阅读说明：本技术 有机化合物的制造方法 (Method for producing organic compound ) 是由 白井淳 黑木克亲 间濑畅之 于 2020-02-07 设计创作，主要内容包括：本发明的目的在于,提供一种有机化合物的制造方法等。该目的通过下述制造方法解决：一种式(1)所示的化合物的制造方法：[式(1)中,X表示-O-、可具有取代基的亚胺基、或-S-,R～1表示氢原子、或可具有1个以上的取代基的烃基,且R～2表示氢原子或1价有机基团；或者,R～1和R～2可以与它们各自相邻的X和1个碳原子一起形成可具有1个以上的取代基的杂环,R～3表示氢原子或1价有机基团,和R～4为-CF-2CH-3或-CH-2CHF-2。],所述制造方法包括：步骤A,其中,使式(2)所示的化合物在光照射下与偏二氟乙烯反应：[式(2)中的标记与前述表示相同含义。]。(An object of the present invention is to provide a method for producing an organic compound. This object is solved by the following production method: a station of formula (1)A process for producing the compound shown below: [ in the formula (1), X represents-O-, an optionally substituted imino group, or-S-, R 1 Represents a hydrogen atom or a hydrocarbon group which may have 1 or more substituents, and R 2 Represents a hydrogen atom or a 1-valent organic group; or, R 1 And R 2 May form a heterocyclic ring which may have 1 or more substituents together with X and 1 carbon atom adjacent to each of them, R 3 Represents a hydrogen atom or a 1-valent organic group, and R 4 is-CF 2 CH 3 or-CH 2 CHF 2 。]The manufacturing method comprises the following steps: a step a in which a compound represented by formula (2) is reacted with vinylidene fluoride under irradiation with light:)

1. A method for producing a compound represented by the formula (1):

in the formula (1), the reaction mixture is,

x represents-O-, an imino group with or without a substituent, or-S-,

R¹represents a hydrogen atom or a hydrocarbon group having 1 or more substituents, and R²Represents a hydrogen atom or a 1-valent organic group; or, R¹And R²Together with their respective adjacent X and 1 carbon atom form a heterocyclic ring with or without 1 or more substituents,

R³represents a hydrogen atom or a 1-valent organic group, and

R⁴is-CF₂CH₃or-CH₂CHF₂，

The manufacturing method comprises the following steps:

a step a of reacting a compound represented by formula (2) with vinylidene fluoride under light irradiation:

the symbols in formula (2) have the same meanings as those described above.

2. The production process according to claim 1, wherein X is-O-.

3. The manufacturing method according to claim 1 or 2,

R¹comprises the following steps:

a hydrogen atom, or

An alkyl group having or not having 1 or more substituents, or

An aryl or heteroaryl group with or without 1 or more substituents.

4. The manufacturing method according to claim 3,

R¹comprises the following steps: a hydrogen atom; or each with or without groups selected from keto, nitrilo, nitro, halo, aryl, -SO₂R、-SOR、-OP(＝O)(OR)₂And alkyl OR aryl of 1 OR more substituents of-OR, and

r, which is the same or different at each occurrence, is a hydrogen atom, an alkyl group or an aryl group.

5. The production method according to any one of claims 1 to 4,

R²comprises the following steps:

a hydrogen atom; or

An alkyl group having 1 or more substituents; or

An aryl group having 1 or more substituents.

6. The manufacturing method according to claim 5,

R²comprises the following steps: a hydrogen atom; or with or without groups selected from keto, nitrilo, nitro, halo, aryl, -SO₂R、-SOR、-OP(＝O)(OR)₂And alkyl OR aryl of 1 OR more substituents of-OR, and

r, which is the same or different at each occurrence, is a hydrogen atom, an alkyl group or an aryl group.

7. The production method according to any one of claims 1 to 6, wherein R is¹And R²Together with their respective adjacent X and 1 carbon atom form a heterocyclic ring with or without 1 or more substituents.

8. The production method according to any one of claims 1 to 7,

R³comprises the following steps:

a hydrogen atom,

A hydrocarbon group, or

A hydrocarbyloxy group.

9. The production method according to any one of claims 1 to 8, wherein R is⁴is-CF₂CH₃or-CH₂CHF₂。

10. The production method according to any one of claims 1 to 9, wherein 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 vinylidene fluoride.

11. The production method according to claim 10, wherein the fine bubbles have a particle diameter in a range of 5nm to 100 μm, and a proportion of the number of bubbles to the total number of bubbles in the gas is 90% or more.

12. The production method according to any one of claims 1 to 11, wherein a ratio of a volume of a vinylidene fluoride-containing gas to a volume of a liquid containing the compound represented by the formula (2) is in a range of 0.01 to 1.

13. The production method according to any one of claims 1 to 12, wherein the reaction temperature in the step A is 130 ℃ or lower.

14. The production method according to any one of claims 1 to 13, wherein the light in the step A contains ultraviolet rays.

15. A compound represented by the formula (1):

in the formula (1), the reaction mixture is,

x represents-O-, an imino group with or without a substituent, or-S-,

R¹represents a hydrogen atom or a hydrocarbon group having 1 or more substituents, and R²Represents a hydrogen atom or a 1-valent organic group; or, R¹And R²Together with their respective adjacent X and 1 carbon atom form a heterocyclic ring with or without 1 or more substituents,

R³represents a hydrogen atom or a 1-valent organic group, and

R⁴represents-CF₂CH₃or-CH₂CHF₂，

Wherein the content of the first and second substances,

the compounds do not include 3, 3-difluoro-2-methyl-2-butanol and 4, 4-difluoro-2-methyl-2-butanol.

16. A vinylidene fluoride-containing composition comprising:

(1) vinylidene fluoride, and

(2) the liquid medium is a mixture of a liquid medium,

and the number of the first and second electrodes,

at least a portion of the vinylidene fluoride is dispersed as fine bubbles in the liquid medium.

17. The vinylidene fluoride-containing composition of claim 16, wherein the liquid medium is a liquid medium comprising one or more selected from the group consisting of water and an organic solvent that is a lean solvent for vinylidene fluoride.

18. The composition according to claim 16 or 17, wherein the fine bubbles have a particle diameter in the range of 5nm to 100 μm, and the proportion of the number of bubbles to the total number of bubbles in the gas is 90% or more.

19. A fluoroolefin-containing composition comprising:

(1) a fluorine-containing olefin other than vinylidene fluoride, and

(2) the liquid medium is a mixture of a liquid medium,

and the number of the first and second electrodes,

at least a portion of the fluorine-containing olefin is dispersed as fine bubbles in the liquid medium.

20. The composition containing a fluorine-containing olefin according to claim 19, wherein the fluorine-containing olefin is a compound represented by formula (3):

in the formula (3), R^a1、R^a2、R^a3And R^a4The same or different, represent a hydrogen atom, a fluorine atom, a chlorine atom, or a fluoroalkyl group; wherein R is^a1、R^a2、R^a3And R^a4At least 1 of them being fluorine atoms.

21. The fluoroolefin-containing composition according to claim 19 or 20, wherein the liquid medium is a liquid medium containing one or more selected from water and organic solvents which are poor solvents of the fluoroolefin represented by the formula (3) except vinylidene fluoride.

22. The composition according to any one of claims 19 to 21, wherein the fine bubbles have a form in which the ratio of the number of bubbles having a particle diameter in the range of 5nm to 100 μm to the total number of bubbles in the gas is 90% or more.

Technical Field

The present invention relates to a method for producing an organic compound (specifically, a method for producing a heteroatom-containing organic compound, and more specifically, a method for producing a heteroatom-containing organic compound under irradiation with light), and the like.

Background

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 irradiation with light), for example, non-patent document 1 reports 1- (polyfluoroalkyl) ethane-1, 2-diol produced under irradiation with UV.

Documents of the prior art

Non-patent document

Non-patent document 1: vladimir Cirkva et al, Journal of Fluorine Chemistry 94(1999), p.141-156

Disclosure of Invention

Technical problem to be solved by the invention

There is a need in the art to provide 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 irradiation with light).

An object of the present invention 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 irradiation with light), and the like.

Means for solving the problems

The present invention provides the following means for solving the above-described problems.

Item 1.

A method for producing a compound represented by the formula (1):

[ CHEM 1 ]

[ in the formula,

x represents-O-, an imino group which may have a substituent, or-S-,

R¹represents a hydrogen atom or a hydrocarbon group which may have 1 or more substituents, and R²Represents a hydrogen atom or a 1-valent organic group; or, R¹And R²May form a heterocyclic ring which may have 1 or more substituents together with their respective adjacent X and 1 carbon atom,

R³represents a hydrogen atom or a 1-valent organic group, and

R⁴is-CF₂CH₃or-CH₂CHF₂。]

The manufacturing method comprises the following steps:

a step a of reacting a compound represented by formula (2) with vinylidene fluoride under light irradiation:

[ CHEM 2 ]

[ in the formula, the symbols have the same meanings as described above. ].

Item 2.

The production process according to item 1, wherein X is-O-.

Item 3.

The production method according to item 1 or 2, wherein,

R¹comprises the following steps:

a hydrogen atom, or

An alkyl group which may have 1 or more substituents, or

An aryl or heteroaryl group which may have 1 or more substituents.

Item 4.

The manufacturing method according to item 3, wherein,

R¹comprises the following steps:

a hydrogen atom, or

Each of which may have a substituent selected from the group consisting of keto, nitrilo, nitro, halo, aryl, -SO₂R、-SOR、-OP(＝O)(OR)₂And alkyl OR aryl of 1 OR more substituents of-OR, and

r, which is the same or different at each occurrence, is a hydrogen atom, an alkyl group or an aryl group.

Item 5.

The production method according to any one of items 1 to 4, wherein,

R²comprises the following steps:

a hydrogen atom, or

An alkyl group which may have 1 or more substituents, or an aryl group which may have 1 or more substituents.

Item 6.

The manufacturing method according to item 5, wherein,

R²comprises the following steps:

a hydrogen atom, or

May have a substituent selected from the group consisting of keto, nitrilo, nitro, halo, aryl, -SO₂R、-SOR、-OP(＝O)(OR)₂And alkyl OR aryl of 1 OR more substituents of-OR, and

r, which is the same or different at each occurrence, is a hydrogen atom, an alkyl group or an aryl group.

Item 7.

The production method according to any one of items 1 to 6, wherein R¹And R²Together with their respective adjacent X and 1 carbon atom, form a heterocyclic ring which may have 1 or more substituents.

Item 8.

The production method according to any one of items 1 to 7, wherein,

R³comprises the following steps:

a hydrogen atom,

A hydrocarbon group, or

A hydrocarbyloxy group.

Item 9.

The production method according to any one of claims 1 to 8, wherein R⁴is-CF₂CH₃or-CH₂CHF₂。

Item 10.

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

Item 11.

The production method according to item 10, wherein the fine bubbles have a particle diameter in a range of 5nm to 100 μm, and a proportion of the number of bubbles having a particle diameter to the total number of bubbles in the gas is 90% or more.

Item 12.

The production method according to any one of items 1 to 11, wherein a ratio of a volume of the vinylidene fluoride-containing gas to a volume of the liquid containing the compound represented by the formula (2) is in a range of 0.01 to 1.

Item 13.

The production method according to any one of claims 1 to 12, wherein the reaction temperature in the step A is 130 ℃ or lower.

Item 14.

The production method according to any one of claims 1 to 13, wherein the light in the step A contains ultraviolet rays.

Item 15.

A compound represented by the formula (1) (wherein 3, 3-difluoro-2-methyl-2-butanol and 4, 4-difluoro-2-methyl-2-butanol are excluded):

[ CHEM 3 ]

[ in the formula,

x represents-O-, an imino group which may have a substituent, or-S-,

R¹represents a hydrogen atom or a hydrocarbon group which may have 1 or more substituents, and R²Represents a hydrogen atom or a 1-valent organic group; or, R¹And R²May form a heterocyclic ring which may have 1 or more substituents together with their respective adjacent X and 1 carbon atom,

R³represents a hydrogen atom or a 1-valent organic group, and

R⁴represents-CF₂CH₃or-CH₂CHF₂。]。

Item 16.

A vinylidene fluoride-containing composition comprising

(1) Vinylidene fluoride, and

(2) the liquid medium is a mixture of a liquid medium,

and the number of the first and second electrodes,

at least a portion of the vinylidene fluoride is dispersed as fine bubbles in the liquid medium.

Item 17.

The vinylidene fluoride-containing composition according to item 16, wherein the liquid medium is a liquid medium containing one or more selected from water and an organic solvent which is a lean solvent for vinylidene fluoride.

Item 18.

The composition according to item 16 or 17, wherein the fine bubbles have a particle diameter in a range of 5nm to 100 μm, and a proportion of the number of bubbles to the total number of bubbles in the gas is 90% or more.

Item 19.

A composition comprising a fluoroolefin comprising

(1) A fluorine-containing olefin (excluding vinylidene fluoride), and

(2) the liquid medium is a mixture of a liquid medium,

and the number of the first and second electrodes,

at least a portion of the fluorine-containing olefin is dispersed as fine bubbles in the liquid medium.

Item 20.

The fluoroolefin-containing composition according to item 19, wherein the fluoroolefin is

A compound represented by the formula (3):

[ CHEM 4 ]

[ in the formula, R^a1、R^a2、R^a3And R^a4The same or different, represent a hydrogen atom, a fluorine atom, a chlorine atom or a fluoroalkyl group; wherein R is^a1、R^a2、R^a3And R^a4At least 1 of them being fluorine atoms.]。

Item 21.

The fluoroolefin-containing composition according to item 19 or 20, wherein the liquid medium is a liquid medium containing one or more selected from water and an organic solvent which is a poor solvent for the fluoroolefin represented by the formula (3) except for vinylidene fluoride.

Item 22.

The composition according to any one of claims 19 to 21, wherein the fine bubbles have a form in which a ratio of the number of bubbles having a particle diameter in a range of 5nm to 100 μm to the total number of bubbles in the gas is 90% or more.

Effects of the invention

According to the present invention, there is provided a novel method for producing an organic compound (specifically, a method for producing a heteroatom-containing organic compound, more specifically, a novel method for producing a heteroatom-containing organic compound under irradiation with light).

Drawings

Fig. 1 is a diagram showing an outline of an apparatus used in the manufacturing method of the present invention (examples 1 to 9).

Fig. 2 is a diagram showing an outline of another apparatus used in the manufacturing method of the present invention (example 10).

Fig. 3 is a diagram showing an outline of another apparatus used in the manufacturing method of the present invention (example 11).

Fig. 4 is a graph showing the measurement results of the particle diameter and number of VdF fine bubbles in water as a liquid medium (example 12).

Fig. 5 is a graph showing the measurement results of the particle diameter and the number of VdF fine bubbles in isopropyl alcohol as a liquid medium (example 12).

FIG. 6 is a graph showing the measurement results of the particle diameter and number of VdF fine bubbles in 1, 3-dioxolane as a liquid medium (example 12).

Fig. 7 is a graph showing the measurement results of the particle diameter and the number of VdF fine bubbles in DMF as a liquid medium (example 12).

Fig. 8 is a graph showing the change in the number of nanobubbles in water with time (example 13).

Fig. 9 is a graph showing the change with time in the concentration of VdF in water (example 13).

Fig. 10 is a graph showing the change with time in the number of nanobubbles in isopropyl alcohol (example 13).

Fig. 11 is a graph showing the change with time in the concentration of VdF in isopropyl alcohol (example 13).

Fig. 12 is a graph showing the change with time in the number of nanobubbles in 1, 3-dioxolane (example 13).

Fig. 13 is a graph showing the change with time in the concentration of VdF in 1, 3-dioxolane (example 13).

Fig. 14 is a graph showing the temporal change in the number of nanobubbles in DMF (example 13).

Fig. 15 is a graph showing the change with time in the concentration of VdF in DMF (example 13).

FIG. 16 is a graph showing the measurement results of the particle diameter and the number of 2,3,3, 3-tetrafluoropropene fine bubbles in 1, 3-dioxolane (example 15).

FIG. 17 is a graph showing the measurement results of the particle diameter and the number of 2,3,3, 3-tetrafluoropropene fine bubbles in DMF.

FIG. 18 is a graph showing the measurement results of the particle diameter and the number of 2,3,3, 3-tetrafluoropropene fine bubbles in isopropanol (example 15).

FIG. 19 is a graph showing the measurement results of the particle diameter and the number of 2,3,3, 3-tetrafluoropropene fine bubbles in water (example 15).

FIG. 20 is a graph showing the measurement results of the particle diameter and number of hexafluoropropylene fine bubbles in 1, 3-dioxolane (example 15).

Fig. 21 is a graph showing the measurement results of the particle diameter and the number of hexafluoropropylene microbubbles in DMF (example 15).

Fig. 22 is a graph showing the measurement results of the particle diameter and the number of hexafluoropropylene fine bubbles in isopropyl alcohol (example 15).

Fig. 23 is a graph showing the measurement results of the particle diameter and the number of hexafluoropropylene fine bubbles in water (example 15).

FIG. 24 is a graph showing the results of measuring the particle diameter and number of 1-bromo-1-fluoroethylene fine bubbles in water (example 15).

Fig. 25 is a graph showing the change with time in the concentration of 2,3,3, 3-tetrafluoropropene in water, and a graph showing the change with time in the number of nanobubbles (example 16).

Fig. 26 is a graph showing the change with time in the concentration of 2,3,3, 3-tetrafluoropropene in isopropanol, and a graph showing the change with time in the number of nanobubbles (example 16).

Fig. 27 is a graph showing the change with time in the concentration of 2,3,3, 3-tetrafluoropropene in 1, 3-dioxolane and a graph showing the change with time in the number of nanobubbles (example 16).

Fig. 28 is a graph showing the change with time in the concentration of 2,3,3, 3-tetrafluoropropene in DMF, and a graph showing the change with time in the number of nanobubbles (example 16).

Fig. 29 is a graph showing the change with time in the concentration of hexafluoropropylene in water, and a graph showing the change with time in the number of nanobubbles (example 16).

Fig. 30 is a graph showing the change with time in the concentration of hexafluoropropylene in isopropyl alcohol, and a graph showing the change with time in the number of nanobubbles (example 16).

Fig. 31 is a graph showing the change with time in the concentration of hexafluoropropylene in 1, 3-dioxolane, and a graph showing the change with time in the number of nanobubbles (example 16).

Fig. 32 is a graph showing the change with time in the concentration of hexafluoropropylene in DMF, and a graph showing the change with time in the number of nanobubbles (example 16).

Fig. 33 is a graph showing the temporal change in the concentration of 1-bromo-1-fluoroethylene in water, and a graph showing the temporal change in the number of nanobubbles (example 16).

Detailed Description

Term(s) for

The terms "label" and "abbreviation" used herein shall be understood to mean those generally used in the art to which the present invention pertains, unless otherwise specified, in the context of the present specification.

In this specification, the phrase "including" is used in a sense including the phrase "substantially formed of … …" and the phrase "consisting of … …".

The steps, treatments, or operations described in the present specification may be performed at room temperature, unless otherwise specified.

In the present specification, the room temperature may be a temperature in the range of 10 to 40 ℃.

In the present specification, the expression "Cn-Cm" (here, n and m are each a number) means that the number of carbon atoms is n or more and m or less, as is generally understood by those skilled in the art.

As understood by those skilled in the art based on the common technical knowledge, the term "content" and the term "purity" in the present specification may be used interchangeably depending on the context.

According to the definition of the international organization for standardization (ISO) micro-bubble technical committee (2013):

in the present specification, "fine bubble (fine bubble)" means a bubble having a diameter of 100 μm or less, and

respectively included in the "minute bubbles

"micro-bubbles" means bubbles having a diameter of 1 to 100 μm, and

"Nanoflubble (ultra fine bubble)" means a bubble having a diameter of 1 μm or less.

In the present specification, examples of the "halogen atom" include fluorine, chlorine, bromine and iodine.

In the present specification, unless otherwise specified, "organic group" means a group containing 1 or more carbon atoms as its constituent atoms.

In the present specification, the "1-valent organic group" includes, without particular limitation, a hydrocarbon group.

In the present specification, examples of the organic group include, but are not particularly limited to, hydrocarbon groups, hydrocarbyloxy groups (e.g., alkoxy groups), ester groups, ether groups (or ether bond-containing groups), acyl groups, and heterocyclic groups (e.g., heteroaryl groups and non-aromatic heterocyclic groups).

The "organic group" may be, for example, a 1-valent organic group.

In the present specification, a hydrocarbon group is exemplified as the "1-valent organic group" without particular limitation.

In the present specification, unless otherwise specified, "hydrocarbyl group" refers to a group containing 1 or more carbon atoms and 1 or more hydrogen atoms as its constituent atoms. "hydrocarbyl" may also be referred to as "hydrocarbyl".

In the present specification, the "hydrocarbon group" includes, but is not limited to, aliphatic hydrocarbon groups (for example, benzyl groups) which may be substituted with 1 or more aromatic hydrocarbon groups, and aromatic hydrocarbon groups (aryl groups) which may be substituted with 1 or more aliphatic hydrocarbon groups.

In the present specification, the "aliphatic hydrocarbon group" may be linear, branched, cyclic, or a combination thereof, unless otherwise specified.

In the present specification, the "aliphatic hydrocarbon group" may be saturated or unsaturated, unless otherwise specified.

In the present specification, examples of the "aliphatic hydrocarbon group" include, but are not particularly limited to, an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group.

In the present specification, the "alkyl group" is not particularly limited, and examples thereof include straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl (e.g., propyl and isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl and tert-butyl), pentyl (e.g., n-pentyl, isopentyl and neopentyl) and hexyl.

In the present specification, the "alkenyl group" is not particularly limited, and examples thereof include straight-chain or branched alkenyl groups having 2 to 10 carbon atoms such as a vinyl group, 1-propenyl group, isopropenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-ethyl-1-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, and 5-hexenyl group.

In the present specification, the "alkynyl group" includes, but is not particularly limited to, straight-chain or branched-chain 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 groups.

In the present specification, the "cycloalkyl group" is not particularly limited, and examples thereof include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopentyl, cyclohexyl, and cycloheptyl groups.

In the present specification, examples of the "aromatic hydrocarbon group (aryl group)" include, but are not particularly limited to, phenyl, naphthyl, phenanthryl, anthryl and pyrenyl.

In the present specification, unless otherwise specified, "alkoxy" is, for example, a group represented by RO- (in the formula, R is an alkyl group).

In the present specification, without particular limitation, "ester group" refers to an organic group having an ester bond (i.e., -C (═ O) -O-, or-O-C (═ O) -). Examples thereof include the formula: RCO₂- (in the formula, R is an alkyl group), and formula (I): r^a-CO₂-R^b- (in the formula, R^aIs alkyl, and R^bIs alkylene).

In the present specification, the "ether group" or "ether bond-containing group" refers to a group having an ether bond (-O-) unless otherwise specified.

Examples of "ether groups" or "ether bond-containing groups" include polyether groups. Examples of polyether groups include those of the formula: r^a-(O-R^b)_n- (in the formula, R^aIs alkyl, R^bIdentical or different at each occurrence and is an alkylene group, n is an integer of 1 or more). Alkylene is a 2-valent group formed by removing 1 hydrogen atom from the alkyl group.

Examples of "ether groups" or "ether bond-containing groups" also include hydrocarbyl ether groups. The hydrocarbyl ether group refers to a hydrocarbyl group having 1 or more ether linkages in the interior and/or at the terminal (or linking site) of the group. The "hydrocarbon group having 1 or more ether bonds" may be a hydrocarbon group into which 1 or more ether bonds are inserted. Examples thereof include hydrocarbyloxy groups (e.g., benzyloxy).

Examples of the "hydrocarbon group having 1 or more ether bonds" include alkyl groups having 1 or more ether bonds. The "alkyl group having 1 or more ether bonds" may be an alkyl group into which 1 or more ether bonds are inserted. In this specification, such a group is sometimes referred to as an alkyl ether group.

In the present specification, unless otherwise specified, "acyl" includes alkanoyl. In the present specification, unless otherwise specified, "alkanoyl" may be, for example, a group represented by RCO- (in the formula, R is an alkyl group).

In the present specification, examples of the "heteroaryl group" include, without particular limitation, a 5-or 6-membered heteroaryl group and a group obtained by fusing the heteroaryl group with a benzene ring.

In the present specification, examples of the "5-or 6-membered monocyclic aromatic heterocyclic group" include, but are not limited to, 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 (for example: 1,2, 4-oxadiazol-3-yl, 1,2, 4-oxadiazol-5-yl), thiadiazolyl (for example: 1,2, 4-thiadiazol-3-yl, 1,2, 4-thiadiazol-5-yl), tetrazolyl, pyridyl (for example: 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridazinyl (e.g.: 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (for example: 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), pyrazinyl, and the like have 1 or more selected from oxygen, sulfur, and nitrogen (for example: 1,2, or 3) heteroatoms as ring-forming atoms.

In the present specification, unless otherwise specified, examples of the "heterocyclic ring" include 5-to 7-membered heterocyclic rings containing 1 to 4 hetero atoms selected from a nitrogen atom, a sulfur atom and an oxygen atom in addition to a carbon atom, and the like.

In the present specification, examples of the "heterocycle" include a non-aromatic heterocycle and an aromatic heterocycle unless otherwise specified.

In the present specification, unless otherwise specified, examples of the "5-to 7-membered heterocyclic ring containing 1 to 4 hetero atoms selected from a nitrogen atom, a sulfur atom and an oxygen atom in addition to a carbon atom" include pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, tetrahydropyran, morpholine, thiomorpholine, piperazine and hexamethyleneimine.

In the present specification, unless otherwise specified, examples of the "non-aromatic heterocyclic ring" include 3 to 8-membered non-aromatic heterocyclic rings, and specific examples thereof include oxetane, aziridine, oxetane, thietane, pyrrolidine, dihydrofuran, tetrahydrofuran, tetrahydrothiophene, imidazolidine, oxazolidine, isoxazoline, piperidine, dihydropyran, tetrahydropyran, tetrahydrothiopyran, morpholine, thiomorpholine, piperazine, dihydrooxazine, tetrahydrooxazine, dihydropyrimidine, tetrahydropyrimidine, azepane, oxepane, thiepanane, oxazepane, thiazepane, azazepane, azooctane, oxcyclooctane, thiacyclooctane, oxazepane, thiaazepane, and the like.

In the present specification, unless otherwise specified, examples of the aromatic heterocyclic ring include a 5-or 6-membered aromatic heterocyclic ring, and examples of the specific examples 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, triazine and the like.

Manufacturing method

The manufacturing method of the invention is

Formula (1):

[ CHEM 5 ]

[ in the formula,

x represents-O-, an imino group which may have a substituent, or-S-,

R¹represents a hydrogen atom or a hydrocarbon group which may have 1 or more substituents, and R²Represents a hydrogen atom or a 1-valent organic group; or, R¹And R²May form a heterocyclic ring which may have 1 or more substituents together with their respective adjacent X and 1 carbon atom,

R³represents a hydrogen atom or a 1-valent organic group, and

R⁴for the purpose ofCF₂CH₃or-CH₂CHF₂。]

A method for producing the compound, which comprises the following step A:

reacting formula (2):

[ CHEM 6 ]

[ in the formula, the symbols have the same meanings as described above ]

The compounds shown

React with vinylidene fluoride under light irradiation.

In the present specification, the compound represented by the formula (1) may be referred to as "the compound of the formula (1)" or "the compound (1)".

In the present specification, the compound represented by the formula (2) may be referred to as "the compound of the formula (2)" or "the compound (2)".

X is preferably-O-.

R¹Preferably, it is

A hydrogen atom, or

An alkyl group which may have 1 or more substituents, or an aryl group which may have 1 or more substituents.

R¹Preferably, it is

A hydrogen atom, or

Each of which may have a substituent selected from the group consisting of keto, nitrilo, nitro, halo, aryl, -SO₂R、-SOR、-OP(＝O)(OR)₂And alkyl OR aryl of 1 OR more substituents of-OR, and

r, which is the same or different at each occurrence, is a hydrogen atom or an alkyl group.

R²Preferably, it is

A hydrogen atom, or

An alkyl group which may have 1 or more substituents, or an aryl group which may have 1 or more substituents.

R²Preferably, it is

A hydrogen atom, or

May have a substituent selected from the group consisting of keto, nitrilo, nitro, halogen, aryl, -SO₂R、-SOR、-OP(＝O)(OR)₂And alkyl OR aryl of 1 OR more substituents of-OR, and

r, which is the same or different at each occurrence, is a hydrogen atom or an alkyl group.

R¹And R²Preferably, it is

Together with their respective adjacent X and 1 carbon atom, form a heterocyclic ring which may have 1 or more substituents.

Here, X is preferably-O-, i.e., the heterocycle is preferably an oxygen-containing heterocycle. The ring is preferably a 5-to 6-membered ring.

Suitable examples of the substituent which the heterocycle may have include alkyl, aryl, heteroaryl, keto, nitrilo, nitro, halogen, -SO₂R、-SOR、-OP(＝O)(OR)₂and-OR.

R³Preferably, it is

A hydrogen atom,

A hydrocarbon group, or

A hydrocarbyloxy group.

R³More preferably

A hydrogen atom,

C1-C6 hydrocarbon group, or

C1-C6 hydrocarbyloxy.

R⁴Preferably, it is

-CF₂CH₃or-CH₂CHF₂。

Preferably, the first and second electrodes are formed of a metal,

x is-O-, and

R¹is composed of

A hydrogen atom, or

An alkyl group which may have 1 or more substituents (preferably, a C1-C6 alkyl group), or an aryl group which may have 1 or more substituents (preferably, a C6-C10 aryl group)

[ preferably a hydrogen atom, or each of them may have a group selected from a ketone group, a nitrilo group, a nitro group, a halogen group, an aryl group, -SO₂R、-SOR、-OP(＝O)(OR)₂And an alkyl group (preferably C1-C6 alkyl group) OR an aryl group (preferably C6-C10 aryl group) of 1 OR more substituents of-OR, and

r, which is the same or different at each occurrence, is a hydrogen atom or an alkyl group (preferably a C1-C6 alkyl group).]，R²Is composed of

A hydrogen atom, or

An alkyl group which may have 1 or more substituents (preferably a C1-C6 alkyl group), or an aryl group which may have 1 or more substituents

[ preferably ] it is

A hydrogen atom, or may have a substituent selected from the group consisting of a ketone group, a nitrilo group, a nitro group, a halogen group, an aryl group (preferably a C6-C10 aryl group), -SO₂R、-SOR、-OP(＝O)(OR)₂And an alkyl group (preferably C1-C6 alkyl group) OR an aryl group (preferably C6-C10 aryl group) of 1 OR more substituents of-OR, and

r, which is the same or different at each occurrence, is a hydrogen atom or an alkyl group (preferably a C1-C6 alkyl group); more preferably

A hydrogen atom, or may have a substituent selected from the group consisting of a keto group, a nitrilo group, a nitro group, a halogen group, an aryl group and a-SO group₂R、-SOR、-OP(＝O)(OR)₂And an alkyl group (preferably C1-C6 alkyl group) OR an aryl group (preferably C6-C10 aryl group) of 1 OR more substituents of-OR, and

r is identical or different on each occurrence and is a hydrogen atom or an alkyl group (preferably a C1-C6 alkyl group) ],

alternatively, the first and second electrodes may be,

R¹and R²Preferably, it is

Together with their respective adjacent X and 1 carbon atom form a heterocyclic ring which may have more than 1 substituent:

R³is composed of

Hydrogen atom or 1-valent organic group

(preferably a hydrogen atom, a hydrocarbon group, or a hydrocarbon oxy group; and

more preferably a hydrogen atom, a C1-C10 hydrocarbon group, or a C1-C10 hydrocarbonoxy group);

R⁴is composed of

-CF₂CH₃or-CH₂CHF₂。

Suitable examples of compound (2) include dioxolanes (e.g., 1, 3-dioxolane), methyl orthoformate and ethyl orthoformate.

Step A

The reaction of step a may be carried out, for example, by contacting a vinylidene fluoride-containing gas with a liquid containing the compound (2).

The content ratio of vinylidene fluoride in the gas is preferably high, and specifically, for example, 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, for example

The method is carried out by introducing fine bubbles containing vinylidene fluoride into a liquid containing the compound (1).

The vinylidene fluoride content in the fine gas is preferably high, and specifically, for example, 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.

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

The liquid (i.e., the liquid medium of step A)

Preferably a lean solvent for vinylidene fluoride.

The liquid medium may be a liquid medium containing one or more selected from water and an organic solvent which is a lean solvent for vinylidene fluoride.

Specific examples of the liquid medium include:

water;

alcohol solvents [ for example: methanol, ethanol, n-propanol, isopropanol, 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 [ for example: pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, n-decane, isododecane, tridecane ];

aromatic hydrocarbon solvents [ for example: benzene, toluene, xylene, tetrahydronaphthalene, veratryl alcohol, ethylbenzene, diethylbenzene, methylnaphthalene, anisole, phenetole, nitrobenzene, o-nitrotoluene, mesitylene, indene, diphenyl sulfide, anisole, propiophenone ];

ketone solvents [ for example: acetone, methyl ethyl ketone, diethyl ketone, hexyl ketone, methyl isobutyl ketone, heptanone, diisobutyl ketone, acetonyl acetone, methyl hexyl ketone, acetophenone, cyclohexanone, diacetone alcohol, propiophenone, isophorone ];

halogenated hydrocarbon solvents [ for example: dichloromethane, chloroform, chlorobenzene ];

ether solvents [ for example: diethyl ether, Tetrahydrofuran (THF), diisopropyl ether, methyl tert-butyl ether (MTBE), dioxane, dimethoxyethane, diethylene glycol dimethyl ether, anisole, phenetole, 1-dimethoxycyclohexane, diisoamyl ether, cyclopentyl methyl ether (CPME), dioxolane, methyl orthoformate, ethyl orthoformate ];

ester solvents [ for example: ethyl acetate, isopropyl acetate, diethyl malonate, 3-methoxy-3-methylbutyl acetate, gamma-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, alpha-acetyl-gamma-butyrolactone ];

nitrile solvents [ for example: acetonitrile, benzonitrile ];

sulfoxide-based solvents [ for example: dimethylsulfoxide, sulfolane ]; and

amide solvents [ for example: n, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMF), N-methylpyrrolidone (NMP), 1, 3-dimethyl-2-imidazolidinone (DMI), N-dimethylacrylamide, N-Dimethylacetoacetamide (DMA), N-diethylformamide, N-diethylacetamide ]; and

combinations of 2 or more thereof.

Some or all of the reaction matrix of the aforementioned step a may also function as the liquid medium and, likewise, some or all of the liquid medium may also function as the reaction matrix.

The ratio of vinylidene fluoride introduced in the form of fine bubbles to the whole vinylidene fluoride introduced into the liquid is preferably large.

The fine bubbles may be generated by a method generally performed.

This method can be exemplified by

(a) A method using supersaturation (specifically, a method in which a sufficient amount of solute gas is dissolved by pressurizing the solute gas in a closed container containing a solvent, and then the solvent in which the solute gas is dissolved by pressurizing is depressurized to generate micro-bubbles of the solute gas in the solvent); and

(b) the gas-liquid shear method (i.e., a method in which a solute gas is supplied into a vortex of a solvent, and the solute gas is sheared in the solvent, thereby generating fine bubbles of the solute gas in the solvent).

The fine bubbles in the method of the present invention may be generated by any method or by using a fine bubble generator.

The fine bubble generating device may be, for example, a device having the following functions: a gas is injected into a liquid, and a shearing force is applied to the fluid of the gas/liquid mixture thus obtained by a static mixer, and the liquid is repeatedly cut, whereby fine bubbles are produced in the liquid.

Examples of the mode for generating fine bubbles include a pressure dissolution mode, a rotary flow mode, a static mixer mode, a cavitation mode, and a venturi mode.

The amount (or rate) of the vinylidene fluoride gas supplied to the reaction system in step a may be determined in consideration of the size of the reaction vessel, the light transmittance, the capacity of the bubble generation apparatus, and the like.

Specifically, for example, the vinylidene fluoride gas may be supplied in an amount of usually 1 to 99 vol%, preferably 5 to 80 vol%, and more preferably 10 to 50 vol% per 1 minute on average based on the volume of the reaction liquid in the reaction system.

The fine bubbles are preferably nanobubbles.

In the present specification, the term "nanobubble" refers to a bubble having a diameter of 1 μm or less, as defined by the international organization for standardization (ISO).

The nanobubbles may be obtained using a commercially available device [ for example: SMX554, SMX374, SMX115T, SMX115, ASG1, ASG2, MA3FS, MA3, MA5S, BA06S and AMB3 (all manufactured by HACK UFB Corp.), and FBG-OS Type1(PMS, Inc.) ].

Suitable forms of the fine bubbles are:

with respect to the total number of bubbles of the gas,

the ratio of the number of bubbles having a particle diameter in the range of 10nm to 1 μm is preferably such that

More than 90% of the form;

more preferably, the ratio of the number of bubbles having a particle diameter in the range of 50nm to 1 μm is

More than 90% of the form;

the ratio of the number of bubbles having a particle diameter in the range of 50nm to 500nm is

More than 90% of the above-mentioned compound.

The particle diameter and number of the fine bubbles, and their distribution and average particle diameter are measured by a method of measuring the brownian diffusion equivalent diameter on a number basis using a laser, that is, a nanoparticle tracking analysis method. This measurement can be carried out by a commercially available device, NanoSight LM-10(NanoSight corporation) or an instrument equivalent thereto.

However, when the measurement cannot be accurately performed by the nanoparticle tracking analysis method, the measurement may be performed by another method.

As such other methods, there may be mentioned

(1) As a method for measuring the diameter of the nano bubbles, a method using a particle sensor PS100 (product name; Beidou electronic industry) or an instrument equivalent thereto, and

(2) as a method for measuring the diameters of both the micro bubbles and the nano bubbles, a method using Shimadzu nano particle size distribution measuring apparatus SALD-7100 (product name; Shimadzu corporation) or an instrument equivalent thereto, and

(3) a method of combining these measurement methods.

The ratio of the volume of the vinylidene fluoride-containing gas to the volume of the liquid containing the compound (2) in the reaction system of the step A,

usually in the range of 0.01 to 1;

preferably in the range of 0.02-0.9;

more preferably in the range of 0.05 to 0.8; and

more preferably in the range of 0.1 to 0.5.

The reaction of step A is carried out under light irradiation.

The irradiation light used for the light irradiation is not particularly limited as long as it is, for example, light that can initiate and/or accelerate the reaction in step a. Examples of the light source include a low-pressure, medium-pressure, or high-pressure mercury lamp, a tungsten lamp, and a Light Emitting Diode (LED).

The irradiation light may be light suitably containing ultraviolet rays.

The initiation of light irradiation may be before, during, simultaneously with, or after the mixing.

The intensity of the light irradiation may be so high as to supply energy capable of initiating and/or accelerating the reaction of step a, and may be appropriately adjusted by adjusting the output of the light source, the distance between the light source and the reaction system of step a, and the like, for example, based on the general technical knowledge, so that the reaction of step a is appropriately performed.

The lower limit of the reaction temperature of step a may be:

preferably at-50 deg.C,

More preferably-10 deg.C,

More preferably at 0 deg.C,

More preferably 10 ℃, and

particularly preferably 20 deg.c.

The upper limit of the reaction temperature of step a may be:

preferably 130 deg.C,

More preferably at 100 deg.C,

More preferably 80 deg.C,

More preferably 50 ℃, and

particularly preferably 30 deg.c.

The reaction temperature of step a may be:

preferably in the range of-10 to 130℃,

More preferably in the range of 0 to 100℃,

More preferably in the range of 10 to 80 ℃ and

particularly preferably in the range of 10 to 50℃,

More preferably in the range of 10 to 30 ℃.

Furthermore, the reaction of step a may suitably be carried out at room temperature.

By setting the reaction temperature to a value that is equal to the reaction temperature,

the reaction in step A may become insufficient.

If the reaction temperature is too high, it is disadvantageous in terms of cost and may cause an undesirable reaction.

When the upper limit of the reaction temperature in step a is lower, side reactions tend to be suppressed.

When the lower limit of the reaction temperature in step a is higher, the progress of the target reaction tends to be promoted.

The lower limit of the amount of vinylidene fluoride in the reaction of step a may be, relative to 1 mole of the compound (2):

preferably 0.001 mol,

More preferably 0.002 mole, and

more preferably 0.003 mol.

The upper limit of the aforementioned amount may be, relative to 1 mole of compound (2):

preferably 10 moles,

More preferably 5 moles, and

more preferably 3 moles.

The aforementioned amount may be, relative to 1 mole 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

more preferably, the amount of the catalyst is in the range of 0.003 to 3 mol.

By carrying out the reaction in this amount, the target product can be obtained efficiently.

The light of step a is preferably:

contains ultraviolet rays.

The ultraviolet ray:

preferably in the range of from 200nm to 400nm, more preferably in the range of from 220nm to 350 nm.

The light of step a may contain light other than the ultraviolet rays.

The irradiation with light may be performed by using, for example, a mercury lamp (e.g., a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp), a UV-LED, an excimer lamp, or a combination thereof.

Preferably, the first and second electrodes are formed of a metal,

excelling inIs selected to be 0.01W/m²The above,

More preferably 0.1W/m²The above,

More preferably 1W/m²The above,

More preferably 10W/m²The above

Reaches at least a part of the reaction system of the step A.

The upper limit of the light irradiation density may be, for example, 1000W/m²、700W/m²、500W/m²。

The light irradiation density may be in the range of, for example

0.01W/m²～1000W/m²、

0.1W/m²～700W/m²、

1W/m²～500W/m²、

Within the range of (1).

The lower limit of the reaction time of step a may be:

preferably 0.5 hour,

More preferably 1 hour,

And further preferably 1.5 hours.

The upper limit of the reaction time of step a may be:

preferably 72 hours,

More preferably 48 hours, and

further preferably 24 hours.

The reaction time of step a may be:

preferably in the range of 0.5 to 72 hours,

More preferably within a range of 1 to 48 hours,

And more preferably in the range of 1.5 to 24 hours.

If the reaction time is too short, the reaction in step A may become insufficient.

If the reaction time is too long, it is disadvantageous in terms of cost and may cause an undesired reaction.

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

The reaction of step A may suitably be carried out in the presence of one or more selected from reaction initiators (e.g.free radical reaction initiators) and photosensitizers.

Examples of the reaction initiator (e.g., radical reaction initiator) include:

alpha-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' -dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl ] -2-morpholinyl-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, trihalomethyl phenyl sulfone),

Acylphosphine oxide compound,

Peroxides (e.g., di-t-butyl peroxide), and

an alkylphenone compound [ for example: igracure 127 (trade name; Merck Co.).

The reaction initiator may be used in an amount of:

preferably 0.00001 to 10 mol,

More preferably 0.0001 to 1 mol, and

more preferably 0.001 to 0.1 mol

Within the range of (1).

Examples of such "photosensitizers" include:

for example,

ketone compounds (e.g. acetone),

Benzophenone compounds [ for example: benzophenone, 4 '-bis (dimethylamino) benzophenone, 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 (cyanine) compounds, rhodamine compounds, pyrylium salt compounds, and the like.

The photosensitizers may be used singly or in combination of 2 or more.

Typically, a styryl compound, a quinoline compound, or a coumarin compound is preferable. Specific examples of the styryl compound or the quinoline compound include:

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.

Specific examples of the coumarin compound include:

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-amino-4-trifluoromethylcoumarin, 1,2,3,4,5,3H,6H, 10H-tetrahydro-8-trifluoromethyl (1) benzopyrano- (9,9A,1-gh) -quinolizin-10-one, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, and 1,2,3,4,5,3H,6H, 10H-tetrahydro-9-ethoxycarbonyl (1) benzopyrano (9,9a,1-gh) -quinolizine-10.

According to the production method of the present invention, the raw material conversion rate may be preferably 10% or more, more preferably 30% or more, and further preferably 50% or more.

According to the production method of the present invention, the selectivity of the target compound may be preferably 80% or more, and more preferably 90% or more.

According to the production method of the present invention, the yield of the target compound may be preferably 50% or more, and more preferably 70% or more.

Compound (I)

The compounds of the present invention are

A compound represented by the formula (1) (wherein 3, 3-difluoro-2-methyl-2-butanol and 4, 4-difluoro-2-methyl-2-butanol are excluded):

[ CHEM 7 ]

[ in the formula,

x represents-O-, an imino group which may have a substituent, or-S-,

R¹represents a hydrogen atom or a hydrocarbon group which may have 1 or more substituents, and R²Represents a hydrogen atom or a 1-valent organic group; or, R¹And R²May form a heterocyclic ring which may have 1 or more substituents together with their respective adjacent X and 1 carbon atom,

R³represents a hydrogen atom or a 1-valent organic group, and

R⁴represents-CF₂CH₃or-CH₂CHF₂。]。

Suitable modes for the compound can be understood from the descriptions for the compound in the aforementioned "method for producing an organic composition".

Composition comprising a metal oxide and a metal oxide

The vinylidene fluoride-containing composition of the present invention comprises:

(1) vinylidene fluoride, and

(2) as a liquid medium lean in the solvent for vinylidene fluoride, and

at least a portion of the vinylidene fluoride is dispersed as fine bubbles in the liquid medium.

The liquid medium is preferably a liquid medium containing one or more selected from water and an organic solvent which is a lean solvent for vinylidene fluoride.

Preferably, the vinylidene fluoride is dispersed almost entirely as fine bubbles except for a portion dissolved in the lean solvent.

The fine bubbles have a particle diameter in the range of 5nm to 100 [ mu ] m, and the ratio of the number of bubbles to the total number of bubbles in the gas is 90% or more.

A ratio of a volume of a vinylidene fluoride-containing gas to a volume of a liquid containing the compound represented by the formula (2) in the composition:

usually in the range of 0.01 to 1;

preferably in the range of 0.02-0.9;

more preferably in the range of 0.05 to 0.8; and

more preferably in the range of 0.1 to 0.5.

The average dispersed particle size may be:

preferably, the thickness is 10 μm or less,

more preferably, it is 5 μm or less,

more preferably 1 μm or less,

more preferably, the particle size is 500nm or less,

particularly preferably 300nm or less.

The average dispersed particle diameter may be, for example, 5nm or more, 10nm or more, 50nm or more, or 100nm or more.

Preferably, the first and second electrodes are formed of a metal,

the composition may be filled into a sealable container, such as a bomb (japanese: ボンベ).

The invention also provides a sealable container (e.g., a bomb) having the composition enclosed therein.

The form of the bubbles is:

with respect to the total number of bubbles of the gas,

the ratio of the number of bubbles having a particle diameter in the range of 10nm to 1 μm is preferably such that

More than 90% of the form;

more preferably, the ratio of the number of bubbles having a particle diameter in the range of 50nm to 1 μm is

More than 90% of the form;

the ratio of the number of bubbles having a particle diameter in the range of 50nm to 500nm is

More than 90% of the above-mentioned compound.

The details of the composition can be understood from the above description of "method for producing organic composition".

The liquid medium is preferably a liquid medium containing one or more selected from water and an organic solvent which is a lean solvent for vinylidene fluoride.

The method for producing the composition can be understood from the method for producing fine bubbles described in the above "method for producing an organic composition".

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 5nm to 100 μm to the total number of bubbles of the gas is 90% or more.

Other forms or more preferable modes of this embodiment can be understood with reference to other descriptions of the present invention.

Compositions containing fluoroolefins

The present invention also provides the following compositions containing a fluoroolefin.

A composition comprising a fluoroolefin comprising

(1) A fluorine-containing olefin (excluding vinylidene fluoride), and

(2) a liquid medium, and

at least a portion of the fluorine-containing olefin is dispersed as fine bubbles in the liquid medium.

The fluorine-containing olefin is preferably

A compound represented by the formula (3):

[ CHEM 8 ]

[ in the formula, R^a1、R^a2、R^a3And R^a4The same or different, represent a hydrogen atom, a fluorine atom, a chlorine atom, or a fluoroalkyl group; wherein R is^a1、R^a2、R^a3And R^a4At least 1 of them being fluorine atoms.]。

Specific examples thereof include tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene.

The liquid medium is preferably a liquid medium containing at least one selected from water and an organic solvent which is a poor solvent for the fluoroolefin represented by the formula (3) except for vinylidene fluoride.

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 5nm to 100 μm to the total number of bubbles of the gas is 90% or more.

The embodiment of the "composition containing a fluoroolefin (excluding vinylidene fluoride)" can be understood by those skilled in the art with reference to the description of the above-mentioned composition containing vinylidene fluoride.

The fine bubbles of the composition can be generated by a commonly performed method.

As such a method, for example, (1) as a method of utilizing supersaturation, there is a method of pressurizing a solute gas in a closed container containing a solvent to dissolve a sufficient amount of the solute gas, and then releasing the pressurization of the solvent in which the solute gas is dissolved by the pressurization to generate micro bubbles of the solute gas in the solvent.

Another method is a gas-liquid shearing method, in which a solute gas is supplied into a vortex of a solvent and the solute gas is sheared in the solvent, thereby generating fine bubbles of the solute gas in the solvent. The fine bubbles of the composition can be generated by using an apparatus for generating fine bubbles, micro bubbles, by any of the methods.

The nanobubble generating device may be a device having the following functions: the nanobubbles are produced in the liquid by injecting a gas into the liquid, applying a shearing force to the fluid of the gas/liquid mixture thus obtained by the static mixer, and repeating the cutting of the liquid.

Examples of the mode of generating fine bubbles include a pressurized dissolution mode, a rotary flow mode, a static mixer mode, a cavitation mode, a venturi mode, and the like.

The measurement of the particle diameter and the number of fine bubbles, and their distribution and average particle diameter can be carried out by the aforementioned method.

While the embodiments have been described above, it is to be understood that various changes in form and details may be made therein without departing from the spirit and scope of the appended claims.

Examples

Hereinafter, various aspects of the present invention will be described in detail by examples, but the aspects of the present invention are not limited thereto.

The meanings of the symbols and abbreviations in the examples are shown below.

VdF: vinylidene fluoride

Examples 1 to 3

In examples 1 to 3, the following compounds A to D were produced from VdF.

[ CHEM 9 ]

In each example, the apparatus and conditions shown in fig. 1 to 3 were used. The straight lines in the figure represent pump lines and the straight arrows represent the direction of flow of the fluid.

In the apparatus shown in fig. 1, the reaction solution taken out from the internal light irradiation type reaction apparatus is supplied to a fine bubble generation apparatus (as shown in fig. 1, a VdF bomb is attached), VdF fine bubbles generated by the apparatus are contained therein, and then the liquid containing the VdF fine bubbles is supplied to the reaction apparatus, thereby circulating the reaction solution.

In the apparatus shown in fig. 2, the reaction solution taken out from the internal light irradiation type reaction apparatus was mixed with VdF gas, and the mixed fluid (gas-liquid bullet flow) was supplied to the reactor, thereby circulating the reaction solution.

In the apparatus shown in FIG. 3, bubbles of VdF gas were supplied to the reaction liquid through a KERAMI filter (cylindrical gas injection tube), and on the other hand, the reaction liquid taken out of the internal light irradiation type reaction apparatus was resupplied to the reaction apparatus, and the reaction liquid was circulated.

From the reactor via a back pressure regulator (BPR in the figure) back to the reactor, circulation.

The internal light irradiation type reaction apparatus had a 100W Hg lamp as a light source.

(example 1)

Using the apparatus shown in fig. 1, a mixed solution of 1, 3-dioxolane (48mL) and acetone (12mL) was introduced into a Pyrex (registered trademark) reactor in a hot water bath. Thereafter, the internal temperature was set to 40 ℃. The solution was circulated at a rate of 30mL/min by a pump (which, as shown in the figure, was replaced with an HPLC pump) under irradiation with a 100W mercury lamp, and VdF was introduced as fine bubbles at a rate of 4.0mL/min using a fine bubble generation apparatus. After 2 hours, the solution was analyzed by F-NMR to obtain an adduct in 11% yield. The generation ratio is shown in table 1.

(example 2)

Using the same apparatus as used in example 1, 3-dioxolane (60mL) and IRGACURE 127(63mg, 0.2. mu. mol) were introduced into a Pyrex (registered trademark) reactor in a hot water bath. Thereafter, the internal temperature was set to 40 ℃. The solution was circulated at a rate of 30mL/min by a pump (which, as shown in the figure, was replaced with an HPLC pump) under irradiation with a 100W mercury lamp, and VdF was introduced as fine bubbles at a rate of 4.0mL/min using a fine bubble generation apparatus. After 2 hours, the solution was analyzed by F-NMR to obtain an adduct in 44% yield. The generation ratio is shown in table 1.

(example 3)

Except that the reaction time was changed to 24 hours, the adduct was obtained in a yield of 87% by performing the same method as example 2. The generation ratio is shown in table 1.

[ TABLE 1 ]

	A	B	C	D
					Example 1	17	3	5	1
Example 2	14	3	3	1
					Example 3	67	13	6	1

[ CHEM 10 ]

Examples 4 to 5

(example 4)

An adduct was obtained in a yield of 32% by the same method as in example 1 except that 1, 3-dioxolane was replaced by isopropyl alcohol.

The generation ratio is shown in table 2.

(example 5)

An adduct was obtained in 14% yield by the same method as in example 2 except that 1, 3-dioxolane was replaced by isopropyl alcohol.

The generation ratio is shown in table 2.

[ TABLE 2 ]

	E	F
			Example 4	2	1
Example 5	2	1

[ CHEM 11 ]

Example 6

Adducts G and H were obtained by the same method as in example 1 except that 1, 3-dioxolane was replaced by 2-methyl-1, 3-dioxolane.

The generation ratio is shown in table 3.

[ TABLE 3 ]

	G	H
			Example 6	3	1

Example 7

[ CHEM 12 ]

An adduct was obtained in 22% yield by the same method as in example 1 except that 1, 3-dioxolane was replaced with methyl orthoformate (48 mL).

Example 8

An adduct was obtained in a yield of 12% by the same method as in example 1 except that the amount of 1, 3-dioxolane used was changed to 60mL without adding acetone.

The generation ratio is shown in table 4.

[ TABLE 4 ]

	A	B	C	D
					Example 8	4	1	0	0

Example 9

A mixed solution of 2- (2H-hexafluoropropyl) tetrahydrofuran (18.5g), acetone (0.4g) and acetonitrile (35mL) was introduced into a reactor as outlined in FIG. 1. Thereafter, the internal temperature was set to-30 ℃. The solution was circulated at a rate of 30mL/min under irradiation with a 100W mercury lamp, and hexafluoropropylene was introduced as fine bubbles. After 2 hours, the solution was analyzed by F-NMR to obtain bis-2, 5- (2H-hexafluoropropyl) tetrahydrofuran in a yield of 90%.

Examples 10 to 11

(example 10)

An adduct was obtained in a yield of 9% by the same method as in example 1 except that the apparatus was replaced with the apparatus shown schematically in fig. 2. The generation ratio is shown in table 5.

(example 11)

The apparatus was replaced with the apparatus having a KERAMI filter as outlined in fig. 3, except that it was performed by the same method as example 1, and the adduct was obtained in 3% yield.

The generation ratio is shown in table 5.

[ TABLE 5 ]

	A	B	C	D
					Example 10	7	3	1	1
Example 11	14	6	1	1

Example 12[ measurement of particle diameter and number of VdF Fine bubbles]

The particle size of the bubbles formed by the fine bubble producing apparatus was measured by a nanoparticle measuring apparatus (NanoSight; Japan Quantum DESIGN). The measurement conditions were as follows.

The liquid medium: water, isopropanol, 1, 3-dioxolane, DMF

Gas: VdF

Nanobubble ejection pressure: 3.0MPa

Liquid flow rate: 28mL/min

Gas flow rate: 14mL/min

As a result of the measurement, the presence of bubbles was confirmed from the measurable particle diameter of 10nm, the smallest dimension. The results are shown in FIGS. 4 to 7. In the figure, the horizontal axis represents the bubble particle size, and the vertical axis represents the number of bubbles having each particle size per 1mL of the gas-liquid mixed fluid on average. Substantially all (100%) of the formed bubbles have a particle diameter of 10 to 500nm, and the bubbles having a particle diameter of 50 to 500nm account for 95% or more of the total number of the bubbles.

Example 13[ time-lapse Observation of nanobubbles of VdF]

50mL of the liquid medium (water, isopropanol, 1, 3-dioxolane, or DMF) used in the measurement was put into a 100mL DURAN bottle, and the dissolved gas in the liquid medium was removed by ultrasonic deaeration and 3 times of Ar replacement.

The reaction temperature was set at 30 ℃ using the same apparatus as that used in example 1, the reaction solution was fed at an actual flow rate of 28mL/min, the VdF was fed at 14mL/min, and the saturation concentration was measured by GC-FID. The time when the VdF concentration reached saturation was taken as 0 hour, and the number and concentration of nanobubbles were measured after 0, 1,2,4, 8, 24, 48 and 168 hours. The results of the observation with time are shown in FIGS. 8 to 15.

Example 14

[ CHEM 13 ]

A mixed solution of 2- (2H-hexafluoropropyl) tetrahydrofuran (18.5g), acetone (0.4g) and acetonitrile (35mL) was introduced into the reactor. Thereafter, the internal temperature was set to-30 ℃. The solution was circulated at a rate of 30mL/min under irradiation with a 100W mercury lamp, and hexafluoropropylene was introduced as fine bubbles. After 2 hours, the solution was analyzed by F-NMR to obtain bis-2, 5- (2H-hexafluoropropyl) tetrahydrofuran in a yield of 90%.

Comparative example 1

[ CHEM 14 ]

Hexafluoropropylene (5.9g) was introduced into an acetonitrile (35mL) solution of 2- (2H-hexafluoropropyl) tetrahydrofuran (18.5g) and acetone (0.4g) in a photoreactor at a temperature of-30 ℃ to-35 ℃ under irradiation with a 100W mercury lamp. After 6 hours, neutralization was carried out with bicarbonate, and the reaction mixture was dried and purified by distillation to give bis-2, 5- (2H hexafluoropropyl) tetrahydrofuran (12.4g, 85% yield) having a boiling point of 98 ℃ to 100 ℃/0.6 kPa. The yield at the time of 2 hours of the reaction was 60%.

Example 15[ measurement of particle diameter and number of various Fine bubbles]

The particle size of the bubbles formed by the fine bubble producing apparatus was measured by a nanoparticle measuring apparatus (NanoSight, japan QUANTUM DESIGN). The measurement conditions were as follows.

The liquid medium: water, isopropanol, 1, 3-dioxolane, DMF

Gas: 2,3,3, 3-tetrafluoropropene, hexafluoropropylene, or 1-bromo-1-fluoroethylene

Nanobubble ejection pressure: 3.0MPa

Liquid flow rate: 28mL/min

Gas flow rate: 14mL/min

As a result of the measurement, the presence of bubbles was confirmed from the measurable particle diameter of 10nm, the smallest dimension. The results are shown in FIGS. 16 to 24. In each figure, the horizontal axis represents the bubble particle size, and the vertical axis represents the number of bubbles having each particle size per 1mL of the gas-liquid mixed fluid on average. Substantially all (100%) of the formed bubbles have a particle diameter of 10 to 500nm, and the bubbles having a particle diameter of 50 to 500nm account for 95% or more of the total number of the bubbles.

Example 16[ time-lapse Observation of nanobubbles of various gases]

50mL of the liquid medium (water, isopropanol, 1, 3-dioxolane, or DMF) used in the measurement was put into a 100mL DURAN bottle, and the dissolved gas in the liquid medium was removed by ultrasonic deaeration and 3 times of Ar replacement.

The same apparatus as used in example 1 was used, the reaction temperature was set to 20 to 30 ℃, the reaction solution was fed at an actual flow rate of 28mL/min, 2,3,3, 3-tetrafluoropropene, hexafluoropropylene, or 1-bromo-1-fluoroethylene was fed at 14mL/min, and the saturation concentration was measured by GC-FID. The time when the concentration reached saturation was taken as 0 hour, and the number and concentration of nanobubbles were measured after 0, 1,2,4, 8, 24, 48 and 168 hours. The results are shown in FIGS. 25 to 33.