Method for manufacturing organic compound

Abstract

To provide a method for manufacturing an organic compound, etc., in the present disclosure.SOLUTION: A vinylidene fluoride-containing composition is used as a raw material for manufacturing a hetero atom-containing organic compound under light irradiation. The composition includes (1) vinylidene fluoride and (2) a liquid medium, and at least a part of the vinylidene fluoride is dispersed as fine bubbles in the liquid medium (except for the case where the composition contains a basic compound).SELECTED DRAWING: None

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). The present disclosure aims 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):

Chem.

Chem.

Chemical formula

Advantages of the Invention

[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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Mode for Carrying Out the Invention

[0009] Term Unless otherwise specified, the symbols and abbreviations in this specification can be understood in the meaning commonly used in the technical field to which the present invention belongs in accordance with the context of this specification. In this specification, the phrase "containing" is used with the intention of including the phrases "consisting essentially of" and "consisting of". Unless otherwise specifically limited, 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 numbers respectively) represents that the number of carbon atoms is n or more and m or less, as is commonly understood by those skilled in the art.

[0010] As those skilled in the art will understand based on common general knowledge in the art, in this specification, the terms "content" and "purity" can be used interchangeably depending on the context.

[0011] According to the definition of the International Organization for Standardization (ISO) Fine Bubble Technology Technical Committee (2013), in this specification, "fine bubble" means a bubble with a diameter of 100 μm or less, and each of which is included in the "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 specified, the "organic group" means a group containing one or more carbon atoms as its constituent atoms. In this specification, unless otherwise specified, the "monovalent organic group" includes a hydrocarbyl group. In this specification, unless otherwise specified, 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 a group containing an ether bond), an acyl group, and a heterocyclyl group (e.g., a heteroaryl group and a non-aromatic heterocyclic group). The "organic group" can be, for example, a monovalent organic group. In this specification, unless otherwise specified, examples of the "monovalent organic group" include a hydrocarbyl group.

[0014] In this specification, unless otherwise specified, 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" can also be referred to as a "hydrocarbon group". As used herein, unless otherwise specifically limited, the "hydrocarbyl group" includes an aliphatic hydrocarbyl group (e.g., benzyl group) which may be substituted with one or more aromatic hydrocarbyl groups, and an aromatic hydrocarbyl group (aryl group) which may be substituted with one or more aliphatic hydrocarbyl groups. As used herein, unless otherwise specifically limited, the "aliphatic hydrocarbyl group" can be linear, branched, cyclic, or a combination thereof. As used herein, unless otherwise specifically limited, the "aliphatic hydrocarbyl group" can be saturated or unsaturated. As used herein, unless otherwise specifically limited, examples of the "aliphatic hydrocarbyl group" include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group. As used herein, unless otherwise specifically 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. As used herein, unless otherwise specifically 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. As used herein, unless otherwise specifically 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 a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. In this specification, unless otherwise particularly limited, examples of the "aromatic hydrocarbyl group (aryl group)" include a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, and a 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: RCO2- (wherein R is an alkyl group) in the formula, and the formula: R a -CO2-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 a polyether group. Examples of the polyether group include a group represented by the formula: R a -(O-R b ) n -(wherein R a is an alkyl group, R b is the same or different at each occurrence and is an alkylene group, and n is an integer of 1 or more.) in the formula. The alkylene group is a divalent group formed by removing one hydrogen atom from the alkyl group. Examples of an "ether group" or an "ether bond-containing group" also include a hydrocarbyl ether group. 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 a hydrocarbyloxy group (e.g., a benzyloxy group). Examples of the "hydrocarbyl group having one or more ether bonds" include an alkyl group 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 particularly limited, the "acyl group" includes an alkanoyl group. In the present specification, unless otherwise particularly limited, the "alkanoyl group" is, for example, a group represented by RCO- (wherein R is an alkyl group).

[0018] In the present specification, unless otherwise particularly limited, examples of the "heteroaryl group" include a 5- or 6-membered heteroaryl group and a group condensed with a benzene ring thereof. 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 the 5-membered heteroaryl group 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, and 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, and 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 an alkyl group or an aryl group, each optionally having 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, -SO2R, -SOR, -OP(=O)(OR)2, and -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 optionally having one or more substituents or an aryl group optionally having one or more substituents thereof.

[0029] R 2 is preferably a hydrogen atom, or an alkyl group or an aryl group, each optionally having 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, -SO2R, -SOR, -OP(=O)(OR)2, and -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 such that together with X and one carbon atom to which they are each adjacent, they form a heterocycle optionally having 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. Suitable examples of the substituents that the heterocycle may have include an alkyl group, an aryl group, a heteroaryl group, a keto group, a nitrilo group, a nitro group, a halogen group, -SO2R, -SOR, -OP(=O)(OR)2, and -OR.

[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 -CF2CH3, or -CH2CHF2 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 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 a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO2R, -SOR, -OP(=O)(OR)2, and -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).] is R 2 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 which may have one or more substituents [Preferably a hydrogen atom, or 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 a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group (preferably a C6-C10 aryl group), -SO2R, -SOR, -OP(=O)(OR)2, and -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 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 a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO2R, -SOR, -OP(=O)(OR)2, and -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 together with X and one carbon atom to which they are each adjacent, they 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 a hydrocarbyloxy; and more preferably a hydrogen atom, a C1-C10 hydrocarbyl group, or a C1-C10 hydrocarbyloxy); R 4 is -CF2CH3, or -CH2CHF2 is. Suitable examples of compound (2) include dioxolane (e.g., 1,3-dioxolane), methyl orthoformate, and ethyl orthoformate.

[0034] Process A The reaction of Project A can be carried out, for example, by bringing a gas containing vinylidene fluoride into contact with a liquid containing 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 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 of Project 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 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 [Examples: pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, n-decane, isododecane, tridecane]; Aromatic hydrocarbon solvents [Examples: benzene, toluene, xylene, tetralin, veratrole, ethylbenzene, diethylbenzene, methylnaphthalene, anisole, phenetole, nitrobenzene, o-nitrotoluene, mesitylene, indene, diphenyl sulfide, anisole, propiophenone]; Ketone solvents [Examples: acetone, methyl ethyl ketone, diethyl ketone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, acetonylacetone, methylhexanone, acetophenone, cyclohexanone, diacetone alcohol, propiophenone, isophorone]; Halogenated hydrocarbon solvents [Examples: dichloromethane, chloroform, chlorobenzene]; Ether solvents [Examples: 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 [Examples: 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 [Examples: acetonitrile, benzonitrile]; Sulfoxide solvents [Examples: dimethyl sulfoxide, sulfolane]; and Amide solvents [Examples: 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 Two or more combinations 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] It is preferable that the ratio of vinylidene fluoride introduced in the form of fine bubbles to the total vinylidene fluoride introduced into the liquid is 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 (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) are exemplified. In the method of the present disclosure, the fine bubbles may be generated by adopting any of these methods and using a fine bubble generator. The fine bubble generator can have, for example, a function of injecting a gas into a liquid and applying a shearing force to the resulting gas / liquid mixture flow with a static mixer to repeatedly divide the liquid to create fine bubbles in the liquid. Examples of the method of generating fine bubbles include a pressure 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 vinylidene fluoride gas to the reaction system in step A can be determined in consideration of the size of the reaction vessel, light transmittance, the capacity of the bubble generator, etc. Specifically, for example, per minute, with respect to the volume of the reaction solution in the reaction system, A gas of vinylidene fluoride in an amount of usually 1 to 99 vol%, preferably 5 to 80 vol%, more preferably 10 to 50 vol% may be supplied.

[0041] The fine bubbles are preferably ultrafine bubbles. In the present specification, the "ultrafine bubbles" refer to bubbles having 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 (from PMS)]. A preferred form of the fine bubbles is with respect to the total number of bubbles of the gas, 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.

[0042] The particle diameter, number, distribution, and average particle diameter 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 a laser beam. The measurement can be carried out using a commercially available device, NanoSight LM-10 (from NanoSight) or its equivalent. However, if accurate measurement cannot be performed by the nanoparticle tracking analysis method, it may be measured by another method. As such another method, (1) A method using a particle sensor PS100 (product name, Beidou Electronic Industry) or its equivalent as a method for measuring the diameter of nanobubbles, and (2) As a method for measuring the diameters of both microbubbles and nanobubbles, a method using a Shimadzu nanoparticle size distribution analyzer SALD-7100 (product name, Shimadzu Corporation) or its equivalent, and (3) A method of carrying out a combination of these measurement methods may 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 in step A is carried out under light irradiation. As the irradiation light used for the light irradiation, for example, any light that can initiate and / or promote the reaction in 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 the light irradiation only needs to be such that energy capable of initiating and / or promoting the reaction in step A is supplied, and this can be appropriately adjusted, for example, based on common general knowledge so that the reaction in step A proceeds appropriately, by adjusting the output of the light source, the distance between the light source and the reaction system in step A, etc.

[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 of 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 and can be. The reaction temperature of 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, and can be. Also, the reaction of Step A can preferably be carried out at room temperature. Due to being at the reaction temperature, there is a risk that the reaction of Step A becomes insufficient. If the reaction temperature is too high, it is disadvantageous in terms of cost and there is a risk that undesirable reactions occur. The lower the upper limit of the reaction temperature of Step A, the more likely it is to suppress side reactions. The higher the lower limit of the reaction temperature of Step A, the more likely it is to promote the progress of the target reaction.

[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 and can be. The upper limit of the amount is, based on 1 mol of compound (2), preferably 10 mol, more preferably 5 mol, and even more preferably 3 mol and can be. The amount is, based on 1 mol of compound (2), Preferably within the range of 0.001 to 10 moles, more preferably within the range of 0.002 to 5 moles, and even more preferably within the range of 0.003 to 3 moles can be. By carrying out the reaction with such an amount, the target product can be efficiently obtained.

[0047] The light in the step A preferably contains ultraviolet rays. The ultraviolet rays are preferably ultraviolet rays having a main wavelength within the range of 200 nm to 400 nm, more preferably 220 nm to 350 nm. The light in the step A may contain light other than the ultraviolet rays. The irradiation of the 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 in 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, it preferably reaches a light irradiation density of 10 W / m 2 or more The upper limit of the light irradiation density can be, for example, 1000 W / m 2 , 700 W / m 2 , 500 W / m 2 2 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, can be within the range of.

[0049] The lower limit of the reaction time of the said step A is, preferably 0.5 hours, more preferably 1 hour, and even more preferably 1.5 hours can be. The upper limit of the reaction time of the said step A is, preferably 72 hours, more preferably 48 hours, and even more preferably 24 hours can be. The reaction time of the said step 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 can be. If the reaction time is too short, there is a risk that the reaction of step A will be insufficient. If the reaction time is too long, it is disadvantageous in terms of cost and there is a risk that undesirable reactions will occur.

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

[0051] The reaction of step 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 said reaction initiator (e.g., radical reaction initiator) are, α-diketone compounds (e.g., benzyl, 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, trihalomethylphenylsulfone), 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 can be in the range of, preferably 0.00001 - 10 moles, more preferably 0.0001 - 1 mole, and even more preferably 0.001 - 0.1 mole with respect to 100 moles of vinylidene fluoride.

[0052] Examples of the “photosensitizer” are, 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, a styryl compound or a quinoline compound, or a coumarin compound is preferred. Specific examples of the styryl compound or the quinoline compound 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 comprising.

[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 even 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 is Formula (1):

Chemical formula

[0057] Composition The vinylidene fluoride-containing composition of the present disclosure (1) 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 size in the range of 5 nm to 100 μm to the total number of gas bubbles 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 formula (2) is usually in the range of 0.01 to 1; Preferably, it is in the range of 0.02 to 0.9; More preferably, it is in the range of 0.05 to 0.8; and Even more preferably, it is in 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) containing 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 above "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 gas bubbles is 90% or more. Other forms or more preferred embodiments of this form can be understood with reference 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. As for the aspect of the "fluorinated olefin-containing composition (excluding vinylidene fluoride)", those skilled in the art can understand it 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 decompressed to generate microbubbles of the solute gas in the solvent. As another method, there is a gas-liquid shearing method, that is, a method in which a solute gas is supplied to a vortex of a solvent, the solute gas is sheared in the solvent, and fine bubbles of the solute gas are generated in the solvent. The fine bubbles of the composition can be generated using a device 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 measurement of the particle size, number, distribution, and average particle size of the microbubbles can be carried out by the above-described method.

[0076] Although the embodiments have been described above, it will be understood that various changes in form and details can be made 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 Fig. 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. Subsequently, 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 with 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, when the solution was analyzed by F-NMR, 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. Subsequently, 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 with 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, when the solution was analyzed by F-NMR, an adduct was obtained in a yield of 44%. The production ratio is shown in Table 1.

[0082] (Example 3) It 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 TIFF2025094051000017.tif251432 - A mixed solution of (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. Under irradiation with a 100W mercury lamp, while circulating the solution at a rate of 30 mL / min, hexafluoropropene was introduced as fine bubbles. After 2 hours, when the solution was analyzed by F - NMR, bis - 2,5 - (2H - hexafluoropropyl)tetrahydrofuran was obtained in a 90% yield.

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

[0089] (Example 11) The experiment was carried out in the same manner as in Example 1 except that the apparatus was replaced with the one equipped with a ceramic filter whose outline is shown in Fig. 3, and an adduct was obtained in a 3% yield. The production 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 by 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-course 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, Kantam 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-course 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 hour, the number and concentration of ultrafine bubbles were measured after 0, 1, 2, 4, 8, 24, 48, and 168 hours. The results are shown in FIGS. 25 to 33.

Claims

1. Formula (1): 【Chemistry 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 each of which may be joined together with the adjacent X and one carbon atom to form a heterocycle 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 It is.] A method for producing a compound represented by the following formula: Formula (2): 【Chemistry 2】 [The symbols in the formula are as defined above.] The compound represented by The method includes a step A of reacting with vinylidene fluoride under light irradiation, Manufacturing method.

2. X is -O-; The method of claim 1 .

3. R １ but, 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 method according to claim 1 or 2.

4. R １ but, A hydrogen atom, or Keto group, nitrilo group, nitro group, halogen group, aryl group, -SO ２ R, -SOR, -OP (=O) (OR) ２ an alkyl group or an aryl group, each of which may have one or more substituents selected from the group consisting of -OR; R, in each occurrence, is the same or different and is a hydrogen atom, an alkyl group, or an aryl group; The method according to claim 3.

5. R ２ but, 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. That is, The method according to any one of claims 1 to 4.

6. R ２ but, A hydrogen atom, or Keto group, nitrilo group, nitro group, halogen group, aryl group, -SO ２ R, -SOR, -OP (=O) (OR) ２ an alkyl group or an aryl group, which may have one or more substituents selected from the group consisting of -OR, and R, in each occurrence, is the same or different and is a hydrogen atom, an alkyl group, or an aryl group; The method according to claim 5 .

7. R １ and R ２ each of which, together with the adjacent X and one carbon atom, forms a heterocycle which may have one or more substituents; The method according to any one of claims 1 to 6.

8. R ３ but, Hydrogen atoms, a hydrocarbyl group, or Hydrocarbyloxy group That is, The method according to any one of claims 1 to 7.

9. R ４ But -CF ２ CH ３ , or -CH ２ CHF ２ That is, The method according to any one of claims 1 to 8.

10. At least a part of vinylidene fluoride is introduced in the form of fine bubbles containing the vinylidene fluoride into the liquid containing the compound represented by formula (2). The method according to any one of claims 1 to 9.

11. The morphology of the fine bubbles is such that the ratio of the number of bubbles having a particle size within a range of 5 nm to 100 μm to the total number of the gas bubbles is 90% or more. The method of claim 10.

12. 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 within the range of 0.01 to 1; The method according to any one of claims 1 to 11.

13. The reaction temperature in step A is 130° C. or less. The method according to any one of claims 1 to 12.

14. The light in step A contains ultraviolet light. The method according to any one of claims 1 to 13.

15. Formula (1): 【Chemistry 3】 [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 each of which may be joined together with the adjacent X and one carbon atom to form a heterocycle 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 represents.] A compound represented by the formula (excluding 3,3-difluoro-2-methyl-2-butanol and 4,4-difluoro-2-methyl-2-butanol).

16. 1. A vinylidene fluoride-containing composition comprising: (1) vinylidene fluoride, and (2) containing a liquid medium; and The composition, wherein at least a portion of said vinylidene fluoride is dispersed as fine bubbles in said liquid medium.

17. The vinylidene fluoride-containing composition according to claim 16, wherein the liquid medium is a liquid medium containing at least one selected from the group consisting of water and organic solvents that are poor solvents for vinylidene fluoride.

18. The composition according to claim 16 or 17, wherein the morphology of the fine bubbles is such that the ratio of the number of bubbles having a particle size within a range of 5 nm to 100 μm to the total number of the gas bubbles is 90% or more.

19. A fluorine-containing olefin-containing composition comprising: (1) Fluorine-containing olefins (excluding vinylidene fluoride), and (2) containing a liquid medium; and A composition, wherein at least a portion of said fluorine-containing olefin is dispersed in said liquid medium as fine bubbles.

20. The fluorine-containing olefin is Formula (3): 【Chemistry 4】 [In the formula, R ａ１ , R ａ２ , R ａ３ , and R ａ４ are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, or a fluoroalkyl group. ａ１ , R ａ２ , R ａ３ , and R ａ４ At least one of these is a fluorine atom. The fluorine-containing olefin-containing composition according to claim 19, wherein the compound is represented by the formula:

21. The fluorine-containing olefin-containing composition according to claim 19 or 20, wherein the liquid medium contains one or more selected from the group consisting of water and organic solvents that are poor solvents for the fluorine-containing olefin represented by formula (3) (excluding vinylidene fluoride).

22. The composition according to any one of claims 19 to 21, wherein the morphology of the fine bubbles is such that a ratio of the number of bubbles having a particle size within a range of 5 nm to 100 µm to the total number of the gas bubbles is 90% or more.

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