Method for producing organic compound

Abstract

The present disclosure aims to provide a method for producing an organic compound, etc. The object is to provide a compound of formula (1): [In the formula, X represents -O-, an imino group which may have a substituent, or -S-; R 1 represents a hydrogen atom or a hydrocarbyl group which may have one or more substituents, and R 2 represents a hydrogen atom or a monovalent organic group, or R 1 and R 2 may form a heterocycle optionally having one or more substituents, together with the adjacent X and one carbon atom; R 3 represents a hydrogen atom or a monovalent organic group; and R 4 is -CF2CH3 or -CH2CHF2. A method for producing a compound represented by the formula: Formula (2): [The symbols in the formula are as defined above.] A compound represented by A step A of reacting with vinylidene fluoride under light irradiation, Manufacturing method is solved by

Description

Technical Field

[0001] The present disclosure relates to a method for producing an organic compound (specifically, a method for producing a heteroatom-containing organic compound, more specifically, a method for producing a heteroatom-containing organic compound under light irradiation), etc.

Background Art

[0002] As a method for producing an organic compound (specifically, a method for producing a heteroatom-containing organic compound), more specifically, a method for producing a heteroatom-containing organic compound under light irradiation, for example, Non-Patent Document 1 reports 1-(polyfluoroalkyl)ethane-1,2-diol under UV irradiation.

Prior Art Documents

Non-Patent Documents

[0003]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] There is a demand for providing a new method for producing an organic compound (specifically, a method for producing a heteroatom-containing organic compound, more specifically, a new method for producing a heteroatom-containing organic compound under light irradiation). An object of the present disclosure is to provide a method for producing an organic compound (specifically, a method for producing a heteroatom-containing organic compound, more specifically, a method for producing a heteroatom-containing organic compound under light irradiation), etc.

Means for Solving the Problems

[0005] As means for solving the above problems, the present disclosure provides the following.

[0006] Item 1. Formula (1): [Chemical formula] [In the formula, X represents -O-, an imino group which may have a substituent, or -S-; R 1 represents a hydrogen atom, or a hydrocarbyl group which may have one or more substituents, and R 2 represents a hydrogen atom, or a monovalent organic group, or R 1 and R 2 may together with the adjacent X and one carbon atom form a heterocyclic ring which may have one or more substituents; R 3 represents a hydrogen atom, or a monovalent organic group; and R 4 is -CF 2 CH 3 or -CH 2 CHF 2 .] A method for producing a compound represented by Formula (2): [Chemical formula] [The symbols in the formula have the same meanings as described above.] reacting the compound represented by with vinylidene fluoride under light irradiation, comprising step A, A production method. Item 2. wherein X is -O-, The production method according to item 1. Item 3. R 1 is a hydrogen atom, or an alkyl group which may have one or more substituents, or an aryl group or heteroaryl group which may have one or more substituents, The production method according to item 1 or 2. Item 4. R 1 is a hydrogen atom, or a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO 2 R, -SOR, -OP(=O)(OR) 2 , and an alkyl group or an aryl group which may each have one or more substituents selected from the group consisting of -OR, and R is, in each occurrence, the same or different and is a hydrogen atom, an alkyl group or an aryl group, The production method according to item 3. Item 5. R 2 is a hydrogen atom, or an alkyl group which may have one or more substituents, or an aryl group which may have one or more substituents is The production method according to any one of items 1 to 4. Item 6. R 2 is a hydrogen atom, or a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO 2 R, -SOR, -OP(=O)(OR) 2 , and an alkyl group or an aryl group which may have one or more substituents selected from the group consisting of -OR, and R is, in each occurrence, the same or different and is a hydrogen atom, an alkyl group or an aryl group, The production method according to item 5. Item 7. R 1 and R 2 together with X and one carbon atom to which they are each adjacent form a heterocycle which may have one or more substituents, The production method according to any one of items 1 to 6. Item 8. R 3 is a hydrogen atom, a hydrocarbyl group, or a hydrocarbyloxy group is The manufacturing method according to any one of items 1 to 7. Item 9. R 4 is -CF 2 CH 3 or -CH 2 CHF 2 and The manufacturing method according to any one of items 1 to 8. Item 10. At least a part of vinylidene fluoride is introduced into the liquid containing the compound represented by the formula (2) in the form of fine bubbles containing the same. The manufacturing method according to any one of items 1 to 9. Item 11. The form of the fine bubbles is such that the ratio of the number of bubbles having a particle diameter in the range of 5 nm to 100 μm to the total number of bubbles of the gas is 90% or more. The manufacturing method according to item 10. Item 12. The ratio of the volume of the gas containing vinylidene fluoride to the volume of the liquid containing the compound represented by the formula (2) is in the range of 0.01 to 1. The manufacturing method according to any one of items 1 to 11. Item 13. The reaction temperature of the step A is 130°C or lower. The manufacturing method according to any one of items 1 to 12. Item 14. The light in the step A contains ultraviolet rays. The manufacturing method according to any one of items 1 to 13. Item 15. Formula (1):

Chemical formula

Chemical formula

[0007] According to the present disclosure, a new method for producing an organic compound (specifically, a method for producing a heteroatom-containing organic compound, more specifically, a new method for producing a heteroatom-containing organic compound under light irradiation) is provided. [Brief Description of the Drawings]

[0008]

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Modes for Carrying Out the Invention

[0009] Term The symbols and abbreviations in this specification can be understood to have the meanings commonly used in the technical field to which the present invention belongs in accordance with the context of this specification, unless otherwise specifically limited. In this specification, the phrase "containing" is used with the intention of including the phrases "consisting essentially of" and "consisting of". Unless otherwise specified, the processes, treatments, or operations described in this specification can be carried out at room temperature. In this specification, room temperature can mean a temperature within the range of 10 to 40 °C. In this specification, the notation “Cn-Cm” (where n and m are each numbers) represents that the number of carbon atoms is n or more and m or less, as is normally understood by those skilled in the art.

[0010] As is understood by those skilled in the art based on common general knowledge, in this specification, the terms “content” and “purity” can be used interchangeably depending on the context.

[0011] In accordance with the definition (2013) of the International Organization for Standardization (ISO) Fine Bubble Technology Technical Committee, in this specification, “fine bubble” means a bubble with a diameter of 100 μm or less, and what is included in each said “fine bubble”, “microbubble” means a bubble with a diameter of 1 to 100 μm, and “ultrafine bubble” means a bubble with a diameter of 1 μm or less.

[0012] In this specification, examples of the “halogen atom” include, for example, fluorine, chlorine, bromine, and iodine.

[0013] In this specification, unless otherwise limited, the “organic group” means a group containing one or more carbon atoms as its constituent atoms. In this specification, unless otherwise limited, the “monovalent organic group” includes a hydrocarbyl group. In this specification, unless otherwise limited, examples of the organic group include a hydrocarbyl group, a hydrocarbyloxy group (e.g., an alkoxy group), an ester group, an ether group, a hydrocarbyloxy group (e.g., an alkoxy group), an ester group, an ether group (or an ether bond-containing group), an acyl group, and a heterocyclyl group (e.g., a heteroaryl group and a non-aromatic heterocyclic group). The said “organic group” can be, for example, a monovalent organic group. In this specification, unless otherwise particularly limited, examples of the "monovalent organic group" include hydrocarbyl groups.

[0014] In this specification, unless otherwise particularly limited, the "hydrocarbyl group" means a group containing one or more carbon atoms and one or more hydrogen atoms as its constituent atoms. The "hydrocarbyl group" may also be referred to as a "hydrocarbon group". In this specification, unless otherwise particularly limited, examples of the "hydrocarbyl group" include aliphatic hydrocarbyl groups (e.g., benzyl group) which may be substituted with one or more aromatic hydrocarbyl groups, and aromatic hydrocarbyl groups (aryl group) which may be substituted with one or more aliphatic hydrocarbyl groups. In this specification, unless otherwise particularly limited, the "aliphatic hydrocarbyl group" can be linear, branched, cyclic, or a combination thereof. In this specification, unless otherwise particularly limited, the "aliphatic hydrocarbyl group" can be saturated or unsaturated. In this specification, unless otherwise particularly limited, examples of the "aliphatic hydrocarbyl group" include, for example, alkyl groups, alkenyl groups, alkynyl groups, and cycloalkyl groups. In this specification, unless otherwise particularly limited, examples of the "alkyl group" include linear or branched alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl (e.g., propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl), and hexyl. In this specification, unless otherwise particularly limited, examples of the "alkenyl group" include linear or branched alkenyl groups having 2 to 10 carbon atoms such as vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, and 5-hexenyl. In this specification, unless otherwise particularly limited, examples of the "alkynyl group" include linear or branched alkynyl groups having 2 to 6 carbon atoms, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, and 5-hexynyl. In this specification, unless otherwise particularly limited, examples of the "cycloalkyl group" include cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopentyl group, cyclohexyl group, and cycloheptyl. In this specification, unless otherwise particularly limited, examples of the "aromatic hydrocarbyl group (aryl group)" include phenyl group, naphthyl group, phenanthryl group, anthryl group, and pyrenyl group.

[0015] In this specification, unless otherwise particularly limited, the "alkoxy group" is, for example, a group represented by RO- (wherein R is an alkyl group) in the formula. In this specification, unless otherwise particularly limited, the "ester group" means an organic group having an ester bond (that is, -C(=O)-O- or -O-C(=O)-). Examples thereof include a group represented by the formula: RCO 2 -(wherein R is an alkyl group) in the formula, and a group represented by the formula: R a -CO 2 -R b -(wherein R a is an alkyl group, and R b is an alkylene group) in the formula.

[0016] In this specification, unless otherwise particularly limited, the "ether group" or "ether bond-containing group" means a group having an ether bond (-O-). Examples of the "ether group" or "ether bond-containing group" include polyether groups. Examples of polyether groups include a group represented by the formula: R a -(O-R b ) n -(wherein R a is an alkyl group, R bis, in each occurrence, the same or different and is an alkylene group, and n is an integer of 1 or more. The group represented by ) is included. The alkylene group is a divalent group formed by removing one hydrogen atom from the alkyl group. Examples of the "ether group" or "ether bond-containing group" also include hydrocarbyl ether groups. A hydrocarbyl ether group means a hydrocarbyl group having one or more ether bonds inside and / or at the terminal (or root) of the group. The "hydrocarbyl group having one or more ether bonds" can be a hydrocarbyl group in which one or more ether bonds are inserted. Examples thereof include hydrocarbyloxy groups (e.g., benzyloxy group). Examples of the "hydrocarbyl group having one or more ether bonds" include alkyl groups having one or more ether bonds. The "alkyl group having one or more ether bonds" can be an alkyl group in which one or more ether bonds are inserted. In the present specification, such a group may be referred to as an alkyl ether group.

[0017] In the present specification, unless otherwise specified, the "acyl group" includes an alkanoyl group. In the present specification, unless otherwise specified, the "alkanoyl group" is, for example, a group represented by RCO- (wherein R is an alkyl group).

[0018] In the present specification, unless otherwise specified, examples of the "heteroaryl group" include 5-membered or 6-membered heteroaryl groups and groups condensed with a benzene ring. In this specification, unless otherwise specifically limited, examples of the "5- or 6-membered monocyclic aromatic heterocyclic group" include pyrrolyl (e.g., 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (e.g., 2-furyl, 3-furyl), thienyl (e.g., 2-thienyl, 3-thienyl), pyrazolyl (e.g., 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (e.g., 1-imidazolyl, 2-imidazolyl, 4-imidazolyl), isoxazolyl (e.g., 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl), oxazolyl (e.g., 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (e.g., 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl), thiazolyl (e.g., 2-thiazolyl, 4-thiazolyl, 5-thiazolyl), triazolyl (e.g., 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxadiazolyl (e.g., 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl), thiadiazolyl (e.g., 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl), tetrazolyl, pyridyl (e.g., 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridazinyl (e.g., 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (e.g., 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), and pyrazinyl, etc. Examples of 5-membered heteroaryl groups having one or more (e.g., 1, 2, or 3) heteroatoms selected from the group consisting of oxygen, sulfur, and nitrogen as ring-constituting atoms are exemplified.

[0019] In this specification, unless otherwise specified, examples of the "heterocyclic ring" include 5- to 7-membered heterocyclic rings containing 1 to 4 heteroatoms selected from nitrogen atoms, sulfur atoms, and oxygen atoms in addition to carbon atoms. In this specification, unless otherwise specified, examples of the "heterocyclic ring" include non-aromatic heterocyclic rings and aromatic heterocyclic rings.

[0020] In this specification, unless otherwise specified, examples of the "5- to 7-membered heterocycle containing 1 to 4 heteroatoms selected from nitrogen, sulfur, and oxygen atoms in addition to carbon atoms" include pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, tetrahydropyran, morpholine, thiomorpholine, piperazine, and hexamethyleneimine.

[0021] In this specification, unless otherwise specified, examples of the "non-aromatic heterocycle" include 3- to 8-membered non-aromatic heterocycles and the like. Specific examples thereof include oxirane, azetidine, oxetane, thietane, pyrrolidine, dihydrofuran, tetrahydrofuran, tetrahydrothiophene, imidazolidine, oxazolidine, isoxazoline, piperidine, dihydropyran, tetrahydropyran, tetrahydrothiopyran, morpholine, thiomorpholine, piperazine, dihydrooxazine, tetrahydrooxazine, dihydropyrimidine, tetrahydropyrimidine, azepane, oxepane, thiepane, oxazepane, thiazepane, azocane, oxocane, thiocane, oxazocane, thiazocane, etc.

[0022] In this specification, unless otherwise specified, examples of the aromatic heterocycle include 5- or 6-membered aromatic heterocycles. Specific examples thereof include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, furazan, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, and triazine, etc.

[0023] Manufacturing method The production method of the present disclosure is Formula (1):

Chemical formula

Chemical formula

[0024] In this specification, the compound represented by the above formula (1) may be referred to as "the compound of formula (1)" or "compound (1)". In this specification, the compound represented by the above formula (2) may be referred to as "the compound of formula (2)" or "compound (2)".

[0025] X is preferably -O-.

[0026] R 1 is preferably a hydrogen atom, or an alkyl group which may have one or more substituents, or an aryl group which may have one or more substituents.

[0027] R 1 is preferably a hydrogen atom, or a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO 2 R, -SOR, -OP(=O)(OR) 2 , and an alkyl group or an aryl group which may each have one or more substituents selected from the group consisting of -OR, and R is, in each occurrence, the same or different and is a hydrogen atom or an alkyl group.

[0028] R 2 is preferably a hydrogen atom, or an alkyl group which may have one or more substituents or an aryl group which may have one or more substituents is.

[0029] R 2 is preferably a hydrogen atom, or a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO 2 R, -SOR, -OP(=O)(OR) 2 , and an alkyl group or an aryl group which may have one or more substituents selected from the group consisting of -OR, and R is, in each occurrence, the same or different and is a hydrogen atom or an alkyl group.

[0030] R 1 and R 2 are preferably forming, together with X and one carbon atom to which they are each adjacent, a heterocycle which may have one or more substituents. Here, X is preferably -O-, that is, the heterocycle is preferably an oxygen-containing heterocycle. The ring is preferably a 5- to 6-membered ring. Preferable examples of the substituents which the heterocycle may have are an alkyl group, an aryl group, a heteroaryl group, a keto group, a nitrilo group, a nitro group, a halogen group, -SO 2R, -SOR, -OP(=O)(OR) 2 and -OR are included.

[0031] R 3 is preferably a hydrogen atom, a hydrocarbyl group, or a hydrocarbyloxy group is. R 3 is more preferably a hydrogen atom, a C1-C6 hydrocarbyl group, or a C1-C6 hydrocarbyloxy group is.

[0032] R 4 is preferably -CF 2 CH 3 or -CH 2 CHF 2 is.

[0033] Preferably, X is -O-, and R 1 is a hydrogen atom, or an alkyl group (preferably a C1-C6 alkyl group) which may have one or more substituents, or an aryl group (preferably a C6-C10 aryl group) which may have one or more substituents [Preferably, a hydrogen atom, or a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO 2 R, -SOR, -OP(=O)(OR) 2 and -OR, respectively, an alkyl group (preferably a C1-C6 alkyl group) or an aryl group (preferably a C6-C10 aryl group) which may each have one or more substituents selected from the group consisting of, and R is, in each occurrence, the same or different and is a hydrogen atom, or an alkyl group (preferably a C1-C6 alkyl group).] is, R2 is a hydrogen atom, or an alkyl group which may have one or more substituents (preferably a C1-C6 alkyl group), or an aryl group which may have one or more substituents [preferably, a hydrogen atom, or a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group (preferably a C6-C10 aryl group), -SO 2 R, -SOR, -OP(=O)(OR) 2 and an alkyl group (preferably a C1-C6 alkyl group) or an aryl group (preferably a C6-C10 aryl group) which may have one or more substituents selected from the group consisting of -OR, and R is, in each occurrence, the same or different and is a hydrogen atom or an alkyl group (preferably a C1-C6 alkyl group); more preferably, a hydrogen atom, or a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO 2 R, -SOR, -OP(=O)(OR) 2 and an alkyl group (preferably a C1-C6 alkyl group) or an aryl group (preferably a C6-C10 aryl group) which may have one or more substituents selected from the group consisting of -OR, and R is, in each occurrence, the same or different and is a hydrogen atom or an alkyl group (preferably a C1-C6 alkyl group).] or R 1 and R 2 are preferably such that they together with X and one carbon atom to which they are each adjacent form a heterocycle which may have one or more substituents: R 3 is a hydrogen atom or a monovalent organic group (preferably a hydrogen atom, a hydrocarbyl group, or hydrocarbyloxy; and More preferably, it is a hydrogen atom, a C1-C10 hydrocarbyl group, or a C1-C10 hydrocarbyloxy); R 4 is -CF 2 CH 3 or -CH 2 CHF 2 is. Preferred examples of the compound (2) include dioxolane (e.g., 1,3-dioxolane), methyl orthoformate, and ethyl orthoformate.

[0034] Process A The reaction of Step A can be carried out, for example, by bringing a gas containing vinylidene fluoride into contact with a liquid containing the compound (2). The content ratio of vinylidene fluoride in the gas is preferably high. Specifically, for example, it is 80 v / v% or more, 90 v / v% or more, 95 v / v% or more, 98 v / v% or more, or 99 v / v% or more. The contact is preferably carried out, for example, by introducing fine bubbles containing vinylidene fluoride into the liquid containing the compound (1). The content ratio of vinylidene fluoride in the fine gas is preferably high. Specifically, for example, it is 80 v / v% or more, 90 v / v% or more, 95 v / v% or more, 98 v / v% or more, or 99 v / v% or more.

[0035] Preferably, at least a part of vinylidene fluoride is introduced into the liquid containing the compound (2) in the form of fine bubbles containing the same.

[0036] The liquid (i.e., the liquid medium in Step A) is preferably a poor solvent for vinylidene fluoride. The liquid medium can be a liquid medium containing one or more selected from the group consisting of water and an organic solvent that is a poor solvent for vinylidene fluoride.

[0037] Specific examples of the liquid medium are as follows: Water; Alcohol solvents [e.g., methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, pentanol, hexanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylene glycol, hexanetriol]; Non-aromatic hydrocarbon solvents [e.g., pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, n-decane, isododecane, tridecane]; Aromatic hydrocarbon solvents [e.g., benzene, toluene, xylene, tetralin, veratrole, ethylbenzene, diethylbenzene, methylnaphthalene, anisole, phenetole, nitrobenzene, o-nitrotoluene, mesitylene, indene, diphenyl sulfide, anisole, propiophenone]; Ketone solvents [e.g., acetone, methyl ethyl ketone, diethyl ketone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, acetonylacetone, methyl hexanone, acetophenone, cyclohexanone, diacetone alcohol, propiophenone, isophorone]; Halogenated hydrocarbon solvents [e.g., dichloromethane, chloroform, chlorobenzene]; Ether solvents [e.g., diethyl ether, tetrahydrofuran (THF), diisopropyl ether, methyl-t-butyl ether (MTBE), dioxane, dimethoxyethane, diglyme, anisole, phenetole, 1,1-dimethoxycyclohexane, diisoamyl ether, cyclopentyl methyl ether (CPME), dioxolane, methyl orthoformate, ethyl orthoformate]; Ester solvents [e.g., ethyl acetate, isopropyl acetate, diethyl malonate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, α-acetyl-γ-butyrolactone]; Nitrile solvents [e.g., acetonitrile, benzonitrile]; Sulfoxide solvents [e.g., dimethyl sulfoxide, sulfolane]; and Amide solvents [e.g., N,N-dimethylformamide (DMF), N,N-dimethylacetamide, N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), N,N-dimethylacrylamide, N,N-dimethylacetoacetamide (DMA), N,N-diethylformamide, N,N-diethylacetamide]; and Combinations of two or more of these are included. Part or all of the reaction substrate in Step A may also function as the liquid medium, and similarly, part or all of the liquid medium may also function as the reaction substrate.

[0038] The ratio of vinylidene fluoride introduced in the form of fine bubbles to the total vinylidene fluoride introduced into the liquid is preferably higher.

[0039] The fine bubbles may be generated by a commonly used method. Examples of such methods include (a) A method using supersaturation (specifically, a method of pressurizing a solute gas in a sealed container containing a solvent to dissolve a sufficient amount, then decompressing the solvent in which the solute gas is dissolved under pressure to generate microbubbles of the solute gas in the solvent); and (b) A gas-liquid shearing method (i.e., a method of supplying a solute gas to a vortex of a solvent, shearing the solute gas in the solvent, and generating fine bubbles of the solute gas in the solvent). are exemplified. The fine bubbles in the method of the present disclosure may be generated by adopting any of these methods and using a fine bubble generator. The fine bubble generator can, for example, have a function of injecting a gas into a liquid and applying a shearing force to the flow of the resulting gas / liquid mixture with a static mixer to repeatedly divide the liquid, thereby creating fine bubbles in the liquid. Examples of the method for generating microbubbles include a pressurized dissolution method, a swirling flow method, a static mixer method, a cavitation method, and a Venturi method.

[0040] The supply amount (or supply rate) of the gas of vinylidene fluoride to the reaction system for Step A can be determined in consideration of the size of the reaction vessel, light transmittance, the capacity of the bubble generator, and the like. Specifically, for example, per minute, with respect to the volume of the reaction solution in the reaction system, usually 1 to 99 vol%, preferably 5 to 80 vol%, more preferably 10 to 50 vol% of the gas of vinylidene fluoride may be supplied.

[0041] The microbubbles are preferably ultrafine bubbles. In this specification, "ultrafine bubbles" refers to bubbles with a diameter of 1 μm or less in accordance with the definition of the International Organization for Standardization (ISO). Ultrafine bubbles can be prepared using commercially available devices [e.g., SMX554, SMX374, SMX115T, SMX115, ASG1, ASG2, MA3FS, MA3, MA5S, BA06S, and AMB3 (all from HACK UFB), and FBG-OS Type1 (by PMS)]. A preferred form of the microbubbles is with respect to the total number of bubbles of the gas, preferably, the ratio of the number of bubbles having a particle diameter in the range of 10 nm to 1 μm is 90% or more; more preferably, the ratio of the number of bubbles having a particle diameter in the range of 50 nm to 1 μm is 90% or more; the ratio of the number of bubbles having a particle diameter in the range of 50 nm to 500 nm is 90% or more is.

[0042] The particle size, number, distribution, and average particle size of the fine bubbles are measured by nanoparticle tracking analysis, which is a method of measuring the Brownian diffusion equivalent diameter on a number basis using laser light. The measurement can be carried out using a commercially available device, NanoSight LM-10 (NanoSight) or its equivalent. However, if accurate measurement cannot be performed by the nanoparticle tracking analysis method, it may be measured by another method. Such alternative methods include (1) A method using Particle Sensor PS100 (product name, Hokuto Denko Industries) or its equivalent as a method for measuring the diameter of nanobubbles, and (2) A method using Shimadzu Nanoparticle Size Distribution Analyzer SALD-7100 (product name, Shimadzu Corporation) or its equivalent as a method for measuring the diameters of both microbubbles and nanobubbles, and (3) A method of performing a combination of these measurement methods can be mentioned.

[0043] In the reaction system of step A, the ratio of the volume of the gas containing vinylidene fluoride to the volume of the liquid containing compound (2) is usually in the range of 0.01 to 1; preferably in the range of 0.02 to 0.9; more preferably in the range of 0.05 to 0.8; and even more preferably in the range of 0.1 to 0.5 is.

[0044] The reaction of step A is carried out under light irradiation. As the irradiation light used for the light irradiation, for example, any light that can start and / or promote the reaction of step A can be used without particular limitation. Examples of the light source include low-pressure, medium-pressure, or high-pressure mercury lamps, tungsten lamps, and light-emitting diodes (LEDs). The irradiation light can preferably be light containing ultraviolet rays. The start of the light irradiation can be before, during, simultaneously with, or after the mixing. The intensity of light irradiation only needs to be such that energy capable of initiating and / or promoting the reaction in Step A is supplied. This can be appropriately adjusted, for example, based on common general knowledge, by adjusting the output of the light source, the distance between the light source and the reaction system in Step A, etc., so that the reaction in Step A proceeds appropriately.

[0045] The lower limit of the reaction temperature in Step A is preferably -50°C, more preferably -10°C, even more preferably 0°C, even more preferably 10°C, and particularly preferably 20°C can be. The upper limit of the reaction temperature in Step A is preferably 130°C, more preferably 100°C, even more preferably 80°C, even more preferably 50°C, and particularly preferably 30°C can be. The reaction temperature in Step A is preferably within the range of -10 to 130°C, more preferably within the range of 0 to 100°C, even more preferably within the range of 10 to 80°C, and particularly preferably within the range of 10 to 50°C, even more particularly preferably within the range of 10 to 30°C, can be. Further, the reaction in Step A can preferably be carried out at room temperature. Due to being at such a reaction temperature, there is a possibility that the reaction in Step A may become insufficient. If the reaction temperature is too high, it is disadvantageous in terms of cost and there is a possibility that undesirable reactions may occur. The upper limit of the reaction temperature in Step A tends to suppress side reactions more when it is lower. The lower limit of the reaction temperature in Step A tends to promote the progress of the target reaction more when it is higher.

[0046] The lower limit of the amount of vinylidene fluoride in the reaction of Step A is, based on 1 mol of Compound (2), preferably 0.001 mol, more preferably 0.002 mol, and even more preferably 0.003 mol can be. The upper limit of said amount is, based on 1 mol of Compound (2), preferably 10 mol, more preferably 5 mol, and even more preferably 3 mol can be. Said amount is, based on 1 mol of Compound (2), preferably in the range of 0.001 to 10 mol, more preferably in the range of 0.002 to 5 mol, and even more preferably in the range of 0.003 to 3 mol can be. By carrying out the reaction with said amount, the target product can be efficiently obtained.

[0047] The light in Step A preferably contains ultraviolet light. Said ultraviolet light preferably has a main wavelength in the range of 200 nm to 400 nm, more preferably 220 nm to 350 nm. The light in Step A may contain light other than said ultraviolet light. The irradiation of said light can be carried out, for example, by using a mercury lamp (e.g., low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp), UV-LED, or excimer lamp, or a combination thereof.

[0048] To at least a part of the reaction system of Step A, preferably 0.01 W / m 2 or more, more preferably 0.1 W / m 2 or more even more preferably 1 W / m 2 or more even more preferably, 10 W / m2 Above It is preferably reached at the light irradiation density of the above. The upper limit of the light irradiation density is, for example, 1000 W / m 2 , 700 W / m 2 , 500 W / m 2 It can be. The range of the light irradiation density is, for example, 0.01 W / m 2 ~1000 W / m 2 , 0.1 W / m 2 ~700 W / m 2 , 1 W / m 2 ~500 W / m 2 , It can be within the range of.

[0049] The lower limit of the reaction time of the process A is Preferably 0.5 hours, More preferably 1 hour, And even more preferably 1.5 hours It can be. The upper limit of the reaction time of the process A is Preferably 72 hours, More preferably 48 hours, and Even more preferably 24 hours It can be. The reaction time of the process A is Preferably within the range of 0.5 to 72 hours, More preferably within the range of 1 to 48 hours, And even more preferably within the range of 1.5 to 24 hours It can be. If the reaction time is too short, the reaction of process A may be insufficient. If the reaction time is too long, it is disadvantageous in terms of cost and there is a risk of undesirable reactions occurring.

[0050] The reaction can be carried out in the presence or absence of an inert gas (e.g., nitrogen gas). The inert gas may be introduced into the reaction system of process A together with vinylidene fluoride.

[0051] The reaction of Project A can preferably be carried out in the presence of one or more selected from the group consisting of a reaction initiator (e.g., radical reaction initiator) and a photosensitizer. Examples of the reaction initiator (e.g., radical reaction initiator) include α-diketone compounds (e.g., benzil, diacetyl), acyloin compounds (e.g., benzoin), acyloin ether compounds (e.g., benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether), thioxanthone compounds (e.g., thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid), acetophenone compounds (e.g., acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one), aminobenzoic acid compounds (e.g., ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate), halogen compounds (e.g., phenacyl chloride, trihalomethylphenyl sulfone), acylphosphine oxide compounds, peroxides (e.g., di-t-butyl peroxide), and alkylphenone compounds [e.g., Igracure 127 (trade name, Merck)] are included. The usage amount of the reaction initiator is preferably 0.00001 to 10 moles, more preferably 0.0001 to 1 mole, per 100 moles of vinylidene fluoride, and More preferably, it can be in the range of 0.001 to 0.1 mol. It can be within the range.

[0052] Examples of the "photosensitizer" include For example, ketone compounds (e.g., acetone), benzophenone compounds [e.g., benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone], anthracene compounds (e.g., anthracene), quinone compounds (e.g., anthraquinone, 1,4-naphthoquinone), thiopyrylium salt compounds, merocyanine compounds, quinoline compounds, styryl compounds, coumarin compounds, ketocoumarin compounds, thioxanthene compounds, xanthene compounds, oxonol compounds, cyanine compounds, rhodamine compounds, pyrilium salt compounds, etc. are exemplified. The photosensitizer can be used alone or in combination of two or more.

[0053] Typically, styryl compounds or quinoline compounds, or coumarin compounds are preferred. Specific examples of styryl compounds or quinoline compounds are 2-(p-dimethylaminostyryl)quinoline, 2-(p-diethylaminostyryl)quinoline, 4-(p-dimethylaminostyryl)quinoline, 4-(p-diethylaminostyryl)quinoline, 2-(p-dimethylaminostyryl)-3,3-3H-indole, 2-(p-diethylaminostyryl)-3,3-3H-indole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-diethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzimidazole, and 2-(p-diethylaminostyryl)benzimidazole are included.

[0054] Specific examples of the coumarin compound are 7 - Diethylamino - 4 - methylcoumarin, 7 - ethylamino - 4 - trifluoromethylcoumarin, 4,6 - diethylamino - 7 - ethylaminocoumarin, 3 - (2 - benzimidazolyl) - 7 - N,N - diethylaminocoumarin, 7 - diethylaminocyclopenta(c)coumarin, 7 - aminotrifluoromethylcoumarin, 1,2,3,4,5,3H,6H,10H - tetrahydro - 8 - trifluoromethyl(1)benzopyrano - (9,9A,1 - gh) - quinolidin - 10 - one, 7 - ethylamino - 6 - methyl - 4 - trifluoromethylcoumarin, and 1,2,3,4,5,3H,6H,10H - tetrahydro - 9 - carbethoxy(1)benzopyrano(9,9a,1 - gh) - quinolidin - 10 comprises.

[0055] According to the production method of the present disclosure, the raw material conversion rate can preferably be 10% or more, more preferably 30% or more, and still more preferably 50% or more. According to the production method of the present disclosure, the selectivity of the target compound can preferably be 80% or more, and more preferably 90% or more. According to the production method of the present disclosure, the yield of the target compound can preferably be 50% or more, and more preferably 70% or more.

[0056] Compound The compound of the present disclosure has the formula (1):

Chemical formula

[0057] Composition The vinylidene fluoride-containing composition of the present disclosure (1) contains vinylidene fluoride and (2) a liquid medium which is a poor solvent for vinylidene fluoride, and at least a part of the vinylidene fluoride is dispersed as fine bubbles in the liquid medium.

[0058] The liquid medium is preferably a liquid medium containing at least one selected from the group consisting of water and an organic solvent which is a poor solvent for vinylidene fluoride.

[0059] Preferably, most of the vinylidene fluoride other than that dissolved in the poor solvent is dispersed as fine bubbles.

[0060] The form of the fine bubbles is such that the ratio of the number of bubbles having a particle diameter in the range of 5 nm to 100 μm to the total number of bubbles of the gas is 90% or more.

[0061] In the composition, the ratio of the volume of the gas containing vinylidene fluoride to the volume of the liquid containing the compound represented by the above formula (2) is Generally, within the range of 0.01 to 1; Preferably, within the range of 0.02 to 0.9; More preferably, within the range of 0.05 to 0.8; and Even more preferably, within the range of 0.1 to 0.5 is.

[0062] The average dispersed particle diameter is Preferably 10 μm or less, More preferably 5 μm or less, Even more preferably 1 μm or less, Even more preferably 500 nm or less, Particularly preferably 300 nm or less can be.

[0063] The average dispersed particle diameter can be, for example, 5 nm or more, 10 nm or more, 50 nm or more, or 100 nm or more. Preferably

[0064] The composition may be placed in a sealable container (e.g., a cylinder). The present disclosure also provides a sealable container (e.g., a cylinder) enclosing the composition.

[0065] The form of the bubbles is with respect to the total number of the gas bubbles, Preferably, the proportion of the number of bubbles having a particle diameter in the range of 10 nm to 1 μm is 90% or more; More preferably, the proportion of the number of bubbles having a particle diameter in the range of 50 nm to 1 μm is 90% or more; The proportion of the number of bubbles having a particle diameter in the range of 50 nm to 500 nm is 90% or more is. Details of the composition can be understood based on the description of the "method for producing an organic composition".

[0066] The liquid medium is preferably a liquid medium containing at least one selected from the group consisting of water and an organic solvent that is a poor solvent for vinylidene fluoride.

[0067] The method for producing the composition can be understood based on the method for generating fine bubbles described in the above "method for producing an organic composition".

[0068] The form of the fine bubbles is preferably a form in which the ratio of the number of bubbles having a particle diameter in the range of 5 nm to 100 μm to the total number of bubbles of the gas is 90% or more. Other forms or more preferred embodiments of this form can be understood by referring to other descriptions of the present disclosure.

[0069] Fluorine-containing olefin-containing composition The present disclosure also provides the following fluorine-containing olefin-containing compositions. A fluorine-containing olefin-containing composition, (1) a fluorine-containing olefin (excluding vinylidene fluoride), and (2) a liquid medium, and at least a part of the fluorine-containing olefin is dispersed as fine bubbles in the liquid medium.

[0070] The fluorine-containing olefin is preferably Formula (3):

Chemical formula

[0071] The liquid medium is preferably a liquid medium containing at least one selected from the group consisting of water and an organic solvent that is a poor solvent for the fluorinated olefin represented by the formula (3) (excluding vinylidene fluoride).

[0072] The form of the fine bubbles is preferably a form in which the ratio of the number of bubbles having a particle diameter in the range of 5 nm to 100 μm to the total number of gas bubbles is 90% or more. The aspect of the "fluorinated olefin-containing composition (excluding vinylidene fluoride)" can be understood by those skilled in the art with reference to the description of the vinylidene fluoride-containing composition.

[0073] The fine bubbles of the composition can be generated by a commonly used method. As such a method, for example, (1) as a method using supersaturation, a solute gas is pressurized in a sealed container containing a solvent to dissolve a sufficient amount, and then the solvent in which the solute gas is dissolved under pressure is depressurized to generate microbubbles of the solute gas in the solvent. Alternatively, as another method, a gas-liquid shearing method, that is, a method of supplying a solute gas to a vortex of a solvent, shearing the solute gas in the solvent, and generating fine bubbles of the solute gas in the solvent, can be mentioned. The fine bubbles of the composition can be generated using an apparatus for generating fine bubble microbubbles by any of these methods.

[0074] The nanobubble generator has a function of injecting gas into a liquid and applying a shearing force with a static mixer to the flow of the gas / liquid mixture to repeatedly divide the liquid, thereby creating nanobubbles in the liquid. Examples of the method for generating microbubbles include a pressure dissolution method, a swirling flow method, a static mixer method, a cavitation method, and a Venturi method.

[0075] The particle size, number of fine bubbles, and their distribution and average particle size can be measured by the above-described method.

[0076] As described above, although the embodiments have been explained, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

Example

[0077] Hereinafter, the aspects of the present disclosure will be described in detail by way of examples, but the aspects of the present disclosure are not limited thereto.

[0078] The meanings of the symbols and abbreviations in the examples are shown below. VdF: Vinylidene fluoride

[0079] Examples 1 to 3 In Examples 1 to 3, Compounds A to D shown below were produced from VdF.

Chemical formula

[0080] (Example 1) Using the apparatus outlined in Figure 1, a mixed solution of 1,3 - dioxolane (48 mL) and acetone (12 mL) was introduced into a Pyrex (registered trademark) reactor in a water bath. Then, the internal temperature was set to 40°C. Under irradiation with a 100W mercury lamp, while circulating the solution at a rate of 30 mL / min by a pump (which was a diverted HPLC pump as described in the figure), VdF was introduced as fine bubbles at a rate of 4.0 mL / min using a fine bubble generator. After 2 hours, the solution was analyzed by F - NMR, and an adduct was obtained in a yield of 11%. The production ratio is shown in Table 1.

[0081] (Example 2) Using the same apparatus as in Example 1, 1,3 - dioxolane (60 mL) and IRGACURE 127 (63 mg, 0.2 μmol) were introduced into a Pyrex (registered trademark) reactor in a water bath. Then, the internal temperature was set to 40°C. Under irradiation with a 100W mercury lamp, while circulating the solution at a rate of 30 mL / min by a pump (which was a diverted HPLC pump as described in the figure), VdF was introduced as fine bubbles at a rate of 4.0 mL / min using a fine bubble generator. After 2 hours, the solution was analyzed by F - NMR, and an adduct was obtained in a yield of 44%. The production ratio is shown in Table 1.

[0082] (Example 3) The reaction was carried out in the same manner as in Example 2 except that the reaction time was changed to 24 hours, and an adduct was obtained in a yield of 87%. The production ratio is shown in Table 1.

Table 1

Chemical formula

[0083] Examples 4 to 5 (Example 4) The reaction was carried out in the same manner as in Example 1 except that 1,3-dioxolane was replaced with isopropyl alcohol, and the adduct was obtained in a yield of 32%. The production ratio is shown in Table 2. (Example 5) The reaction was carried out in the same manner as in Example 2 except that 1,3-dioxolane was replaced with isopropyl alcohol, and the adduct was obtained in a yield of 14%. The production ratio is shown in Table 2. [Table 2] [Chemical formula]

[0084] Example 6 The reaction was carried out in the same manner as in Example 1 except that 1,3-dioxolane was replaced with 2-methyl-1,3-dioxolane, and adducts G and H were obtained. The production ratio is shown in Table 3. [Table 3]

[0085] Example 7 [Chemical formula] The reaction was carried out in the same manner as in Example 1 except that 1,3-dioxolane was replaced with methyl orthoformate (48 mL), and the adduct was obtained in a yield of 22%.

[0086] Example 8 The reaction was carried out in the same manner as in Example 1 except that acetone was not added and the amount of 1,3-dioxolane used was changed to 60 mL, and the adduct was obtained in a yield of 12%. The production ratio is shown in Table 4. [Table 4]

[0087] Example 9 TIFF0007691061000017.tifA mixed solution of 251432-(2H-hexafluoropropyl)tetrahydrofuran (18.5 g), acetone (0.4 g) and acetonitrile (35 mL) was introduced into the reactor whose outline was described in Fig. 1. Then, the internal temperature was set to -30°C. While circulating the solution at a rate of 30 mL / min under irradiation with a 100 W mercury lamp, hexafluoropropene was introduced as fine bubbles. When the solution was analyzed by 19F-NMR after 2 hours, bis-2,5-(2H-hexafluoropropyl)tetrahydrofuran was obtained in a 90% yield.

[0088] Examples 10 to 11 (Example 10) The procedure was carried out in the same manner as in Example 1 except that the apparatus was replaced with the apparatus whose outline is shown in Fig. 2, and an adduct was obtained in a 9% yield. The formation ratio is shown in Table 5.

[0089] (Example 11) The procedure was carried out in the same manner as in Example 1 except that the apparatus was replaced with the apparatus equipped with a ceramic filter whose outline is shown in Fig. 3, and an adduct was obtained in a 3% yield. The formation ratio is shown in Table 5.

Table 5

[0090] Example 12 [Measurement of particle size and number of VdF fine bubbles] The particle size of the bubbles formed by the fine bubble generator was measured with a nanoparticle measuring device (NanoSight, manufactured by Nanosight Japan Co., Ltd.). The measurement conditions were as follows. · Liquid medium: water, isopropyl alcohol, 1,3-dioxolane, DMF · Gas: VdF · Nanobubble discharge pressure: 3.0 MPa · Liquid flow rate: 28 mL / min · Gas flow rate: 14 mL / min As a result of the measurement, the presence of bubbles was confirmed from the smallest measurable particle size of 10 nm. The results are shown in Figs. 4 to 7. In the figures, the horizontal axis represents the particle size of the bubbles, and the vertical axis represents the number of bubbles having each particle size per 1 mL of the gas-liquid mixed fluid. Substantially all (100%) of the formed bubbles have a particle size of 10 to 500 nm, and the bubbles having a particle size of 50 to 500 nm account for 95% or more of the total number of bubbles.

[0091] Example 13 [Time-dependent observation of ultra-fine bubbles of VdF] 50 mL of the liquid medium (water, isopropyl alcohol, 1,3-dioxolane, or DMF) used for the measurement was placed in a 100 mL Duran bottle, and the dissolved gas in the liquid medium was removed by ultrasonic degassing and three Ar replacements. Using the same apparatus as that used in Example 1, the reaction temperature was set to 30 °C, the reaction solution was fed at an actual flow rate of 28 mL / min and VdF at 14 mL / min, and the saturation concentration was measured by GC-FID. Taking the time when the VdF concentration reached saturation as 0 hour, the number and concentration of ultrafine bubbles were measured at 0, 1, 2, 4, 8, 24, 48, and 168 hours later. The results of the time-course observation are shown in Figs. 8 to 15.

[0092] Example 14

Chemical formula

[0093] Comparative Example 1

Chemical formula

[0094] Example 15 [Measurement of particle size and number of various fine bubbles] The particle size of the bubbles formed by the microbubble generator was measured by a nanoparticle measuring device (NanoSight, Custom Design Co., Ltd., Japan). The measurement conditions were as follows. · Liquid medium: water, isopropyl alcohol, 1,3-dioxolane, DMF · Gas: 2,3,3,3-tetrafluoropropylene, hexafluoropropylene, or 1-bromo-1-fluoroethylene · Nanobubble discharge pressure: 3.0 MPa · Liquid flow rate: 28 mL / min · Gas flow rate: 14 mL / min As a result of the measurement, the presence of bubbles was confirmed from the measured minimum particle size of 10 nm. The results are shown in FIGS. 16 to 24. In each figure, the horizontal axis represents the particle size of the bubbles, and the vertical axis represents the number of bubbles having each particle size per 1 mL of the gas-liquid mixed fluid. Substantially all (100%) of the formed bubbles had a particle size of 10 to 500 nm, and the bubbles having a particle size of 50 to 500 nm accounted for 95% or more of the total number of bubbles.

[0095] Example 16 [Time-dependent observation of ultra-fine bubbles of various gases] 50 mL of the liquid medium (water, isopropyl alcohol, 1,3-dioxolane, or DMF) used for the measurement was placed in a 100 mL Duran bottle, and the operation of removing the dissolved gas in the liquid medium was performed by ultrasonic degassing and three Ar replacements. Using the same apparatus as that used in Example 1, the reaction temperature was set to 20 - 30 °C, the reaction solution was fed at an actual flow rate of 28 mL / min, and 2,3,3,3-tetrafluoropropylene, hexafluoropropylene, or 1-bromo-1-fluoroethylene was fed at 14 mL / min, respectively, and the saturation concentration was measured by GC-FID. Taking the time when the concentration reached saturation as 0 h, the number and concentration of ultra-fine bubbles were measured after 0, 1, 2, 4, 8, 24, 48, and 168 h. The results are shown in Figs. 25 - 33.

Claims

1. Formula (1): 【Chemical 1】 [wherein, X represents -O-; R １ is a hydrogen atom, or A keto group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO ２ R, -SOR, -OP(=O)(OR) ２ and represents an alkyl group or an aryl group which may have one or more substituents selected from the group consisting of -OR, and R ２ is a hydrogen atom, or A keto group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO ２ R, -SOR, -OP(=O)(OR) ２ , and may have one or more substituents selected from the group consisting of -OR, represents an alkyl group or an aryl group, or R １ and R ２ together with X and one carbon atom to which they are each adjacent form an alkyl group, an aryl group, a heteroaryl group, a keto group, a nitrilo group, a nitro group, a halogen group, -SO ２ R, -SOR, -OP(=O)(OR) ２ , and -OR, and may form an oxygen-containing heterocycle which may have one or more substituents selected from the group consisting of; R ３ represents a hydrogen atom, a C1-6 hydrocarbyl group, or a C1-6 hydrocarbyloxy group; R ４ is -CF ２ CH ３ or -CH ２ CHF ２ and R is, in each occurrence, the same or different and is a hydrogen atom, an alkyl group, or an aryl group.] A method for producing a compound represented by Formula (2): 【Chemical 2】 [The symbols in the formula have the same meanings as described above.] reacting a compound represented by with vinylidene fluoride under light irradiation, comprising Step A A production method.

2. R １ and R ２ together with X and one carbon atom to which they are each adjacent form an oxygen-containing heterocycle which may have one or more substituents selected from the group consisting of an alkyl group, an aryl group, a heteroaryl group, a keto group, a nitrilo group, a nitro group, a halogen group, -SO ２ R, -SOR, -OP(=O)(OR) ２ , and -OR The production method according to Claim 1.

3. Formula (1): 【Chemical Formula 3】 [wherein, X represents -O-; R1 is a hydrogen atom or an alkyl group or an aryl group which may have one or more substituents selected from the group consisting of a keto group, a nitrile group, a nitro group, a halogen group, an aryl group, -SO2R, -SOR, -OP(=O)(OR)2, and -OR; R2 represents an alkoxy group; R3 represents a hydrogen atom, a C1-6 hydrocarbyl group, or a C1-6 hydrocarbyloxy group; R4 is -CF2CH3 or -CH2CHF2; and R is, in each occurrence, the same or different and is a hydrogen atom, an alkyl group, or an aryl group.] A method for producing a compound represented by Formula (2): 【Chemical Formula 4】 [The symbols in the formula have the same meanings as described above.] reacting a compound represented by with vinylidene fluoride under light irradiation, comprising Step A A production method.

4. At least a part of vinylidene fluoride is introduced into the liquid containing the compound represented by Formula (2) in the form of fine bubbles containing the same The production method according to any one of Claims 1 to 3.

5. The form of the fine bubbles is such that the ratio of the number of bubbles having a particle diameter in the range of 5 nm to 100 μm to the total number of the bubbles is 90% or more The production method according to Claim 4.

6. The ratio of the volume of the gas containing vinylidene fluoride to the volume of the liquid containing the compound represented by Formula (2) is in the range of 0.01 to 1 The production method according to Claim 4.

7. The reaction temperature of Step A is 130°C or lower The production method according to any one of Claims 1 to 6.

8. The light in Step A contains ultraviolet rays The production method according to any one of Claims 1 to 7.

9. Formula (1): 【Chemical Formula 5】 [wherein, X represents -O-; R １ represents an alkyl group which may have one or more substituents selected from the group consisting of a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO ２ R, -SOR, -OP(=O)(OR) ２ , and -OR; R ２ represents an alkoxy group; R ３ represents an alkoxy group; and R ４ represents -CF ２ CH ３ or -CH ２ CHF ２ and; R is, in each occurrence, the same or different and is a hydrogen atom, an alkyl group, or an aryl group.] A compound represented by

10. Formula (1): 【Chemical Formula 6】 [wherein, X represents -O-; R １ and R ２ together with X and one carbon atom to which they are respectively adjacent form a 1,3-dioxolane ring having no substituent; R ３ represents a hydrogen atom, a C1-6 hydrocarbyl group, or a C1-6 hydrocarbyloxy group; and R ４ represents -CF ２ CH ３ , or -CH ２ CHF ２ .] The compound represented by

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