JP2021011474A - Manufacturing method of fluorinated vinyl compound - Google Patents

Abstract

To provide a method capable of obtaining a fluorinated vinyl compound at high yield and high selectivity.SOLUTION: Under the presence of alkali metal fluoride, a fluorinated vinyl compound is obtained which expressed by CHR1=CFR2 [In the formula, R1 denotes a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R2 denotes a halogen atom, an alkyl group or a fluoroalkyl group. Where, when R2 denotes a fluoroalkyl group, R1 denotes a halogen atom, an alkyl group or a fluoroalkyl group.] by reacting a halogenated vinyl compound which is expressed by CHR1=CXR3 [In the formula, R1 denotes a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group. R3 denotes a halogen atom, an alkyl group, or a fluoroalkyl group. Where, when the R3 is a fluoroalkyl group, R1 is a halogen atom, an alkyl group, or a fluoroalkyl group. X denotes a halogen atom other than a fluorine atom.].SELECTED DRAWING: None

Description

The present disclosure relates to a method for producing a vinyl fluoride compound.

When replacing a halogen atom other than the fluorine atom bonded to the SP2 carbon atom in the vinyl halide compound with a fluorine atom, for example, for tetrachloroethylene (PCE), a chlorine atom is added by hydrogen fluoride and boron trifluoride (BF ₃ ). Is also known as a method for fluorinating (see, for example, Non-Patent Document 1).

Journal of American Chemical Society, 1948, 70 (2), pp 758-760.

An object of the present disclosure is to provide a method capable of obtaining a vinyl fluoride compound in a high yield and a high selectivity.

The present disclosure includes the following configurations.

Item 1. General formula (1):
CHR ¹ = CFR ² (1)
[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R ² represents a halogen atom, an alkyl group or a fluoroalkyl group. However, if R ² is a fluoroalkyl group, then R ¹ is a halogen atom, an alkyl group or a fluoroalkyl group. ]
It is a method for producing a vinyl fluoride compound represented by.
In the presence of alkali metal fluoride
General formula (2):
CHR ¹ = CXR ³ (2)
[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R ³ represents a halogen atom, an alkyl group or a fluoroalkyl group. However, if R ³ is a fluoroalkyl group, then R ¹ is a halogen atom, an alkyl group or a fluoroalkyl group. X indicates a halogen atom other than a fluorine atom. ]
A production method comprising a reaction step of reacting a vinyl halide compound represented by the above formula (1) to obtain a vinyl fluoride compound represented by the general formula (1).

Item 2. The vinyl fluoride compound represented by the general formula (1) is the general formula (1A):

[In the equation, R ¹ and R ² are the same as above. ]
Item 2. The production method according to Item 1, which is a vinyl fluoride compound represented by.

Item 3. The vinyl halide compound represented by the general formula (2) is the general formula (2A):

[In the equation, R ¹ , R ³ and X are the same as above. ]
Item 3. The production method according to Item 1 or 2, which is a vinyl halide compound represented by.

Item 4. Item 8. The production method according to any one of Items 1 to 3, wherein the specific surface area of the alkali metal fluoride is 500 to 2000 m ² / g.

Item 5. Item 8. The production method according to any one of Items 1 to 4, wherein the alkali metal fluoride is supported on a carrier.

Item 6. Item 5. The production method according to Item 5, wherein the content of the alkali metal fluoride is 0.1 to 75% by mass, where the total amount of the carrier and the alkali metal fluoride is 100% by mass.

Item 7. Item 2. The production method according to any one of Items 1 to 6, wherein the reaction step is carried out in the presence of a gas containing fluorine.

Item 8. Item 8. The item according to any one of Items 1 to 7, wherein in the reaction step, the contact time (W / F) of the vinyl halide compound with the catalyst containing the alkali metal fluoride is 5 to 200 g · sec / cc. Production method.

Item 9. Item 8. The production method according to any one of Items 1 to 8, wherein the reaction temperature in the reaction step is 200 to 500 ° C.

Item 10. General formula (1A):

[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R ² represents a halogen atom, an alkyl group or a fluoroalkyl group. However, if R ² is a fluoroalkyl group, then R ¹ is a halogen atom, an alkyl group or a fluoroalkyl group. ]
Vinyl fluoride compound represented by and general formula (3):
R ¹ −C ≡ C−R ² (3)
[In the equation, R ¹ and R ² are the same as above. ]
A composition containing an alkyne compound represented by.

Item 11. When the total amount of the composition is 100 mol%, the content of the vinyl fluoride compound represented by the general formula (1) is 60 to 99.9 mol%, and the content of the alkyne compound represented by the general formula (3) is 60 to 99.9 mol%. Item 2. The composition according to Item 10, wherein the content is 0.1 to 20 mol%.

Item 12. The vinyl fluoride compound represented by the general formula (1A) is the general formula (1A1):

[In the equation, R ¹ is the same as above. ]
With the difluorovinyl compound represented by
General formula (1A2):

[In the equation, R ¹ is the same as above. X ¹ indicates a halogen atom other than a fluorine atom. ]
Item 2. The composition according to Item 10 or 11, which contains a vinyl fluoride compound represented by.

Item 13. When the total amount of the composition is 100 mol%, the content of the difluorovinyl compound represented by the general formula (1A1) is 40 to 98 mol%, and the content of the vinyl fluoride compound represented by the general formula (1A2) is 40 to 98 mol%. Item 2. The composition according to Item 12, wherein the content is 2 to 30 mol%.

Item 14. Item 6. The composition according to any one of Items 10 to 13, which is used as a cleaning gas, an etching gas, a refrigerant, or a building block for organic synthesis.

According to the present disclosure, the vinyl fluoride compound can be obtained in high yield and high selectivity.

As used herein, "contains" is a concept that includes any of "comprise," "consist essentially of," and "consist of." Further, in the present specification, when the numerical range is indicated by "A to B", it means A or more and B or less.

In the present disclosure, the "selectivity" means the ratio (mol%) of the total molar amount of the target compound contained in the effluent gas to the total molar amount of the compound other than the raw material compound in the effluent gas from the reactor outlet. To do.

In the present disclosure, the "conversion rate" is the ratio (mol%) of the total molar amount of compounds other than the raw material compound contained in the outflow gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor. means.

In the present disclosure, the "yield" means the ratio (mol%) of the total molar amount of the target compound contained in the outflow gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

1. 1. Method for Producing Vinyl Fluoride Compound The method for producing the vinyl fluoride compound of the present disclosure is as follows.
General formula (1):
CHR ¹ = CFR ² (1)
[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R ² represents a halogen atom, an alkyl group or a fluoroalkyl group. However, if R ² is a fluoroalkyl group, then R ¹ is a halogen atom, an alkyl group or a fluoroalkyl group. ]
It is a method for producing a vinyl fluoride compound represented by.
In the presence of alkali metal fluoride
General formula (2):
CHR ¹ = CXR ³ (2)
[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R ³ represents a halogen atom, an alkyl group or a fluoroalkyl group. However, if R ³ is a fluoroalkyl group, then R ¹ is a halogen atom, an alkyl group or a fluoroalkyl group. X indicates a halogen atom other than a fluorine atom. ]
The present invention comprises a reaction step of reacting a vinyl halide compound represented by the above formula (1) to obtain a vinyl fluoride compound represented by the general formula (1).

Conventionally, a fluorine atom has been introduced by performing a hydrogen fluoride addition reaction once and then a dehydrohalogenation reaction. According to this method, a two-step reaction step is required separately, and when the dehydrohalogenation reaction is carried out, the dehydrogenation hydrogen reaction also occurs at the same time, and a large amount of by-products are produced. The selection rate of the target product was low. Further, as in Non-Patent Document 1, a method of fluorinating a chlorine atom with hydrogen fluoride and boron trifluoride (BF ₃ ) with respect to tetrachlorethylene (PCE) is also known, but the yield in this case is also known. Was only about 20%.

According to the present disclosure, as described above, a vinyl halide compound having a halogen atom other than a fluorine atom is used as a substrate and reacted in the presence of an alkali metal fluoride to obtain a high yield of the vinyl fluoride compound in one step. It can be obtained with a high selectivity and a high selectivity.

(1-1) Vinyl halide compound As described above, the vinyl halide compound as a substrate that can be used in the production method of the present disclosure has the general formula (2):
CHR ¹ = CXR ³ (2)
[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R ³ represents a halogen atom, an alkyl group or a fluoroalkyl group. However, if R ³ is a fluoroalkyl group, then R ¹ is a halogen atom, an alkyl group or a fluoroalkyl group. X indicates a halogen atom other than a fluorine atom. ]
It is a vinyl halide compound represented by.

This vinyl halide compound may contain both a cis form and a trans form, but the trans form is particularly effective in producing a vinyl fluoride compound with a high conversion rate, yield and selectivity. Preferably, the general formula (2A):

[In the equation, R ¹ , R ³ and X are the same as above. ]
The vinyl halide compound represented by is preferable.

In the general formulas (2) and (2A), examples of the halogen atom represented by R ¹ and R ³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formulas (2) and (2A), the alkyl groups represented by R ¹ and R ³ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and sec-. Examples thereof include alkyl groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms such as butyl groups and tert-butyl groups. This alkyl group may also have 1 to 6, particularly 1 to 3 substituents such as the halogen atom described above.

In the general formulas (2) and (2A), examples of the fluoroalkyl group represented by R ¹ and R ³ include fluoromethyl groups having 1 to 10 carbon atoms, particularly fluoroalkyl groups having 1 to 6 carbon atoms, such as trifluoromethyl groups and pentacleuroethyl groups. Alkyl groups (particularly perfluoroalkyl groups) can be mentioned.

However, when R ¹ is a hydrogen atom and R ³ is a fluoroalkyl group, it is not a vinyl fluoride compound represented by the general formula (1), but the general formula (3):
R ¹ −C ≡ C−R ² (3)
[In the equation, R ¹ and R ² are the same as above. ]
The alkyne compound represented by is easily synthesized. Therefore, when R ³ is a fluoroalkyl group, R ¹ is a halogen atom, an alkyl group or a fluoroalkyl group.

In the general formulas (2) and (2A), examples of the halogen atom represented by X include a chlorine atom, a bromine atom and an iodine atom.

As the vinyl halide compound as a substrate, both R ¹ and R ³ are fluoroalkyl groups (particularly perfluoroalkyl) from the viewpoint that the vinyl fluoride compound can be produced with a particularly high conversion rate, yield and selectivity. Group), and X is preferably a chlorine atom.

When both R ³ and X are halogen atoms other than fluorine atoms, only one halogen atom is generated by the reaction of the vinyl halide compounds represented by the above general formulas (2) and (2A). CHR ¹ = CFX ¹ substituted with a fluorine atom, especially the general formula (1A2):

[In the equation, R ¹ is the same as above. X ¹ indicates a halogen atom other than the above-mentioned fluorine atom. ]
The vinyl fluoride compound represented by and the general formula (1A1) in which two halogen atoms are replaced with fluorine atoms:

[In the equation, R ¹ is the same as above. ]
Both of the difluorovinyl compounds represented by can be synthesized. Both the difluorovinyl compound represented by the general formula (1A1) and the vinyl fluoride compound represented by the general formula (1A2) are the target compounds.

The above-mentioned R ¹ , R ³ and X may be the same or different from each other.

Specifically, as a vinyl halide compound as a substrate satisfying the above conditions,

And so on. These vinyl halide compounds can be used alone or in combination of two or more. As such a vinyl halide compound, a known or commercially available product can be adopted.

(1-2) Substitution reaction In the reaction step of reacting the vinyl halide compound represented by the general formula (2) in the present disclosure, for example, the vinyl halide compound represented by the general formula (2) is used as a substrate. Both R ¹ and R ³ are preferably a trifluoromethyl group, X is preferably a chlorine atom, and a trans compound is preferable. Further, as the substrate, in the vinyl halide compound represented by the general formula (2), it is also preferable that R ¹ is a hydrogen atom and R ³ and X are chlorine atoms.

That is, the following reaction formula:

Therefore, it is preferable to obtain a vinyl fluoride compound in one step.

(1-3) Alkali Metal Fluoride In the reaction step of reacting the vinyl halide compound represented by the general formula (2) in the present disclosure, a halogen atom is converted into a fluorine atom in one step in the presence of alkali metal fluoride. It is a replacement. Alkali metal fluorides act as catalysts and can produce vinyl fluoride compounds with particularly high conversions, yields and selectivity.

The alkali metal fluoride is not particularly limited, but the alkali metal of the 4th to 7th periods can be produced from the viewpoint that the vinyl fluoride compound can be produced with a particularly high conversion rate, yield and selectivity. Fluoride is preferable, for example, potassium fluoride (KF), cesium fluoride (CsF) and the like are more preferable, and cesium fluoride (CsF) is further preferable. These alkali metal fluorides can be used alone or in combination of two or more.

The specific surface area of the alkali metal fluoride is preferably 500 to 2000 m ² / g, preferably 800 to 1500 m ² / g, from the viewpoint that the vinyl fluoride compound can be produced with a particularly high conversion rate, yield and selectivity. More preferred. In the present disclosure, the specific surface area of alkali metal fluoride is measured by the BET method. When the specific surface area of the alkali metal fluoride is in such a range, the density of the alkali metal fluoride particles is not too small, so that the target compound can be obtained with a higher selectivity. It is also possible to further improve the conversion rate of the substrate. As will be described later, there is no large difference in the specific surface area when the alkali metal fluoride is supported on the carrier, and the specific surface area when the alkali metal fluoride is supported on the carrier is preferably in the above range.

In the present disclosure, when the reaction is carried out in the gas phase, the above-mentioned substrate and the fluorine source are brought into contact with each other. In that case, from the viewpoint of reactivity, the alkali metal fluoride is in a solid state (solid phase) with the substrate. It is preferable to bring them into contact.

In the present disclosure, for example, when a gas phase continuous flow type reaction is carried out, the alkali metal fluoride may be in the form of powder, but is preferably in the form of pellets from the viewpoint of reactivity. Further, the above-mentioned alkali metal fluoride can be used as it is, but it can be used by supporting it on a carrier (hereinafter, the alkali metal fluoride supported on the carrier is referred to as "carrier-supported alkali metal fluoride". May be said). Thereby, the specific surface area of the fluorine source can be increased to improve the reaction efficiency, and the vinyl fluoride compound can be produced with a particularly high conversion rate, yield and selectivity. The carrier to be supported is not particularly limited, and examples thereof include carbon, alumina, zirconia, silica, titania, zeolite, silica alumina, and chromium oxide. Examples of carbon include activated carbon, amorphous carbon, graphite, diamond and the like. These carriers can be used alone or in combination of two or more. Of these, carbon is preferable, and activated carbon is more preferable, from the viewpoint of having a large specific surface area and easy support of alkali metal fluoride.

When the carrier-supported alkali metal fluoride is used, the amount supported is not particularly limited, but from the viewpoint that the vinyl fluoride compound can be produced with a particularly high conversion rate, yield and selectivity, the carrier-supported alkali metal fluoride is used. The total amount of the compound is 100% by mass, and the alkali metal fluoride is preferably contained in an amount of 0.1 to 75% by mass, more preferably 1 to 60% by mass.

The bulk density of the carrier-supported alkali metal fluoride is preferably 0.01 to 10 g / mL, preferably 0.1 to 5 g / mL, from the viewpoint that the vinyl fluoride compound can be produced with a particularly high conversion rate, yield and selectivity. More preferred. In the present disclosure, the bulk density of the carrier-supported alkali metal fluoride is measured by a bulk density measuring device. When the bulk density of the carrier-supported alkali metal fluoride is in such a range, the density of the particles of the carrier-supported alkali metal fluoride is not too small, so that the target compound can be obtained with a higher selectivity. It is also possible to further improve the conversion rate of the substrate.

The pore volume of the carrier-supported alkali metal fluoride is preferably 0.1 to 1.5 mL / g, preferably 0.25 to 1.0 mL, from the viewpoint that the vinyl fluoride compound can be produced with a particularly high conversion rate, yield and selectivity. / g is more preferred. In the present disclosure, the pore volume of the carrier-supported alkali metal fluoride is measured by the BET method. When the pore volume of the carrier-supported alkali metal fluoride is in such a range, the density of the particles of the carrier-supported alkali metal fluoride is not too small, so that the target compound can be obtained with a higher selectivity. It is also possible to further improve the conversion rate of the substrate.

The average pore size of the carrier-supported alkali metal fluoride is preferably 5 to 20 μm, more preferably 8 to 15 μm, from the viewpoint that the vinyl fluoride compound can be produced with a particularly high conversion rate, yield and selectivity. In the present disclosure, the average pore size of the carrier-supported alkali metal fluoride is measured by the BET method.

(1-4) Fluorine-Containing Gas The above-mentioned alkali metal fluoride also functions as a catalyst, and a vinyl fluoride compound can be produced with a particularly high conversion rate, yield and selectivity. However, the alkali metal fluoride contains a fluorine atom, and the fluorine atom can be extracted during the reaction for obtaining the vinyl fluoride compound represented by the general formula (1). Therefore, as the reaction proceeds for a long time, the amount of alkali metal fluoride that functions effectively as a catalyst may decrease. Therefore, the above reaction is preferably carried out in the presence of a fluorine-containing gas with the intention of replenishing fluorine atoms.

As the gas containing such fluorine is not particularly limited, for _{example, F 2, HF, CFCl 3} , CF 2 Cl 2, CFHCl 2, CF 2 HCl, CF 3 H, NF 3, IF 5, IF 7 , FCl, ClF _3, etc.

In the present disclosure, when the reaction is carried out in the gas phase, it is preferable that the above-mentioned fluorine-containing gas is blown in a gaseous state (gas phase).

(1-5) Reaction Temperature In the step of reacting the vinyl halide compound in the present disclosure to obtain a vinyl fluoride compound, the reaction temperature is such that the vinyl fluoride compound is produced at a particularly high conversion rate, yield and selectivity. From the viewpoint of being able to do so, it is usually preferably 200 to 500 ° C, more preferably 250 to 450 ° C, and even more preferably 300 to 400 ° C.

(1-6) Reaction time In the present disclosure, when the reaction is carried out in the gas phase, the reaction time is the catalyst (alkali metal fluoride) of the raw material compound (vinyl halide compound) when, for example, the gas phase flow method is adopted. ) (W / F) [W: Weight of catalyst containing alkali metal fluoride (total amount including carrier in the case of carrier-supported alkali metal fluoride) (g), F: Raw material compound (vinyl halide compound) ) Flow rate (cc / sec)] is preferably 5 to 200 g · sec./cc from the viewpoint that the conversion rate of the reaction is particularly high and the vinyl fluoride compound can be obtained in a higher yield and higher selectivity. , 10 to 150 g · sec./cc is more preferable, and 15 to 100 g · sec./cc is even more preferable. The contact time means the time during which the raw material compound and the catalyst are in contact with each other.

The above contact time indicates the conditions when the reaction proceeds in the gas phase, particularly in the gas phase continuous flow system, but can be appropriately adjusted when the reaction proceeds in the batch system.

In the present disclosure, when the reaction step is carried out in the presence of a fluorine-containing gas, the content of the fluorine-containing gas has a particularly high conversion rate of the reaction, and the vinyl fluoride compound has a higher yield and higher selectivity. From the viewpoint that it can be obtained, 0.1 to 10 mol is preferable, 0.5 to 5 mol is more preferable, and 1 to 2.5 mol is further preferable with respect to 1 mol of the raw material compound (vinyl halide compound).

(1-7) Reaction Pressure The reaction pressure when the vinyl halide compound in the present disclosure is reacted to obtain a vinyl fluoride compound is such that the vinyl fluoride compound is produced with a particularly high conversion rate, yield and selectivity. -0.05 to 2 MPa is preferable, -0.01 to 1 MPa is more preferable, and normal pressure to 0.5 MPa is further preferable. In this disclosure, the pressure is a gauge pressure unless otherwise specified.

In the reaction in the present disclosure, the reactor that reacts the raw material compound (vinyl halide compound) in the presence of an alkali metal fluoride and, if necessary, a fluorine-containing gas, can withstand the above temperature and pressure. For example, the shape and structure are not particularly limited. Examples of the reactor include a vertical reactor, a horizontal reactor, a multi-tube reactor and the like. Examples of the material of the reactor include glass, stainless steel, iron, nickel, iron-nickel alloy and the like.

(1-8) Example of Reaction In the reaction step of reacting a vinyl halide compound in the present disclosure to obtain a vinyl fluoride compound, a raw material compound (vinyl halide compound) is continuously charged into a reactor and the reaction device is used. It can be carried out by either a vapor phase continuous flow method or a batch method in which the target compound (vinyl fluoride compound) is continuously extracted. When the target compound stays in the reactor, the elimination reaction can proceed further. Therefore, it is preferable to carry out the gas phase continuous flow system. The reaction step of reacting the vinyl halide compound in the present disclosure to obtain the vinyl fluoride compound is preferably carried out in the gas phase, and particularly preferably in the gas phase continuous flow method using a fixed bed reactor. When the gas phase continuous flow system is used, the equipment, operation, etc. can be simplified and it is economically advantageous.

Regarding the atmosphere when the reaction step of reacting the vinyl halide compound in the present disclosure to obtain the vinyl fluoride compound is performed, an inert gas atmosphere is preferable from the viewpoint of suppressing deterioration of the alkali metal fluoride. Examples of the inert gas include nitrogen, helium, argon and the like. Among these inert gases, nitrogen is preferable from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gas component introduced into the reactor. When the reaction is carried out in the presence of a fluorine-containing gas, the reaction may be carried out in the atmosphere of the fluorine-containing gas or in the mixed atmosphere of the inert gas and the fluorine-containing gas. .. The concentration of the fluorine-containing gas is preferably 0.1 to 90 mol% of the gas component introduced into the reactor.

After completion of the reaction, if necessary, purification treatment is carried out according to a conventional method to obtain a vinyl fluoride compound represented by the general formula (1).

(1-9) Target Compound The target compound of the present disclosure thus obtained is the general formula (1):
CHR ¹ = CFR ² (1)
[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R ² represents a halogen atom, an alkyl group or a fluoroalkyl group. However, if R ² is a fluoroalkyl group, then R ¹ is a halogen atom, an alkyl group or a fluoroalkyl group. ]
It is a vinyl fluoride compound represented by.

Although this vinyl fluoride compound may contain both a cis form and a trans form, the trans form is preferable from the viewpoint of being able to be produced with a high conversion rate, yield and selectivity, and the general formula (1A). :

[In the equation, R ¹ and R ² are the same as above. ]
The vinyl fluoride compound represented by is preferable.

R ¹ and R ² in the general formulas (1) and (1A) correspond to R ¹ and R ³ in the general formulas (2) and (2A) described above. When R ³ in the general formulas (2) and (2A) is a halogen atom other than a fluorine atom, the target compound, the vinyl fluoride compound, includes a compound in which the halogen atom is replaced with a fluorine atom and the halogen. Compounds in which atoms remain as they are can be included. Therefore, the vinyl fluoride compounds represented by the general formulas (1) and (1A) to be produced are, for example, specifically.

And so on.

The vinyl fluoride compound thus obtained can be effectively used in various applications such as an etching gas for forming a state-of-the-art fine structure such as a semiconductor and a liquid crystal, a cleaning gas, and a building block for organic synthesis. The building block for organic synthesis will be described later.

2. 2. Composition The vinyl fluoride compound can be obtained as described above, and the vinyl fluoride compound represented by the general formulas (1) and (1A) and the general formula (3):
R ¹ −C ≡ C−R ² (3)
[In the equation, R ¹ and R ² are the same as above. ]
It may also be obtained in the form of a composition containing an alkyne compound represented by.

In this case, assuming that the total amount of the compositions of the present disclosure is 100 mol%, the content of the vinyl fluoride compound represented by the general formula (1) is preferably 60 to 99.9 mol%, more preferably 80 to 99 mol%. Further, assuming that the total amount of the compositions of the present disclosure is 100 mol%, the content of the alkyne compound represented by the general formula (3) is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%. When the vinyl fluoride compound represented by the general formula (1) contains both the general formulas (1A1) and (1A2) as described later, the above content is the total amount thereof.

Further, as described above, when R ³ in the general formulas (2) and (2A) is a halogen atom other than the fluorine atom, the vinyl fluoride compound which is the target compound is a compound in which the halogen atom is replaced with a fluorine atom. And a compound in which the halogen atom remains as it is can be included.

Therefore, for the vinyl fluoride compounds represented by the general formulas (1) and (1A), the general formula (1A1):

[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. ]
With the difluorovinyl compound represented by
General formula (1A2):

[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. X ¹ indicates a halogen atom other than a fluorine atom. ]
It may include a vinyl fluoride compound represented by.

In the general formulas (1A) and (1B), the above-mentioned one can be adopted as R ¹ , and examples of the halogen atom other than the fluorine atom represented by X ¹ include a chlorine atom, a bromine atom and an iodine atom.

In this case, assuming that the total amount of the compositions of the present disclosure is 100 mol%, the content of the difluorovinyl compound represented by the general formula (1A1) is preferably 40 to 98 mol%, more preferably 50 to 90 mol%. Further, assuming that the total amount of the compositions of the present disclosure is 100 mol%, the content of the difluorovinyl compound represented by the general formula (1A2) is preferably 2 to 30 mol%, more preferably 3 to 20 mol%.

According to the production method of the present disclosure, even when the composition is obtained as described above, the vinyl fluoride compound represented by the general formula (1) can be used in one step to increase the conversion rate of the reaction. In addition, since it can be obtained in high yield and high selectivity, it is possible to reduce the components other than the vinyl fluoride compound represented by the general formula (1) in the composition, and thus the general formula ( The purification labor for obtaining the vinyl fluoride compound represented by 1) can be reduced.

Such a composition of the present disclosure can be effectively used in various applications such as a building block for organic synthesis and a cleaning gas, in addition to an etching gas for forming a state-of-the-art fine structure such as a semiconductor or a liquid crystal. The building block for organic synthesis means a substance that can be a precursor of a compound having a highly reactive skeleton. For example, when the composition of the present disclosure is reacted with a fluorine-containing organosilicon compound such as CF ₃ Si (CH ₃ ) _3, a fluoroalkyl group such as CF ₃ is introduced to form a cleaning agent or a fluorine-containing pharmaceutical intermediate. It can be converted into the substance to be obtained.

Although the embodiments of the present disclosure have been described above, various modifications of the forms and details are possible without departing from the spirit and scope of the claims.

Examples are shown below to clarify the features of the present disclosure. The present disclosure is not limited to these examples.

Synthesis example 1: 50% CsF / AC
Activated carbon (specific surface area 1200 m ² / g) and cesium fluoride are mixed so that the total amount of activated carbon and cesium fluoride is 100% by mass and the amount of cesium fluoride used is 50% by mass. A 50% CsF / AC catalyst carried by cesium fluoride was obtained. The specific surface area of the obtained catalyst was 600 cm ² / g, the pore volume was 0.7 mL / g, and the pore diameter was 10 μm.

Synthesis example 2: 5% CsF / AC
Activated carbon (specific surface area 1200 m ² / g) and cesium fluoride are mixed so that the total amount of activated carbon and cesium fluoride is 100% by mass and the amount of cesium fluoride used is 5% by mass. A 5% CsF / AC catalyst carried by cesium fluoride was obtained. The specific surface area of the obtained catalyst was 900 cm ² / g, the pore volume was 0.8 mL / g, and the pore diameter was 10 μm.

Synthesis example 3: 5% KF / AC
Activated carbon (specific surface area 1200 m ² / g) and potassium fluoride are mixed so that the total amount of activated carbon and potassium fluoride is 100% by mass and the amount of potassium fluoride used is 5% by mass, and the mixture is added to the activated carbon. A 5% KF / AC catalyst carried by cesium fluoride was obtained. The specific surface area of the obtained catalyst was 900 cm ² / g, the pore volume was 0.8 mL / g, and the pore diameter was 10 μm.

Examples 1-5
In the method for producing a vinyl fluoride compound of Examples 1 to 5, the raw material compound is a vinyl halide compound represented by the general formula (2), where R ¹ and R ³ are trifluoromethyl groups and X is a chlorine atom. , The following reaction formula:

Therefore, a vinyl fluoride compound was obtained.

To the SUS pipe (outer diameter: 1/2 inch), which is a reaction tube, 10 g of the catalyst obtained in Synthesis Example 1, 2 or 3 was added. After drying at 200 ° C for 2 hours in a nitrogen atmosphere, the pressure is normal pressure, and the contact time (W / F) between CF ₃ CH = CClCF ₃ (raw material compound) and the catalyst is 16.0 g ・ sec / cc or 42.0 g ・CF ₃ CH = CClCF ₃ (raw material compound) was circulated in the reaction tube so as to be sec / cc.

The reaction proceeded in a gas phase continuous flow system.

The reaction tube was heated at 300 ° C. or 400 ° C. to initiate the reaction.

One hour after the reaction was started, the distillate that passed through the abatement tower was collected.

After that, mass spectrometry was performed by gas chromatography / mass spectrometry (GC / MS) using gas chromatography (manufactured by Shimadzu Corporation, trade name "GC-2014"), and NMR (manufactured by JEOL Ltd., trade name). Structural analysis by NMR spectrum was performed using "400YH").

From the results of mass spectrometry and structural analysis, it was confirmed that CF ₃ CH = CFCF ₃ was produced as the target compound. The results are shown in Table 1.

Examples 6-8
In the method for producing the vinyl fluoride compound of Examples 6 to 8, the raw material compound is a vinyl halide compound represented by the general formula (2), where R ¹ is a hydrogen atom and R ³ and X are chlorine atoms. Reaction formula:

Therefore, a vinyl fluoride compound was obtained.

To the SUS pipe (outer diameter: 1/2 inch), which is a reaction tube, 10 g of the catalyst obtained in Synthesis Example 1 or 3 was added. After drying at 200 ° C for 2 hours under a nitrogen atmosphere, the pressure is normal pressure, and the contact time (W / F) between CH ₂ = CCl ₂ (raw material compound) and the catalyst is 10.0 g · sec / cc or 20.0 g · sec. CH ₂ = CCl ₂ (raw material compound) was circulated in the reaction tube so as to be / cc.

The reaction proceeded in a gas phase continuous flow system.

The reaction tube was heated at 400 ° C. to start the reaction.

One hour after the reaction was started, the distillate that passed through the abatement tower was collected.

After that, mass spectrometry was performed by gas chromatography / mass spectrometry (GC / MS) using gas chromatography (manufactured by Shimadzu Corporation, trade name "GC-2014"), and NMR (manufactured by JEOL Ltd., trade name). Structural analysis by NMR spectrum was performed using "400YH").

From the results of mass spectrometry and structural analysis, it was confirmed that CH ₂ = CClF and CH ₂ = CF ₂ were produced as the target compounds. The results are shown in Table 2.

Claims (14)

General formula (1):
CHR ¹ = CFR ² (1)
[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R ² represents a halogen atom, an alkyl group or a fluoroalkyl group. However, if R ² is a fluoroalkyl group, then R ¹ is a halogen atom, an alkyl group or a fluoroalkyl group. ]
It is a method for producing a vinyl fluoride compound represented by.
In the presence of alkali metal fluoride
General formula (2):
CHR ¹ = CXR ³ (2)
[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R ³ represents a halogen atom, an alkyl group or a fluoroalkyl group. However, if R ³ is a fluoroalkyl group, then R ¹ is a halogen atom, an alkyl group or a fluoroalkyl group. X indicates a halogen atom other than a fluorine atom. ]
A production method comprising a reaction step of reacting a vinyl halide compound represented by the above formula (1) to obtain a vinyl fluoride compound represented by the general formula (1). The vinyl fluoride compound represented by the general formula (1) is the general formula (1A):

[In the equation, R ¹ and R ² are the same as above. ]
The production method according to claim 1, which is a vinyl fluoride compound represented by. The vinyl halide compound represented by the general formula (2) is the general formula (2A):

[In the equation, R ¹ , R ³ and X are the same as above. ]
The production method according to claim 1 or 2, which is a vinyl halide compound represented by. The production method according to any one of claims 1 to 3, wherein the specific surface area of the alkali metal fluoride is 500 to 2000 m ² / g. The production method according to any one of claims 1 to 4, wherein the alkali metal fluoride is supported on a carrier. The production method according to claim 5, wherein the total amount of the carrier and the alkali metal fluoride is 100% by mass, and the content of the alkali metal fluoride is 0.1 to 75% by mass. The production method according to any one of claims 1 to 6, wherein the reaction step is carried out in the presence of a gas containing fluorine. The invention according to any one of claims 1 to 7, wherein in the reaction step, the contact time (W / F) of the vinyl halide compound with the catalyst containing the alkali metal fluoride is 5 to 200 g · sec / cc. Manufacturing method. The production method according to any one of claims 1 to 8, wherein the reaction temperature in the reaction step is 200 to 500 ° C. General formula (1A):

[In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group. R ² represents a halogen atom, an alkyl group or a fluoroalkyl group. However, if R ² is a fluoroalkyl group, then R ¹ is a halogen atom, an alkyl group or a fluoroalkyl group. ]
Vinyl fluoride compound represented by and general formula (3):
R ¹ −C ≡ C−R ² (3)
[In the equation, R ¹ and R ² are the same as above. ]
A composition containing an alkyne compound represented by. When the total amount of the composition is 100 mol%, the content of the vinyl fluoride compound represented by the general formula (1) is 60 to 99.9 mol%, and the content of the alkyne compound represented by the general formula (3) is 60 to 99.9 mol%. The composition according to claim 10, wherein the content is 0.1 to 20 mol%. The vinyl fluoride compound represented by the general formula (1A) is the general formula (1A1):

[In the equation, R ¹ is the same as above. ]
With the difluorovinyl compound represented by
General formula (1A2):

[In the equation, R ¹ is the same as above. X ¹ indicates a halogen atom other than a fluorine atom. ]
The composition according to claim 10 or 11, which contains a vinyl fluoride compound represented by. When the total amount of the composition is 100 mol%, the content of the difluorovinyl compound represented by the general formula (1A1) is 40 to 98 mol%, and the content of the vinyl fluoride compound represented by the general formula (1A2) is 40 to 98 mol%. The composition according to claim 12, wherein the content is 2 to 30 mol%. The composition according to any one of claims 10 to 13, which is used as a cleaning gas, an etching gas, a refrigerant, or a building block for organic synthesis.