Cross-reference of related applications

[0001] This application claims priority to Japanese Patent Application No. 2021-083519, filed on 17 May 2021, the entirety of which is incorporated herein by special reference. [Technical Field]

[0002] The present invention relates to a method for producing a 1,4-dioxane derivative, a composition containing a 1,4-dioxane derivative and a 1,4-dioxane derivative, and a method for producing a (1,3-dioxolane)-2-carboxylic acid derivative, a composition containing a (1,3-dioxolane)-2-carboxylic acid derivative and a (1,3-dioxolane)-2-carboxylic acid derivative. [Background technology]

[0003] Poly[perfluoro(2,4-dimethyl-1,3-dioxolane)] can be obtained by polymerizing perfluoro(2-methylene-4-methyl-1,3-dioxolane), which is derived from a 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid derivative. Poly[perfluoro(2-methylene-4-methyl-1,3-dioxolane)] is a promising polymer for use as a resin for gas separation membranes, a transparent resin for optical fibers, and the like. (1,3-dioxolane)-2-carboxylic acid derivatives, such as 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid derivatives, are raw materials for the above-mentioned promising polymers. Patent documents 1 and 2 disclose the following method for producing 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid derivatives: Trifluoropyruvic acid fluoride prepared from hexafluoropropylene oxide and benzophenone is reacted with hexafluoropropylene oxide in a diethylene glycol dimethyl ether solvent in the presence of cesium fluoride to obtain perfluoro(dimethyl-2-oxo-1,4-dioxane). The obtained perfluoro(dimethyl-2-oxo-1,4-dioxane) is subjected to a ring reduction reaction under heating conditions in the presence of cesium fluoride to obtain 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid fluoride.

[0004] Furthermore, Patent Document 2 discloses a method for obtaining the above-mentioned perfluoro(dimethyl-2-oxo-1,4-dioxane) by reacting perfluoro(4-oxo-2,5-dimethyl-2-fluorocarbonyl-1,3-dioxane), which is obtained by reacting hexafluoropropylene oxide with benzophenone, as a raw material, in the presence of cesium fluoride and in a diethylene glycol dimethyl ether solvent.

[0005] Patent documents 3 and 4 describe a method for obtaining perfluoro(dimethyl-2-oxo-1,4-dioxane) by reacting hexafluoropropylene oxide in the presence of dimethylformamide and hexamethylphosphate triamide, or in the presence of dimethylformamide and cesium fluoride. Non-patent document 1 also discloses a method for obtaining perfluoro(dimethyl-2-oxo-1,4-dioxane) by reacting hexafluoropropylene oxide with dimethylformamide.

[0006] [Patent Document 1] U.S. Patent No. 3308107

Patent Document 2

Patent Document 3

Patent Document 4

[0007]

Non-Patent Document 1

Summary of the Invention

[0008] In a method for producing perfluoro(dimethyl-2-oxo-1,4-dioxane) from hexafluoropropylene oxide, in the methods described in Patent Document 2, Patent Document 3, Patent Document 4 and Non-Patent Document 1, it is necessary to use an organic carbonyl compound such as benzophenone or dimethylformamide as an oxygen source and a fluorine atom scavenger. However, since organic fluorine waste is by-produced from these, their separation and disposal are required.

[0009] In view of the above, one aspect of the present invention aims to provide a new production method for an intermediate for producing a (1,3-dioxolan)-2-carboxylic acid derivative, a 1,4-dioxane derivative and a composition containing the 1,4-dioxane derivative, a new production method for a (1,3-dioxolan)-2-carboxylic acid derivative, a (1,3-dioxolan)-2-carboxylic acid derivative and a composition containing the (1,3-dioxolan)-2-carboxylic acid derivative.

[0010] As a result of intensive studies, the present inventors have newly found that a 1,4-dioxane derivative, which is an intermediate for producing a (1,3-dioxolan)-2-carboxylic acid derivative, can be produced from water, an inorganic base, and a fluoroalkene oxide. That is, it has been found that, instead of the organic carbonyl compound that was conventionally required, a 1,4-dioxane derivative can be produced in a single step using water, which does not by-produce organic fluorine waste as an oxygen source. Further, it has been found that the obtained 1,4-dioxane derivative can be converted into a (1,3-dioxolan)-2-carboxylic acid derivative.

[0011] That is, one aspect of the present invention is as follows. [1] A method for producing one or more 1,4-dioxane derivatives selected from the group consisting of a 1,4-dioxane derivative represented by the formula (2):

Chemical formula

Chemical formula

Chemical formula

[10] A method for producing a 1,4-dioxane derivative according to [1], wherein R is a fluoroalkyl group having 1 to 10 carbon atoms.

[11] A method for producing a 1,4-dioxane derivative according to [1], wherein R is a perfluoroalkyl group having 1 to 4 carbon atoms. To produce a 1,4-dioxane derivative by the manufacturing method described in any of

[12] [1] to

[11] , and The manufactured 1,4-dioxane derivative is subjected to ring reduction under heating. A method for producing one or more (1,3-dioxolane)-2-carboxylic acid derivatives selected from the group consisting of formulas (5), (6), (7), and (9), including the above. Formula (5): [ka] (In formula (5), R represents a fluorine atom or a fluoroalkyl group, and any two Rs may be the same or different.) (1,3-dioxolane)-2-carboxylic acid fluoride Formula (6): [ka] (1,3-Dioxolane)-2-carboxylic acid represented by formula (6), where R represents a fluorine atom or a fluoroalkyl group, and any two Rs may be the same or different. Formula (7): [ka] (In formula (7), M + (1,3-dioxolane)-2-carboxylate salts are represented by , where R represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and two Rs may be the same or different. Formula (9): [ka] (In formula (9), M + ) represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and any two Rs may be the same or different. ) 1,3-dioxolane derivatives represented by )

[13] A method for producing a (1,3-dioxolane)-2-carboxylic acid derivative according to

[12] , wherein the ring reduction is carried out in the presence of a fluoride.

[14] The method for producing a (1,3-dioxolane)-2-carboxylic acid derivative according to

[13] , wherein the fluoride is one or more fluorides selected from the group consisting of cesium fluoride, potassium fluoride, and sodium fluoride.

[15] A method for producing a (1,3-dioxolane)-2-carboxylic acid derivative according to

[12] , wherein the reaction temperature for the ring reduction is in the range of 100°C to 200°C.

[16] Equation (10): [ka] (In formula (10), M ’+∫ represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and any two Rs may be the same or different. ) A 1,4-dioxane derivative represented by ).

[17] Formula (2): [ka] A 1,4-dioxane derivative represented by formula (2) (wherein R represents a fluorine atom or a fluoroalkyl group, and the two Rs are either the same or different), Equation (10): [ka] (In formula (10), M ’+ ) represents a 1,4-dioxane derivative, where R represents a cation, R represents a fluorine atom or a fluoroalkyl group, and the two Rs are either the same or different. A composition containing the following:

[18] Equation (9): [ka] (In formula (9), M + ) represents a 1,3-dioxolane derivative represented by ).

[19] Equation (5): [ka] (1,3-dioxolane)-2-carboxylic acid fluoride, represented by formula (5) (wherein R represents a fluorine atom or a fluoroalkyl group, and the two Rs are either the same or different), Formula (6): [ka] (1,3-dioxolane)-2-carboxylic acid represented by formula (6), where R represents a fluorine atom or a fluoroalkyl group, and the two Rs are either the same or different. Formula (7): [ka] (In formula (7), M + (1,3-dioxolane)-2-carboxylate salts are represented as follows: where represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and two Rs may be the same or different. One or more (1,3-dioxolane)-2-carboxylic acid derivatives selected from the group consisting of, Formula (9): [ka] (In formula (9), M + ) represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and the two Rs present may be the same or different. ) and a 1,3-dioxolane derivative represented by A composition containing the following:

[0012] According to one aspect of the present invention, a novel single-step method for producing 1,4-dioxane derivatives from water, an inorganic base, and a fluoroalkene oxide raw material, which are industrially inexpensive and readily available, can be provided. This production method does not require the organic carbonyl compounds that were conventionally necessary. Furthermore, a 1,4-dioxane derivative represented by formula (10), obtained according to one aspect of the present invention, can be converted to a (1,3-dioxolane)-2-carboxylic acid derivative by a low-pressure ring contraction reaction. Furthermore, a 1,3-dioxolane derivative represented by formula (9), obtained according to one aspect of the present invention, can be converted to (1,3-dioxolane)-2-carboxylic acid or a salt thereof by hydrolysis. [Modes for carrying out the invention]

[0013] One aspect of the present invention relates to a method for producing a 1,4-dioxane derivative. The above method for producing a 1,4-dioxane derivative comprises a reaction step of reacting water, an inorganic base, and a fluoroalkene oxide to obtain a 1,4-dioxane derivative.

[0014] Furthermore, one aspect of the present invention relates to a method for producing a (1,3-dioxolane)-2-carboxylic acid derivative. The above method for producing a (1,3-dioxolane)-2-carboxylic acid derivative includes a reaction step of ring-contracting the 1,4-dioxane derivative obtained in the above method for producing a 1,4-dioxane derivative into a (1,3-dioxolane)-2-carboxylic acid derivative.

[0015] In the present invention and this specification, "1,4-dioxane derivative" refers to one or more compounds selected from the group consisting of the 1,4-dioxane derivative represented by formula (2) and the 1,4-dioxane derivative represented by formula (10). That is, "1,4-dioxane derivative" in the present invention and this specification includes the 1,4-dioxane derivative represented by formula (2) and the 1,4-dioxane derivative represented by formula (10). In one embodiment, the product of the above method for producing a 1,4-dioxane derivative is one or more 1,4-dioxane derivatives represented by formula (2); one or more 1,4-dioxane derivatives represented by formula (10); or a mixture of one or more 1,4-dioxane derivatives represented by formula (2) and one or more 1,4-dioxane derivatives represented by formula (10).

[0016] In the present invention and this specification, (1,3-dioxolane)-2-carboxylic acid derivatives refer to one or more compounds selected from the group consisting of (1,3-dioxolane)-2-carboxylic acid fluoride represented by formula (5), (1,3-dioxolane)-2-carboxylic acid represented by formula (6), (1,3-dioxolane)-2-carboxylate salt represented by formula (7), and 1,3-dioxolane derivatives represented by formula (9). That is, "(1,3-dioxolane)-2-carboxylic acid derivatives" in the present invention and this specification include (1,3-dioxolane)-2-carboxylic acid represented by formula (6), (1,3-dioxolane)-2-carboxylate salt represented by formula (7), 1,3-dioxolane derivatives represented by formula (9), and (1,3-dioxolane)-2-carboxylic acid fluoride represented by formula (5). In one form, the product of the above method for producing (1,3-dioxolane)-2-carboxylic acid derivatives is one or more (1,3-dioxolane)-2-carboxylic acid fluorides represented by formula (5); one or more (1,3-dioxolane)-2-carboxylic acids represented by formula (6); one or more (1,3-dioxolane)-2-carboxylic acid salts represented by formula (7); one or more 1,3-dioxolane derivatives represented by formula (9); a mixture of one or more (1,3-dioxolane)-2-carboxylic acid fluorides represented by formula (5) and one or more (1,3-dioxolane)-2-carboxylic acids represented by formula (6); and (1,3-dioxolane)-2-carboxylates represented by formula (5). A mixture of one or more fluoride compounds represented by formula (9) and one or more 1,3-dioxolane derivatives represented by formula (9); a mixture of one or more 2-(1,3-dioxolane)carboxylic acids represented by formula (6) and one or more 1,3-dioxolane derivatives represented by formula (9); a mixture of one or more (1,3-dioxolane)-2-carboxylic acid fluorides represented by formula (5), one or more (1,3-dioxolane)-2-carboxylic acids represented by formula (6) and one or more 1,3-dioxolane derivatives represented by formula (9); a mixture of one or more 2-(1,3-dioxolane)carboxylate salts represented by formula (7) and one or more 1,3-dioxolane derivatives represented by formula (9);A mixture of one or more (1,3-dioxolane)-2-carboxylic acid fluorides represented by formula (5), one or more (1,3-dioxolane)-2-carboxylate salts represented by formula (7), and one or more 1,3-dioxolane derivatives represented by formula (9); a mixture of one or more 2-(1,3-dioxolane)carboxylic acids represented by formula (6), one or more 2-(1,3-dioxolane)carboxylate salts represented by formula (7), and one or more 1,3-dioxolane derivatives represented by formula (9); one or more (1,3-dioxolane)-2-carboxylic acid fluorides represented by formula (5), one or more (1,3-dioxolane)-2-carboxylic acids represented by formula (6), and one or more (1,3-dioxolane)-2-carboxylate salts represented by formula (7) A mixture of one or more 1,3-dioxolane derivatives represented by formula (9); a mixture of one or more (1,3-dioxolane)-2-carboxylic acids represented by formula (6) and one or more (1,3-dioxolane)-2-carboxylate salts represented by formula (7); a mixture of one or more (1,3-dioxolane)-2-carboxylic acid fluorides represented by formula (5) and one or more (1,3-dioxolane)-2-carboxylate salts represented by formula (7); or a mixture of one or more (1,3-dioxolane)-2-carboxylic acid fluorides represented by formula (5), one or more (1,3-dioxolane)-2-carboxylic acids represented by formula (6), and one or more (1,3-dioxolane)-2-carboxylate salts represented by formula (7).

[0017] The methods for producing the 1,4-dioxane derivative, the method for producing the (1,3-dioxolane)-2-carboxylic acid derivative, and the compositions described above will be explained in more detail below.

[0018] [Method for producing 1,4-dioxane derivatives] The above method for producing the 1,4-dioxane derivative involves reacting water, an inorganic base, and a fluoroalkene oxide represented by formula (1). This reaction is shown in the following reaction equation. Details of R in the following reaction equation will be described later.

[0019] [ka]

[0020] The fluoroalkene oxide represented by the above formula (1) will be described below.

[0021] In formula (1), R represents a fluorine atom or a fluoroalkyl group.

[0022] In the present invention and this specification, the "fluoroalkyl group" means a group in which one or more hydrogen atoms of an alkyl group are substituted with fluorine atoms, and also includes a perfluoroalkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms.

[0023] Examples of the fluoroalkyl group represented by R include linear or branched fluoroalkyl groups such as monofluoromethyl group, difluoromethyl group, trifluoromethyl group, monofluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, monofluoropropyl group, difluoropropyl group, trifluoropropyl group, tetrafluoropropyl group, pentafluoropropyl group, hexafluoropropyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, perfluoroisopropyl group, perfluoro t-butyl, etc. In terms of good yield, in the fluoroalkene oxide represented by formula (1), R is preferably a fluoroalkyl group having 1 to 10 carbon atoms, more preferably a perfluoroalkyl group having 1 to 4 carbon atoms, and still more preferably a trifluoromethyl group.

[0024] In the present invention and this specification, R in each formula has the same meaning as R in formula (1), and the details are as described above. When two Rs are present in the formula, these two Rs may be the same or different.

[0025] In formula (10), M ’+ represents a counter cation. M ’+The countercation represented by can be the countercation of the inorganic base used in the reaction or the countercation of the inorganic salt added in the post-treatment. ’+ The counter cation may be a single type of cation or multiple types of cations. Specific examples of monovalent counter cations include cesium ions, potassium ions, sodium ions, tetrabutylammonium ions, tetraethylammonium ions, tetrabutylphosphonium ions, triethylmethylammonium ions, triethylammonium ions, pyridinium ions, and ammonium ions. Examples of divalent counter cations include calcium ions and magnesium ions, and in the case of divalent counter cations, M ’+ (Ca 2+ ) 1 / 2 , (Mg 2+ ) 1 / 2 It can be represented as M. ’+ As the countercation represented by , from the viewpoint of availability and yield improvement, cesium ions, potassium ions, and sodium ions are preferred, cesium ions and potassium ions are more preferred, and potassium ions are even more preferred.

[0026] Examples of fluoroalkene oxides represented by formula (1) include hexafluoropropylene oxide, perfluoro-1-butene oxide, perfluoro-1-pentene oxide, perfluoro-1-hexene oxide, perfluoro-1-heptene oxide, perfluoro-1-octen oxide, 2-(1,1,2,2-tetrafluoroethyl)-2,3,3-trifluorooxirane, 2-(1,1,2,2,3,3,4,4-octafluorobutyl)-2,3,3-trifluorooxirane, 2-(1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl)-2,3,3-trifluorooxirane, 1,1,2,3-tetrafluoro-1-propylene oxide, 1,1,2,3,3-pentafluoro-1-propylene oxide, and others, among which hexafluoroalkene oxide is preferred. The reaction may use one type of fluoroalkene oxide, or a mixture of two or more fluoroalkene oxides in any proportion. These fluoroalkene oxides can be commercially available, or they can be prepared by oxidizing the corresponding fluoroalkene with an oxidizing agent such as m-chloroperbenzoic acid.

[0027] The water used in the above reaction is not particularly limited, and for example, tap water, deionized water, or distilled water can be used. Furthermore, water contained in the organic solvent and / or inorganic base described later may also be used in the reaction. The amount of water used in the reaction can be, for example, a catalytic amount, preferably 0.50 molar times or less, and more preferably 0.30 molar times or less, per mole of fluoroalkene oxide represented by formula (1). Also, the amount of water used in the reaction can be, for example, 0.10 molar times or more, 0.15 molar times or more, 0.20 molar times or more, or 0.21 molar times or more, per mole of fluoroalkene oxide represented by formula (1), or less than the values ​​exemplified herein.

[0028] The inorganic base used in the above reaction is not particularly limited. Preferably, one or more inorganic bases are selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal bicarbonates, fluoride salts, and alkaline earth metal bicarbonates. Examples of such inorganic bases include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate; alkaline earth metal bicarbonates such as magnesium bicarbonate and calcium bicarbonate; fluoride salts such as cesium fluoride, potassium fluoride, sodium fluoride, potassium hydrogen fluoride, calcium fluoride, sodium hydrogen fluoride, tetrabutylammonium fluoride, tetraethylammonium fluoride, tetramethylammonium fluoride, tetrabutylphosphonium fluoride, and triethylmethylammonium fluoride. In terms of good yield, it is preferable to use one or more inorganic bases selected from the group consisting of alkali metal carbonates and fluoride salts as the inorganic base, and it is more preferable to use one or more inorganic bases selected from the group consisting of potassium carbonate and potassium fluoride. The amount of inorganic base used in the reaction is preferably 0.1 molar times or more per mole of fluoroalkene oxide represented by formula (1). Furthermore, the amount of inorganic base used in the reaction is preferably 2 molar times or less per mole of fluoroalkene oxide represented by formula (1). The molar ratio of inorganic base to water used in the reaction is not particularly limited, but from the viewpoint of improving yield, when alkali metal carbonates are used as inorganic bases, a ratio of 0.90 to 1.25 is preferred, 0.95 to 1.20 is more preferred, and 1.00 to 1.15 is even more preferred. When fluoride salts are used as inorganic bases, a ratio of 1.98 to 2.50 is preferred, 1.90 to 2.40 is more preferred, and 2.00 to 2.50 is even more preferred.

[0029] The above reaction can be carried out in or without an organic solvent, and it is preferable to carry it out in the presence of an organic solvent for better yield. The above method for producing the 1,4-dioxane derivative can be obtained, for example, by charging an organic solvent, water, and an inorganic base into a pressure vessel, cooling, and then adding a fluoroalkene oxide represented by formula (1) to the mixture and reacting it to obtain the 1,4-dioxane derivative represented by formula (2) and / or formula (10).

[0030] The organic solvent is not particularly limited as long as it is inert to the reaction. Examples of organic solvents include aromatic solvents such as toluene, ethylbenzene, xylene, and mesitylene, and ether-based solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether (also called Diglyme), triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. The organic solvent may be used alone or mixed in any proportion of two or more. Preferably, ether-based solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether are used alone or mixed in any proportion of two or more, with diethylene glycol dimethyl ether being particularly preferred. The amount of organic solvent used is not particularly limited. For example, the organic solvent can be used in amounts of 0.3 parts by weight or more per 1 part by weight of the fluoroalkene oxide represented by formula (1) used in the reaction. Alternatively, the organic solvent can be used in amounts of 5.0 parts by weight or less per 1 part by weight of the fluoroalkene oxide represented by formula (1) used in the reaction.

[0031] The above reaction can be carried out at a reaction temperature appropriately selected within the range of -20°C to 200°C, for example. A reaction temperature of -20°C to 40°C is preferable for good yield. In this invention and specification, the reaction temperature refers to the temperature of the reaction solution unless otherwise specified.

[0032] In one embodiment, a fluoride can be added to accelerate the above reaction, and the reaction can be carried out in the presence of one or more fluorides. Examples of fluorides include one or more fluorides selected from the group consisting of cesium fluoride, potassium fluoride, sodium fluoride, potassium hydrogen fluoride, calcium fluoride, sodium hydrogen fluoride, tetrabutylammonium fluoride, tetraethylammonium fluoride, tetramethylammonium fluoride, tetrabutylphosphonium fluoride, triethylmethylammonium fluoride, triethylamine trihydrofluoride, triethylamine pentahydrofluoride, triethylamine heptahydrofluoride, pyridinium poly(hydrogen fluoride), pyridine monohydrofluoride, pyridine xahydrofluoride, ammonium hydrogen fluoride, and ammonium fluoride. Any commercially available anhydrous, spray-dried, or hydrated fluoride can be used. Alternatively, a form supported on calcium fluoride or the like may be used. From the viewpoint of improving yield, it is preferable to use one or more fluorides selected from the group consisting of cesium fluoride, potassium fluoride, and sodium fluoride, more preferably potassium fluoride, and even more preferably anhydrous or spray-dried potassium fluoride. The amount of fluoride added is not particularly limited. The amount of fluoride is preferably 0.05 molar times or more per mole of fluoroalkene oxide (1) represented by formula (1). The amount of fluoride is preferably 1.0 molar time or less per mole of fluoroalkene oxide (1) represented by formula (1).

[0033] The 1,4-dioxane derivatives represented by formula (2) and / or formula (10) obtained in the above reaction can be purified after the reaction is complete, if necessary. There are no particular limitations on the purification method. For example, the 1,4-dioxane derivatives represented by formula (2) and / or formula (10) can be purified by methods commonly used by those skilled in the art, such as solvent extraction, silica gel column chromatography, thin-layer preparative chromatography, preparative liquid chromatography, or distillation.

[0034] In the present invention and this specification, the 1,4-dioxane derivative represented by formula (2) and / or formula (10) includes the following 1,4-dioxane derivative represented by formula (2), the following 1,4-dioxane derivative represented by formula (2a) which is its diastereomer, the following 1,4-dioxane derivative represented by formula (10), and the following 1,4-dioxane derivative represented by formula (10a) which is its diastereomer. The product of the above method for producing 1,4-dioxane derivatives may be only the 1,4-dioxane derivative represented by formula (2), only the 1,4-dioxane derivative represented by formula (2a), only the 1,4-dioxane derivative represented by formula (10), only the 1,4-dioxane derivative represented by formula (10a), or a mixture of two or more of the 1,4-dioxane derivative represented by formula (2), the 1,4-dioxane derivative represented by formula (2a), the 1,4-dioxane derivative represented by formula (10), and the 1,4-dioxane derivative represented by formula (10a).

[0035] [ka] (In formula (2), R represents a fluorine atom or a fluoroalkyl group, and any two Rs are either the same or different.)

[0036] [ka] (In formula (2a), R represents a fluorine atom or a fluoroalkyl group, and any two Rs are either the same or different.)

[0037] [ka] (In formula (10), M ’+ (where R represents a countercation, and R represents a fluorine atom or a fluoroalkyl group; two Rs may be the same or different.)

[0038] [ka] (In formula (10a), M ’+(where R represents a countercation, and R represents a fluorine atom or a fluoroalkyl group; two Rs may be the same or different.)

[0039] The 1,4-dioxane derivative represented by formula (2) obtained by the above method for producing 1,4-dioxane derivatives can be perfluoro(dimethyl-1,4-dioxane). Examples of perfluoro(dimethyl-1,4-dioxane) include perfluoro(3,6-dimethyl-1,4-dioxane) and perfluoro(3,5-dimethyl-1,4-dioxane), and a mixture of these isomers may also be used.

[0040] The 1,4-dioxane derivative represented by formula (10) obtained by the above method for producing 1,4-dioxane derivatives can be perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salt. Examples of perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salts include perfluoro(3,6-dimethyl-2-hydroxy-1,4-dioxane) potassium salt and perfluoro(3,5-dimethyl-2-hydroxy-1,4-dioxane) potassium salt, and a mixture of these isomers may also be used.

[0041] [Method for producing (1,3-dioxolane)-2-carboxylic acid derivatives] One aspect of the present invention relates to a method for producing (1,3-dioxolane)-2-carboxylic acid derivatives.

[0042] In the above method for producing (1,3-dioxolane)-2-carboxylic acid derivatives, for example, the 1,4-dioxane derivative obtained in the above method for producing 1,4-dioxane derivatives can be subjected to a ring reduction step under heating while the reaction mixture obtained by the above reaction is still in use, thereby obtaining the (1,3-dioxolane)-2-carboxylic acid derivative.

[0043] The product of the above method for producing (1,3-dioxolane)-2-carboxylic acid derivatives is one or more (1,3-dioxolane)-2-carboxylic acid derivatives selected from the group consisting of (1,3-dioxolane)-2-carboxylic acid fluoride represented by formula (5), (1,3-dioxolane)-2-carboxylic acid represented by formula (6), (1,3-dioxolane)-2-carboxylic acid salt represented by formula (7), and 1,3-dioxolane derivatives represented by formula (9).

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] In the above formula, R represents a fluorine atom or a fluoroalkyl group, and any two Rs may be the same or different. + and M in equation (9) + M represents a countercation. + The countercation represented by can be the countercation of the inorganic base used in the reaction described above, the countercation derived from the fluoride added in the ring reduction step, or the countercation of the inorganic salt added in the post-treatment. +The counter cation may be a single type of cation or multiple types of cations. Specific examples of monovalent counter cations include cesium ions, potassium ions, sodium ions, tetrabutylammonium ions, tetraethylammonium ions, tetrabutylphosphonium ions, triethylmethylammonium ions, triethylammonium ions, pyridinium ions, and ammonium ions. Examples of divalent counter cations include calcium ions and magnesium ions, and in the case of divalent counter cations, M + (Ca 2+ ) 1 / 2 , (Mg 2+ ) 1 / 2 It can be represented as M. + As the countercation represented by , from the viewpoint of availability and yield improvement, cesium ions, potassium ions, and sodium ions are preferred, cesium ions and potassium ions are more preferred, and potassium ions are even more preferred.

[0049] The ring reduction step can be carried out, for example, by heating the reaction mixture obtained in the reaction described above to a reaction temperature appropriately selected from 100°C to 200°C. Alternatively, it may be heated under microwave irradiation, for example. In terms of good yield, the reaction temperature for the ring reduction step is preferably 100°C to 160°C.

[0050] There are no particular limitations on the reaction time for the ring reduction process. For example, the ring reduction process can be completed by reacting for 1 to 72 hours. It is preferable to carry out the ring reduction process in a pressure vessel.

[0051] In one embodiment, a ring reduction step in the presence of a fluoride can be carried out to accelerate the reaction. Here, "present" means the residue from the previous step or newly added. Examples of fluorides include one or more fluorides selected from the group consisting of cesium fluoride, potassium fluoride, sodium fluoride, potassium hydrogen fluoride, calcium fluoride, sodium hydrogen fluoride, tetrabutylammonium fluoride, tetraethylammonium fluoride, tetramethylammonium fluoride, tetrabutylphosphonium fluoride, triethylmethylammonium fluoride, triethylamine trihydrofluoride, triethylamine pentahydrofluoride, triethylamine heptahydrofluoride, pyridinium poly(hydrogen fluoride), pyridine monohydrofluoride, pyridine xahydrofluoride, ammonium hydrogen fluoride, and ammonium fluoride. For example, one or more fluorides can be added to a reaction mixture containing a 1,4-dioxane derivative represented by formula (2) and / or formula (10) to carry out the ring reduction step. Any commercially available anhydrous, spray-dried, or hydrated fluoride can be used. Alternatively, a form supported on calcium fluoride or the like may be used. From the viewpoint of improving yield, it is preferable to use one or more fluorides selected from the group consisting of cesium fluoride, potassium fluoride, and sodium fluoride; potassium fluoride is more preferable; and anhydrous or spray-dried potassium fluoride is even more preferable. The amount of fluoride added is not particularly limited. For example, the amount of fluoride added can be 0.05 molar times or more per mole of the 1,4-dioxane derivative represented by formula (2) and / or formula (10). Furthermore, it is preferable that the amount of fluoride added is 1.0 molar times or less per mole of the 1,4-dioxane derivative represented by formula (2) and / or formula (10).

[0052] In one embodiment, an additive can be added to the ring-contraction step to improve the reactivity of the fluoride. By using an additive, the yield of the (1,3-dioxolane)-2-carboxylic acid derivative can be improved, and / or the amount of fluoride used can be reduced. Examples of such additives include crown ethers such as 18-crown-6 and 15-crown-5, polyetheramines such as tris[2-(2-methoxyethoxy)ethyl]amine (TDA-1), polar solvents such as dimethylformamide and dimethyl sulfoxide. When the additive is a crown ether and / or a polyetheramine, the amount of additive used can be, for example, 0.05 molar times or more, and 1.0 molar times or less, per mole of the 1,4-dioxane derivative represented by formula (2) and / or formula (10) subjected to the ring-contraction step.

[0053] In one embodiment, a pretreatment can be performed before the ring reduction step. For example, the following pretreatment can be performed: The reaction mixture before being subjected to the ring reduction step is heated to a temperature appropriately selected from, for example, 40°C to 100°C, and then cooled to room temperature and depressurized. In the present invention and this specification, "room temperature" refers to a temperature in the range of 20°C to 25°C.

[0054] In one embodiment, the (1,3-dioxolane)-2-carboxylic acid derivative can be obtained by post-treatment after the ring reduction step, for example, by cooling to room temperature and depressurizing, followed by filtration and separation and removal of the upper organic solvent layer. Alternatively, the target product can be obtained by distillation of the reaction mixture after the ring reduction step. Furthermore, the (1,3-dioxolane)-2-carboxylic acid derivative can be obtained by adding water or an alkaline aqueous solution such as potassium carbonate aqueous solution to the reaction mixture and then performing separation and removal.

[0055] The (1,3-dioxolane)-2-carboxylic acid derivative obtained by the above manufacturing method may be, for example, 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid fluoride represented by the following formula (5a) and / or perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane) potassium salt represented by the following formula (9a). The 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid fluoride represented by the following formula (5a) can be converted to perfluoro(2-methylene-4-methyl-1,3-dioxolane) represented by the following formula (8) by, for example, the method described in U.S. Patent No. 3308107 (Patent Document 1).

[0056] Furthermore, by the synthesis method shown in the following formula, described in Macromolecules 2005, Vol. 38, pp. 4237-4245, 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid fluoride represented by formula (5a) and / or perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane) potassium salt represented by formula (9a) can be converted to perfluoro(2-methylene-4-methyl-1,3-dioxolane) represented by formula (8). In other words, fluoride of 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid represented by the following formula (5a) and / or potassium perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane) salt represented by the following formula (9a) can be hydrolyzed with an aqueous potassium hydroxide solution to obtain potassium 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid represented by the following formula (7a), and then a decarboxylation reaction can be carried out to produce perfluoro(2-methylene-4-methyl-1,3-dioxolane) represented by the following formula (8). Potassium 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid, represented by formula (6a) below, or its potassium salt, represented by formula (7a) below, is a synthetic intermediate for producing perfluoro(2-methylene-4-methyl-1,3-dioxolane), represented by formula (8), from fluoride of 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid, represented by formula (5a) below, and / or potassium salt of perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane), represented by formula (9a) below. As described above, in the present invention and this specification, the term "(1,3-dioxolane)-2-carboxylic acid derivative" as used in the present invention and this specification includes (1,3-dioxolane)-2-carboxylic acid represented by formula (6), (1,3-dioxolane)-2-carboxylic acid salt represented by formula (7), 1,3-dioxolane derivative represented by formula (9), and (1,3-dioxolane)-2-carboxylic acid fluoride represented by formula (5).Therefore, 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid represented by formula (6a) below and potassium 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid represented by formula (7a) below are equivalent to 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid fluoride represented by formula (5a) below and potassium perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane) salt represented by formula (9a) below.

[0057] [ka]

[0058] Examples of (1,3-dioxolane)-2-carboxylic acid derivatives represented by formula (5) include 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid fluoride, 2-[perfluoro(2,4-diethyl-1,3-dioxolane)]carboxylic acid fluoride, 2-[perfluoro(2,4-di-n-propyl-1,3-dioxolane)]carboxylic acid fluoride, 2-[perfluoro(2,4-di-n-butyl-1,3-dioxolane)]carboxylic acid fluoride, 2-[perfluoro(2,4-di-n-pentyl-1,3-dioxolane)]carboxylic acid fluoride, and 2-[perfluoro Examples include fluoride of ruoro(2,4-di-n-hexyl-1,3-dioxolane)]carboxylic acid, fluoride of 2-[2,4-bis(1,1,2,2-tetrafluoroethyl)-4,5,5-trifluoro-1,3-dioxolane]carboxylic acid, fluoride of 2-[2,4-bis(1,1,2,2,3,3,4,4,-octafluorobutyl)-4,5,5-trifluoro-1,3-dioxolane]carboxylic acid, and fluoride of 2-[2,4-bis(1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl)-4,5,5-trifluoro-1,3-dioxolane]carboxylic acid.

[0059] Examples of (1,3-dioxolane)-2-carboxylic acid derivatives represented by formula (6) include 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid, 2-[perfluoro(2,4-diethyl-1,3-dioxolane)]carboxylic acid, 2-[perfluoro(2,4-di-n-propyl-1,3-dioxolane)]carboxylic acid, 2-[perfluoro(2,4-di-n-butyl-1,3-dioxolane)]carboxylic acid, 2-[perfluoro(2,4-di-n-pentyl-1,3-dioxolane)]carboxylic acid, and 2-[perfluoro Examples include (2,4-di-n-hexyl-1,3-dioxolane)]carboxylic acid, 2-[2,4-bis(1,1,2,2-tetrafluoroethyl)-4,5,5-trifluoro-1,3-dioxolane]carboxylic acid, 2-[2,4-bis(1,1,2,2,3,3,4,4,-octafluorobutyl)-4,5,5-trifluoro-1,3-dioxolane]carboxylic acid, and 2-[2,4-bis(1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl)-4,5,5-trifluoro-1,3-dioxolane]carboxylic acid.

[0060] Examples of (1,3-dioxolane)-2-carboxylic acid derivatives represented by formula (7) include potassium 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylate, potassium 2-[perfluoro(2,4-diethyl-1,3-dioxolane)]carboxylate, potassium 2-[perfluoro(2,4-di-n-propyl-1,3-dioxolane)]carboxylate, potassium 2-[perfluoro(2,4-di-n-butyl-1,3-dioxolane)]carboxylate, and potassium 2-[perfluoro(2,4-di-n-pentyl-1,3-dioxolane)] Potassium carboxylate, 2-[perfluoro(2,4-di-n-hexyl-1,3-dioxolane)]carboxylate, 2-[2,4-bis(1,1,2,2-tetrafluoroethyl)-4,5,5-trifluoro-1,3-dioxolane]carboxylate, 2-[2,4-bis(1,1,2,2,3,3,4,4,-octafluorobutyl)-4,5,5-trifluoro-1,3-dioxolane]carboxylate, 2-[2,4-bis(1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl)-4,5,5-tri Potassium fluoro-1,3-dioxolane]carboxylate, sodium 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylate, sodium 2-[perfluoro(2,4-diethyl-1,3-dioxolane)]carboxylate, sodium 2-[perfluoro(2,4-di-n-propyl-1,3-dioxolane)]carboxylate, sodium 2-[perfluoro(2,4-di-n-butyl-1,3-dioxolane)]carboxylate, sodium 2-[perfluoro(2,4-di-n-pentyl-1,3-dioxolane)]carboxylate, 2-[perfluoro(2,4-di-n-hexyl-1,3-dioxolane)]carboxylate sodium, 2-[2,4-bis(1,1,2,2-tetrafluoroethyl)-4,5,5-trifluoro-1,3-dioxolane]carboxylate sodium, 2-[2,4-bis(1,1,2,2,3,3,4,4,-octafluorobutyl)-4,5,5-trifluoro-1,3-dioxolane]carboxylate sodium, 2-[2,4-bis(1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl)-4,5,5-trifluoro-1,Examples include sodium 3-dioxolane carboxylate.

[0061] Examples of (1,3-dioxolane)-2-carboxylic acid derivatives represented by formula (9) include perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane) potassium salt, perfluoro(2-hydroxymethyl-2,4-diethyl-1,3-dioxolane) potassium salt, perfluoro(2-hydroxymethyl-2,4-di-n-propyl-1,3-dioxolane) potassium salt, perfluoro(2-hydroxymethyl-2,4-di-n-butyl-1,3-dioxolane) potassium salt, and perfluoro(2-hydroxymethyl-2,4-di-n -Pentyl-1,3-dioxolane) potassium salt, perfluoro(2-hydroxymethyl-2,4-di-n-hexyl-1,3-dioxolane) potassium salt, 2-(difluorohydroxymethyl)-2,4-bis(1,1,2,2-tetrafluoroethyl)-4,5,5-trifluoro-1,3-dioxolane potassium salt, 2-(difluorohydroxymethyl)-2,4-bis(1,1,2,2,3,3,4,4-octafluorobutyl)-4,5,5-trifluoro-1,3-dioxolane potassium salt, 2-(difluorohydroxymethyl)-2,4 -Bis(1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl)-4,5,5-trifluoro-1,3-dioxolane potassium salt, perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane) sodium salt, perfluoro(2-hydroxymethyl-2,4-diethyl-1,3-dioxolane) sodium salt, perfluoro(2-hydroxymethyl-2,4-di-n-propyl-1,3-dioxolane) sodium salt, perfluoro(2-hydroxymethyl-2,4-di-n-butyl-1,3-dioxolane ) sodium salt, perfluoro(2-hydroxymethyl-2,4-di-n-pentyl-1,3-dioxolane) sodium salt, perfluoro(2-hydroxymethyl-2,4-di-n-hexyl-1,3-dioxolane) sodium salt, 2-(difluorohydroxymethyl)-2,4-bis(1,1,2,2-tetrafluoroethyl)-4,5,5-trifluoro-1,3-dioxolane sodium salt, 2-(difluorohydroxymethyl)-2,4-bis(1,1,2,2,3,3,4,4,-octafluorobutyl)-4,5,5-trifluoro-1,Examples include 3-dioxolane sodium salt, 2-(difluorohydroxymethyl)-2,4-bis(1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl)-4,5,5-trifluoro-1,3-dioxolane sodium salt, etc.

[0062] [Composition] One aspect of the present invention relates to a composition (Composition A) containing a 1,4-dioxane derivative represented by formula (2) and a 1,4-dioxane derivative represented by formula (10). Furthermore, one aspect of the present invention relates to a composition (Composition B) containing one or more (1,3-dioxolane)-2-carboxylic acid derivatives selected from the group consisting of (1,3-dioxolane)-2-carboxylic acid fluoride represented by formula (5), (1,3-dioxolane)-2-carboxylic acid represented by formula (6), and (1,3-dioxolane)-2-carboxylic acid salt represented by formula (7), and a 1,3-dioxolane derivative represented by formula (9).

[0063] In composition A, the content ratio of the 1,4-dioxane derivative represented by formula (2) and the 1,4-dioxane derivative represented by formula (10) is preferably perfluoro(dimethyl-2-oxo-1,4-dioxane):perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salt = 1:0.01 to 1:1, and more preferably 1:0.02 to 1:0.20.

[0064] In composition B, the content ratio of one or more (1,3-dioxolane)-2-carboxylic acid derivatives selected from the group consisting of (1,3-dioxolane)-2-carboxylic acid fluoride represented by formula (5), (1,3-dioxolane)-2-carboxylic acid represented by formula (6), and (1,3-dioxolane)-2-carboxylic acid salts represented by formula (7), and a 1,3-dioxolane derivative represented by formula (9) is preferably represented by formula (5). One or more (1,3-dioxolane)-2-carboxylic acid derivatives selected from the group consisting of (1,3-dioxolane)-2-carboxylic acid fluoride, (1,3-dioxolane)-2-carboxylic acid represented by formula (6), and (1,3-dioxolane)-2-carboxylic acid salts represented by formula (7): 1,3-dioxolane derivative represented by formula (9) = 0.01:1 to 100:1, more preferably 0.02:1 to 50:1. [Examples]

[0065] The present invention will be further described below with reference to examples. However, the present invention is not limited to the embodiments shown in the examples.

[0066] The following equipment was used for the analysis below. 19 F NMR: Bruker AVANCE II 400 or JEOL GSX-400 spectrometer.

[0067] [Example 1] In a 30 mL SUS316 autoclave, under an argon atmosphere, diethylene glycol dimethyl ether (9.37 g, 69.8 mmol), potassium carbonate (1.10 g, 7.90 mmol), and water (0.14 g, 7.8 mmol) were charged. The mixture was cooled to -78°C in a dry ice / acetone bath, hexafluoropropylene oxide (6.60 g, 39.8 mmol) was introduced, and the mixture was stirred at 0°C (reaction temperature) for 18 hours. After depressurization, the resulting solution was distilled under reduced pressure at 50°C to obtain a fraction of 4.28 g. This fraction was analyzed using hexafluorobenzene as an internal standard. 19NMR analysis using FNMR confirmed the formation of 3.83 g of perfluoro(dimethyl-2-oxo-1,4-dioxane) (formula (2)) (yield 62% / based on hexafluoropropylene oxide). Furthermore, it was confirmed that perfluoro(dimethyl-2-oxo-1,4-dioxane) was formed as two diastereomers. 19 F NMR (376MHz, CDCl3) (isomer 1) δ (ppm): -81.6, -81.8, -82.2, -83.0, -117.2, -126.3. (Isomer 2) δ (ppm): -81.6, -82.2, -83.0, -94.6, -113.7, -128.5.

[0068] [Example 2] In a 30 mL SUS316 autoclave, under an argon atmosphere, diethylene glycol dimethyl ether (9.37 g, 69.8 mmol), potassium carbonate (1.09 g, 7.89 mmol), and water (0.14 g, 7.8 mmol) were charged. The mixture was cooled to -78°C in a dry ice / acetone bath, hexafluoropropylene oxide (6.60 g, 39.8 mmol) was introduced, and the mixture was stirred at 0°C (reaction temperature) for 18 hours. Next, under an argon atmosphere, potassium fluoride (0.58 g, 10.0 mmol) and diethylene glycol dimethyl ether (2.81 g, 21.0 mmol) were added to the reaction mixture obtained above. As a pretreatment for the ring reduction step, the mixture was heated at 80°C for 1 hour, cooled to room temperature, depressurized, and then purged with argon. Subsequently, the temperature was raised to 130°C, and the reaction (ring reduction process) was carried out for 18 hours. The obtained solution was subjected to vacuum distillation at 50°C, yielding a fraction of 2.82 g. This fraction was analyzed using hexafluorobenzene as an internal standard. 19 NMR analysis using FNMR confirmed the formation of 2.65 g of 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid fluoride (formula (5a)) (yield 43% / based on hexafluoropropylene oxide). Furthermore, 30 mL of water was added to the residue after vacuum distillation, potassium carbonate was added to a portion of the collected solution, and trifluoroacetic acid was used as an internal standard.19 NMR analysis using FNMR confirmed the formation of 1.72 g of potassium 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylate (formula (7a)) (yield 25% / based on hexafluoropropylene oxide) (total yield of 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid derivatives 68%). It was confirmed that the obtained substances were produced as two types of diastereomers. 19 F NMR (376MHz, CDCl3) (isomer 1) δ (ppm): 23.6, -77.8 (d, J = 132 Hz), -80.1, -81.57, -83.56 (d, J = 135 Hz), -124.9. (Isomer 2) δ (ppm): 23.2, -78.5 (d, J = 132 Hz), -80.4, -81.6, -84.1 (d, J = 139 Hz), -123.7. Furthermore, it was confirmed that potassium 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylate is also produced as two diastereomers. 19 F NMR (376MHz, D2O) (isomer 1) δ (ppm): -78.8, -81.0, -81.9, -84.4, -124.8. (Isomer 2) δ (ppm): -79.5, -81.4, -82.0, -84.8, -124.9.

[0069] [Example 3] In a 30 mL SUS316 autoclave under an argon atmosphere, diethylene glycol dimethyl ether (9.37 g, 69.8 mmol), potassium carbonate (1.08 g, 7.8 mmol), and water (0.14 g, 7.8 mmol) were charged. The mixture was cooled to -78°C in a dry ice / acetone bath, hexafluoropropylene oxide (5.50 g, 33.1 mmol) was introduced, and the mixture was stirred at 0°C (reaction temperature) for 18 hours. After depressurization, the resulting solution was distilled under reduced pressure at 50°C to obtain a fraction of 4.67 g. This fraction was analyzed using hexafluorobenzene as an internal standard. 19NMR analysis using FNMR confirmed the formation of 4.51 g of perfluoro(dimethyl-2-oxo-1,4-dioxane) (formula (2)) (yield 88% / based on hexafluoropropylene oxide). Furthermore, it was confirmed that perfluoro(dimethyl-2-oxo-1,4-dioxane) was formed as two diastereomers.

[0070] [Example 4] In a 100 mL SUS316 autoclave under a nitrogen atmosphere, diethylene glycol dimethyl ether (34.67 g), potassium carbonate (4.623 g, 33.45 mmol), and water (0.622 g, 34.52 mmol) were charged. The mixture was cooled to 0°C in an ice bath, hexafluoropropylene oxide (21.71 g, 130.77 mmol) was introduced, and the mixture was stirred at 0°C (reaction temperature) for 18 hours. After stirring at 20-25°C for 2 hours, the mixture was cooled again to 0°C, depressurized, and the reaction solution was removed from the container. Benzotrifluoride was used as the internal standard for this reaction solution. 19 NMR analysis using 1F NMR confirmed the formation of 11.16 g of perfluoro(dimethyl-2-oxo-1,4-dioxane) (formula (2)) (yield 55% / based on hexafluoropropylene oxide).

[0071] [Examples 5-8] The same procedure as in Example 4 was carried out, except that the size of the reaction vessel and the amounts of diethylene glycol dimethyl ether, potassium carbonate, water, and hexafluoropropylene oxide used were changed as shown in Table 1, to obtain perfluoro(dimethyl-2-oxo-1,4-dioxane) (formula (2)) and perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salt (formula (10)). The results are shown in Table 1. Examples 6 to 8 are compositions containing perfluoro(dimethyl-2-oxo-1,4-dioxane) and perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salt, with the content ratios being perfluoro(dimethyl-2-oxo-1,4-dioxane):perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salt = 1:0.09 (Example 6), 1:0.18 (Example 7), and 1:0.25 (Example 8).

[0072] [Table 1]

[0073] The analysis results for perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salt were as follows: 19 F NMR (376MHz, solvent-free) δ (ppm): -24.63, -74.97 (d, J = 150Hz), -81.72, -82.58, -86.25, -122.34. -129.98.

[0074] [Example 9] In a 250 mL SUS316 autoclave under a nitrogen atmosphere, diethylene glycol dimethyl ether (77.87 g), potassium carbonate (11.192 g, 80.98 mmol), potassium fluoride (4.641 g, 79.88 mmol, spray-dried), and water (1.443 g, 80.12 mmol) were charged. The mixture was cooled to 0°C in an ice bath, hexafluoropropylene oxide (55.20 g, 332.49 mmol) was introduced, and the mixture was stirred at 0°C (reaction temperature) for 18 hours. After stirring at 20-25°C for 2 hours, the mixture was cooled again to 0°C, depressurized, and the reaction solution was removed from the container. Benzotrifluoride was used as the internal standard for this reaction solution. 19 NMR analysis using 1F NMR confirmed the formation of 24.91 g of perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salt (formula (10)) (yield 41% / based on hexafluoropropylene oxide).

[0075] [Example 10] In a 190 mL SUS316 autoclave under a nitrogen atmosphere, diethylene glycol dimethyl ether (59.37 g), potassium fluoride (14.244 g, 245.18 mmol, spray-dried), and water (2.101 g, 116.65 mmol) were charged. The mixture was cooled to 0°C in an ice bath, hexafluoropropylene oxide (41.10 g, 247.56 mmol) was introduced, and the mixture was stirred at 0°C (reaction temperature) for 66 hours. After stirring at 20-25°C for 2 hours, the mixture was cooled again to 0°C, depressurized, and the reaction solution was removed from the container. Benzotrifluoride was used as the internal standard for this reaction solution. 19 NMR analysis using 1F NMR confirmed the formation of 20.42 g of perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salt (formula (10)) (yield 53% / based on hexafluoropropene oxide).

[0076] [Example 11] In a 30 mL SUS316 autoclave, under a nitrogen atmosphere, 16.13 g of the reaction solution obtained in Example 5 (containing 3.72 g (12.00 mmol) of perfluoro(dimethyl-2-oxo-1,4-dioxane)), 2.79 g of diethylene glycol dimethyl ether, and 0.556 g of potassium fluoride (9.58 mmol, spray-dried) were charged. As a pretreatment for the ring reduction step, the autoclave was heated at 80°C for 1 hour, cooled to 0°C, and depressurized. Subsequently, the temperature was raised to 120°C, and the reaction (ring reduction process) was carried out for 24 hours. The resulting solution was prepared using benzotrifluoride as an internal standard. 19 NMR analysis using 1F NMR confirmed the formation of 3.26 g of perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane) potassium salt (formula (9a)) (yield 74% / based on perfluoro(dimethyl-2-oxo-1,4-dioxane)). The analysis results for perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane) potassium salt were as follows: 19F NMR (376MHz, solvent-free) δ (ppm): -31.62, -77.54 (d, J = 132Hz), -80.11, -81.11, -81.66, -82.00~-83.50, -121.83.

[0077] [Example 12] 21.73 g of the reaction solution obtained in Example 9 (containing 3.74 g (10.15 mmol) of perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salt (formula (10))) was charged into a 30 mL SUS316 autoclave under a nitrogen atmosphere. The temperature was raised to 130°C and the reaction (ring reduction step) was carried out for 66 hours. Note that the reaction solution obtained in Example 9 contains diethylene glycol dimethyl ether. The resulting solution was prepared using benzotrifluoride as an internal standard. 19 NMR analysis using 1F NMR confirmed the formation of 3.48 g of perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane) potassium salt (93% yield / based on perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salt) and 0.10 g of [perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylic acid fluoride (3% yield / based on perfluoro(dimethyl-2-hydroxy-1,4-dioxane) potassium salt).

[0078] [Example 13] A 25% potassium hydroxide aqueous solution (7.48 g) was placed in a 30 mL round-bottom flask, cooled to 0°C in an ice bath, and 11.72 g of the reaction solution obtained in Example 11 (containing 2.15 g (5.85 mmol) of perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane) potassium salt) was added dropwise while stirring with a stirring bar. The reaction solution separated into two layers. 2,2,2-trifluoroethanol was used as the internal standard for the upper layer. 19NMR analysis using 1F NMR confirmed the formation of 2.02 g of potassium 2-[perfluoro(2,4-dimethyl-1,3-dioxolane)]carboxylate (100% yield / based on potassium perfluoro(2-hydroxymethyl-2,4-dimethyl-1,3-dioxolane) salt).

[0079] A (1,3-dioxolane)-2-carboxylic acid derivative obtained by one aspect of the present invention can be used as a raw material for the synthesis of poly[perfluoro(2-methylene-4-methyl-1,3-dioxolane)], which is promising as a resin for gas separation membranes, a transparent resin for optical fibers, and the like.

Claims

1. Water, inorganic base and formula (1): 【Chemistry 1】 Formula (2) includes reacting a fluoroalkene oxide represented by formula (1) (wherein R represents a fluorine atom or a fluoroalkyl group): 【Chemistry 2】 1,4-dioxane derivatives represented by formula (2) (wherein R represents a fluorine atom or a fluoroalkyl group, and the two Rs are either the same or different). and equation (10): 【Transformation 3】 (In formula (10), M ’＋ (where R represents a countercation, and R represents a fluorine atom or a fluoroalkyl group; two Rs may be the same or different.) A method for producing one or more 1,4-dioxane derivatives selected from the group consisting of 1,4-dioxane derivatives represented by .

2. A method for producing a 1,4-dioxane derivative according to claim 1, wherein the reaction is carried out in the presence of an organic solvent.

3. The method for producing a 1,4-dioxane derivative according to claim 2, wherein the organic solvent is an ether-based solvent.

4. The method for producing a 1,4-dioxane derivative according to claim 3, wherein the ether solvent is one or more ether solvents selected from the group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

5. The method for producing a 1,4-dioxane derivative according to claim 1, wherein the inorganic base is one or more inorganic bases selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal bicarbonates, fluoride salts, and alkaline earth metal bicarbonates.

6. The method for producing a 1,4-dioxane derivative according to claim 5, wherein the inorganic base is one or more inorganic bases selected from the group consisting of alkali metal carbonates and fluoride salts.

7. The method for producing a 1,4-dioxane derivative according to claim 5, wherein the inorganic base is an alkali metal carbonate.

8. The method for producing a 1,4-dioxane derivative according to claim 5, wherein the inorganic base is a fluoride salt.

9. A method for producing a 1,4-dioxane derivative according to claim 1, wherein the reaction temperature of the above reaction is in the range of -20°C to 200°C.

10. A method for producing a 1,4-dioxane derivative according to claim 1, wherein R is a fluoroalkyl group having 1 to 10 carbon atoms.

11. A method for producing a 1,4-dioxane derivative according to claim 1, wherein R is a perfluoroalkyl group having 1 to 4 carbon atoms.

12. To produce a 1,4-dioxane derivative by the manufacturing method described in any one of claims 1 to 11, and The manufactured 1,4-dioxane derivative is subjected to ring reduction under heating. A method for producing one or more (1,3-dioxolane)-2-carboxylic acid derivatives selected from the group consisting of formulas (5), (6), (7), and (9), including the above. Formula (5): 【Chemistry 4】 (1,3-dioxolane)-2-carboxylic acid fluoride (In formula (5), R represents a fluorine atom or a fluoroalkyl group, and any two Rs may be the same or different.) Formula (6): 【Transformation 5】 (1,3-dioxolane)-2-carboxylic acid represented by formula (6) (wherein R represents a fluorine atom or a fluoroalkyl group, and the two Rs are either the same or different). Formula (7): 【Transformation 6】 (In formula (7), M ＋ (1,3-dioxolane)-2-carboxylate salts are represented by , where R represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and two Rs may be the same or different. Formula (9): 【Transformation 7】 (In formula (9), M ＋ ) represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and any two Rs may be the same or different. ) 1,3-dioxolane derivatives represented by )

13. A method for producing a (1,3-dioxolane)-2-carboxylic acid derivative according to claim 12, wherein the ring reduction is carried out in the presence of a fluoride.

14. The method for producing a (1,3-dioxolane)-2-carboxylic acid derivative according to claim 13, wherein the fluoride is one or more fluorides selected from the group consisting of cesium fluoride, potassium fluoride, and sodium fluoride.

15. A method for producing a (1,3-dioxolane)-2-carboxylic acid derivative according to claim 12, wherein the reaction temperature for the ring contraction is in the range of 100°C to 200°C.

16. Formula (10): 【Transformation 8】 (In formula (10), M ’＋ A 1,4-dioxane derivative represented by (where R represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and the two Rs are either the same or different).

17. Formula (2): 【Chemistry 9】 A 1,4-dioxane derivative represented by formula (2) (wherein R represents a fluorine atom or fluoroalkyl group in formula (1), and the two Rs are either the same or different), Formula (10): 【Chemistry 10】 (In formula (10), M ’＋ ) represents a 1,4-dioxane derivative, where R represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and the two Rs are either the same or different. A composition containing the following:

18. Formula (9): 【Chemistry 11】 (In formula (9), M ＋ A 1,3-dioxolane derivative represented by (where R represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and the two Rs are either the same or different).

19. Formula (5): 【Chemistry 12】 (1,3-dioxolane)-2-carboxylic acid fluoride, represented by formula (5), (wherein R represents a fluorine atom or a fluoroalkyl group, and the two Rs are the same or different.) Formula (6): 【Chemistry 13】 (1,3-dioxolane)-2-carboxylic acid represented by formula (6), (wherein R represents a fluorine atom or a fluoroalkyl group, and the two Rs are either the same or different.) Formula (7): 【Chemistry 14】 (In formula (7), M ＋ (1,3-dioxolane)-2-carboxylate salts are represented as follows: where represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and two Rs may be the same or different. One or more (1,3-dioxolane)-2-carboxylic acid derivatives selected from the group consisting of, Formula (9): 【Chemistry 15】 (In formula (9), M ＋ ) represents a countercation, R represents a fluorine atom or a fluoroalkyl group, and the two Rs present may be the same or different. ) and a 1,3-dioxolane derivative represented by A composition containing the following:

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