JP2020193173A - Method of producing halide - Google Patents

Abstract

To provide a novel method of producing a halide.SOLUTION: A method of producing a halide comprises reacting a halogen with a compound of general formula (1) in the figure, where X and Y each independently represent H, F or CF3. The halide is an unsaturated halide or a saturated halide.SELECTED DRAWING: None

Description

The present disclosure relates to a method for producing a halide, particularly an unsaturated halide or a method for producing a saturated halide.

The unsaturated halide 1,2-difluoroethylene (HFO-1132) and the saturated halide 1,1,2,2-tetrafluoroethane (HFC-134) are considered to be useful as a refrigerant or a raw material thereof. It is promising as a next-generation refrigerant.
A method for producing an unsaturated halide such as HFO-1132 is characterized in that, for example, 1-chloro-1,2-difluoroethylene and hydrogen are reacted in a gas phase in the presence of a hydrogenation catalyst 1. A method for producing 2-difluoroethylene (Patent Document 1) is known.

Japanese Unexamined Patent Publication No. 2016-056132

It is an object of the present disclosure to provide a novel method for producing a halide.

Item 1. General formula (1)
(In the formula, X and Y independently represent H, F or CF ₃ , respectively.)
A method for producing a halide, which comprises reacting a compound of the above with a halogen.
Item 2. The compound of the general formula (1) is
Item 2. The production method according to Item 1, which is at least one compound selected from the group consisting of.
Item 3. Item 2. The production method according to Item 1 or 2, wherein the halogen is a fluorine gas.
Item 4. Item 3. The production method according to Item 3, wherein the molar ratio of the fluorine gas to the compound of the general formula (1) present in the reaction field (fluorine gas / compound of the general formula (1)) is 0.04 or less.
Item 5. Item 3. The production method according to Item 3 or 4, wherein the fluorine gas is diluted with an inert gas and used.
Item 6. The production method according to any one of Items 3 to 5, wherein the fluorine gas is permeated through a molded product made of a material capable of permeating the fluorine gas and reacted with the compound of the general formula (1).
Item 7. Item 6. The production method according to Item 6, wherein the molded product made of a material capable of transmitting fluorine gas is a film or a tube.
Item 8. Item 8. The production method according to any one of Items 1 to 7, wherein the halide is an unsaturated halide.
Item 9. Item 8. The production method according to Item 8, wherein the obtained unsaturated halide is immediately separated.
Item 10. Item 9. The production method according to Item 9, which separates using an adsorbent.
Item 11. The term in which the unsaturated halide is at least one compound selected from the group consisting of CHF = CHF, CF ₂ = CFH, CF ₃ CF = CFH, CF ₃ CF = CF ₂ and CF ₃ CF = CFCF _3. The production method according to any one of 8 to 10.
Item 12. Item 8. The production method according to any one of Items 1 to 3, wherein the halide is a saturated halide.
Item 13. Item 12. The production method according to Item 12, wherein the halogen is supplied from at least one solid fluorine source selected from the group consisting of CoF ₃ , WF ₆ , VF ₆ , MoF ₆ and UF ₆ .
Item 14. Item 13. The production method according to Item 13, wherein the solid fluorine source is CoF ₃ .
Item 15. The saturated halide is at least one selected from the group consisting of CHF ₂ CHF ₂ , CF ₃ CF ₂ H, CF ₃ CF ₂ CF ₂ H, CF ₃ CF ₂ CF ₃ and CF ₃ CF ₂ CF ₂ CF ₃ . The production method according to any one of Items 12 to 14, which is a compound.

The present disclosure provides a novel method for producing a halide.

It is a figure which shows an example of a reaction apparatus.

The present disclosure is based on the general formula (1).
(In the formula, X and Y independently represent H, F or CF ₃ , respectively.)
The present invention relates to a method for producing a halide, which comprises reacting a compound of the above with a halogen.

As the compound of the above general formula (1),
It is preferably at least one compound selected from the group consisting of
Is more preferable.

The compound of the above general formula (1), for example, acetylene can be produced by contacting calcium carbide with water or the like.

Examples of the halide include unsaturated halides and saturated halides. That is, as the method for producing the above-mentioned halide, more specifically, a method for producing an unsaturated halide and a method for producing a saturated halide can be mentioned. In the method for producing an unsaturated halide, the unsaturated halide may be predominantly (mainly) produced, and in the method for producing a saturated halide, the saturated halide may be predominantly produced. Good.

1. 1. Method for Producing Unsaturated Halide In order to produce an unsaturated halide, the reaction is carried out by maintaining a large amount of the compound of the general formula (1) and a small amount of halogen in the reaction field, that is, a reaction field. It is preferable to keep the molar ratio of halogen (halogen / compound of general formula (1)) to the compound of general formula (1) present in the above small and react.
This is because the reactivity of the halogen to the double bond is higher than the reactivity of the halogen to the triple bond, so the reaction is carried out while keeping the molar ratio of the halogen to the compound of the general formula (1) existing in the reaction field small. This is because it is considered that the reaction does not proceed until the saturated halide is formed, and the unsaturated halide can obtain a dominant product.
The reaction field means the inside of the reactor, and specifically, the inside of the reactor in which a halogen is reacted with the compound of the general formula (1).

The concentration of the compound of the general formula (1) is not particularly limited, but is preferably 0.1 to 100% by volume, preferably 1 to 100% by volume, from the viewpoint of predominantly obtaining an unsaturated halide and from the viewpoint of safety. Is more preferable.
The concentration of the compound of the general formula (1) can be adjusted (diluted) with an inert gas.
The inert gas is not particularly limited, and examples thereof include nitrogen gas, helium gas, neon gas, argon gas and the like, and nitrogen gas is preferable.

The halogen is not particularly limited, and examples thereof include fluorine, chlorine, bromine, and iodine. From the viewpoint of usefulness, fluorine gas is preferable as the halogen.
Further, the halogen can be manufactured or obtained from a commercially available product by a known method.

The halogen is preferably diluted with an inert gas before use. It is more preferable to dilute the fluorine gas with an inert gas before use.
The inert gas is not particularly limited, and examples thereof include nitrogen gas, helium gas, neon gas, argon gas and the like, and nitrogen gas is preferable.
When fluorine gas is used as the halogen, the upper limit of the gas concentration is preferably 2% by volume or less, more preferably 0.5% by volume or less, and 0.25% by volume from the viewpoint of predominantly producing an unsaturated halide. The following is more preferable. The lower limit of the gas concentration is preferably 0.05% by volume or more, more preferably 0.1% by volume or more, from the viewpoint of ease of separation of the obtained halide.

The molar ratio of halogen to the compound of the general formula (1) present in the reaction field (halogen / compound of the general formula (1)) is not particularly limited, but is preferably reduced. For example, when fluorine gas is used as the halogen, the upper limit of the molar ratio of fluorine gas to the compound of the general formula (1) (fluorine gas / compound of the general formula (1)) existing in the reaction field is predominantly unsaturated halides. From the viewpoint of producing, 0.04 or less is preferable, 0.02 or less is more preferable, and 0.005 or less is further preferable. The lower limit of the molar ratio is preferably 0.001 or more, more preferably 0.002 or more, from the viewpoint of ease of separation of the obtained unsaturated halide.

The method for adjusting the molar ratio of halogen to the compound of the general formula (1) existing in the reaction field (halogen / compound of the general formula (1)) is not particularly limited, but for example, the general formula (1) in the reaction field. ), A method of adjusting the flow rate of halogen with respect to the compound, a method of using a mass flow controller, and the like.

In the production method of the present disclosure, it is preferable that fluorine gas is permeated through a molded product made of a material capable of permeating fluorine gas and reacted with the compound of the general formula (1).
By permeating fluorine gas little by little through a molded product made of a material that can permeate fluorine gas, the molar ratio of fluorine gas to the compound of the general formula (1) existing in the reaction field (fluorine gas / general formula). The compound (1) can be reacted in a small state, and the reaction amount and the reaction rate of the compound of the general formula (1) and the fluorine gas can be controlled. In addition, it becomes easy to separate the reaction mixture after the reaction, and various separation methods can be adopted.

The material that can permeate fluorine gas is not particularly limited as long as it is a material that can permeate fluorine gas and can withstand fluorine gas (it is not denatured by fluorine gas), but for example, PFA (perfluoroalkoxyalkane), Examples thereof include FEP (perfluoroethylene propene copolymer), ETFE (ethylene tetrafluoroethylene copolymer), PTFE (polytetrafluoroethylene), amorphous fluoropolymer, fluorine rubber, and fluorine-based polymer.

The molded product made of a material capable of transmitting fluorine gas is not particularly limited, and examples thereof include a membrane, a tube, and a laminate, and a membrane and a tube are preferable.
Further, as the membrane, an ion exchange membrane, a porous membrane or the like can also be used. The reaction rate can also be controlled by controlling the flow rate of fluorine gas using a fine porous membrane.

A solvent can be used in the production method.
The solvent is not particularly limited as long as it does not react with halogen. Examples of the solvent include acetonitrile, alcohols (ethanol, methanol, etc.), chloroform, perfluorohexane, perfluoroether, and the like, and acetonitrile and alcohols are preferable.
Further, when a molded product made of a material capable of transmitting the fluorine gas is used, it is preferable to use the solvent on the side where the compound of the general formula (1) is present from the viewpoint of work efficiency.

The reaction temperature in the production method is not particularly limited, but is preferably −200 ° C. to 200 ° C. The reaction temperature can be appropriately selected depending on the raw materials used.
When fluorine gas is used as the halogen, the reaction temperature is preferably −50 ° C. to 100 ° C., more preferably −20 ° C. to 80 ° C., and even more preferably 0 ° C. to 40 ° C.

The reaction pressure in the production method is not particularly limited and depends on each concentration of the compound and halogen of the general formula (1), but from the viewpoint of safety, 0 to 0.05 MPa is preferable, and 0 to 0.02 MPa is preferable. Is more preferable.
In the present specification, the pressure indicates a gauge pressure unless otherwise specified.

The reaction time in the production method is not particularly limited and depends on other reaction conditions and the like, but from the viewpoint of workability, 0.1 to 100 hours is preferable, and 1.0 to 20 hours is more preferable.

In the production method, various reactors such as a vertical reactor, a horizontal reactor, a multi-tube reactor, a flask, and an autoclave can be used. The material of the reactor is not particularly limited as long as it does not react with halogen, and examples thereof include glass, nickel, stainless steel, Hastelloy, and Inconel.

In the production method, it is preferable to stir and react the raw material mixture or the mixture of the raw material mixture and the solvent. The stirring means is not particularly limited, but for example, a stirrer provided with a mechanical seal, an electromagnetic stirring device, a means for rotating the entire reaction vessel, vibration, sound waves, ultrasonic waves, natural convection (density difference, temperature difference), forced convection. (Pump, etc.) and the like can be used. The stirring means (mixing method) can be used as a means for transporting the product from the reactor to the separator or the like, or as a means for returning the separated residue to the reactor.

The unsaturated halide obtained by the above reaction is preferably separated immediately.
As a result, the remaining compound of the general formula (1) can be further reacted with the halogen, and the compound of the general formula (1) can be efficiently converted into an unsaturated halide.

Since the reaction between the compound of the general formula (1) and the halogen proceeds extremely fast, when a small amount of halogen is used for the compound of the general formula (1), almost no halogen remains in the reaction product. Further, in the reaction product, there are an unsaturated halide of the target substance, an unreacted compound of the general formula (1), an inert gas used for dilution, a by-product and the like.

The separation method is not particularly limited, and examples thereof include methods such as distillation, adsorption, permeation, absorption with a solvent, and extraction distillation. These can be used alone or in combination.
For example, in the case of separation by distillation, it can be separated by the difference in boiling point of each compound present in the reaction product. Further, for the separation of compounds having different fluorine contents, it is possible to separate them by extraction using a solvent, and extraction distillation can also be applied.

From the viewpoint of separation efficiency, it is preferable to separate using an adsorbent.
The adsorbent is not particularly limited, and examples thereof include activated carbon and molecular sieves, and activated carbon is preferable. When activated carbon is used, unsaturated halides can be selectively adsorbed and separated efficiently, and the raw materials are hardly adsorbed and can be reused in the reaction.

By the above production method, an unsaturated halide can be efficiently produced.
As the obtained unsaturated halide, at least one selected from the group consisting of CHF = CHF, CF ₂ = CFH, CF ₃ CF = CFH, CF ₃ CF = CF ₂ and CF ₃ CF = CFCF ₃ is preferable.

Further, it is particularly preferable that the compound of the general formula (1) is acetylene and CHF = CHF (1,2-difluoroethylene, HFO-1132) is produced by using fluorine gas as a halogen.

HFO-1132 contains isomers of trans-1,2-difluoroethylene (HFO-1132 (E)) and cis-1,2-difluoroethylene (HFO-1132 (Z)). In the present disclosure, HFO-1132 includes any of HFO-1132 (E) alone, HFO-1132 (Z) alone, and a mixture of HFO-1132 (E) and HFO-1132 (Z).

2. 2. Method for Producing Saturated Halide In order to produce a saturated halide, the reaction between the compound of the general formula (1) and the halogen should proceed well, so that a sufficient amount of halogen is present in the reaction field, that is, It is preferable to maintain a large molar ratio of halogen (halogen / compound of general formula (1)) to the compound of general formula (1) existing in the reaction field for the reaction.

The concentration of the compound of the general formula (1) is not particularly limited, but is preferably 0.1 to 100% by volume, more preferably 1 to 100% by volume, from the viewpoint of obtaining a saturated halide and safety.
The concentration of the compound of the general formula (1) can be adjusted (diluted) with an inert gas.
The inert gas is not particularly limited, and examples thereof include nitrogen gas, helium gas, neon gas, argon gas and the like, and nitrogen gas is preferable.

The halogen is not particularly limited, and examples thereof include fluorine, chlorine, bromine, and iodine. From the viewpoint of usefulness, fluorine gas is preferable as the halogen.

The halogen is preferably diluted with an inert gas before use. It is more preferable to dilute the fluorine gas with an inert gas before use.
The inert gas is not particularly limited, and examples thereof include nitrogen gas, helium gas, neon gas, argon gas and the like, and nitrogen gas is preferable.
When fluorine gas is used as the halogen, there is no particular upper limit on the gas concentration, but from the viewpoint of safety, it is preferably 30% by volume or less. The lower limit of the gas concentration is preferably 0.05% by volume or more, more preferably 0.1% by volume or more, from the viewpoint of ease of separation of the obtained halide.

In the method for producing a saturated halide, halogen can also be supplied from a solid fluorine source. Fluorine is supplied from the solid fluorine source. Since the solid fluorine source is a solid, it is a local but high-concentration fluorine source, and is therefore preferable for the production of saturated halides. Further, as a halogen supply source, a fluorine gas and a solid fluorine source can be used in combination.
The solid fluorine source is not particularly limited, but for example, at least one selected from the group consisting of CoF ₃ , WF ₆ , VF ₆ , MoF ₆ and UF ₆ is preferable, and CoF ₃ is particularly preferable.

The molar ratio of halogen to the compound of the general formula (1) present in the reaction field (halogen / compound of the general formula (1)) is not particularly limited, but is preferably increased. For example, when fluorine gas is used as the halogen, the lower limit of the molar ratio of fluorine gas to the compound of the general formula (1) (fluorine gas / compound of the general formula (1)) existing in the reaction field is predominantly saturated halide. From the viewpoint of production, more than 0.04 is preferable.
When halogen is supplied from a solid fluorine source, the molar ratio of the solid fluorine source to the compound of the general formula (1) existing in the reaction field (solid fluorine source / compound of the general formula (1)) is a saturated halide. From the viewpoint of predominant production, more than 0.04 is preferable.

A solvent can be used in the production method. As the solvent, the same solvent as described in the above-mentioned method for producing an unsaturated halide is preferably used.
When a solid fluorine source is used, it can be dispersed in a fixed bed (gas flow type) or a solvent and reacted with the compound of the general formula (1).

The reaction temperature in the production method is not particularly limited, but is preferably −200 ° C. to 200 ° C. The reaction temperature can be appropriately selected depending on the raw materials used.
When fluorine gas is used as the halogen, the reaction temperature is preferably −50 ° C. to 100 ° C., more preferably −20 ° C. to 80 ° C., and even more preferably 0 ° C. to 40 ° C.
When the halogen is supplied from a solid fluorine source (particularly CoF ₃ ), the reaction temperature is preferably −20 ° C. to 200 ° C., more preferably 0 ° C. to 150 ° C.

The reaction pressure in the production method is not particularly limited and depends on each concentration of the compound and halogen of the general formula (1), but from the viewpoint of safety, 0 to 0.05 MPa is preferable, and 0 to 0.02 MPa is preferable. Is more preferable.

The reaction time in the production method is not particularly limited and depends on other reaction conditions and the like, but from the viewpoint of workability, 0.1 to 100 hours is preferable, and 1.0 to 20 hours is more preferable.

In the production method, various reactors can be used, and the same ones as described in the above-mentioned method for producing an unsaturated halide can be mentioned.

In the production method, it is preferable to stir and react the mixture of the raw material and the solvent. Examples of the stirring means include those described in the above-mentioned method for producing an unsaturated halide.

A saturated halide can be efficiently produced by the above production method.
The saturated halide obtained is at least one selected from the group consisting of CHF ₂ CHF ₂ , CF ₃ CF ₂ H, CF ₃ CF ₂ CF ₂ H, CF ₃ CF ₂ CF ₃ and CF ₃ CF ₂ CF ₂ CF _3. Seeds are preferred.

The compound of the general formula (1) is acetylene, and CHF ₂ CHF ₂ (1,1,2,2-tetrafluoro) by using fluorine gas as a halogen and / or supplying the halogen from CoF _{3 of a} solid fluorine source. It is particularly preferred to produce ethane, HFC-134).

In the above-mentioned method for producing a saturated halide, a method for producing a saturated halide from the compound of the general formula (1) by a one-step reaction has been described. As a method for producing a saturated halide, an unsaturated halide is produced and separated by the above-mentioned method for producing an unsaturated halide, and then the unsaturated halide is further reacted with a halogen to produce a saturated halide. You can also do it.

All of the conventional methods for producing halides go through multi-step reactions, the yield of each process is not necessarily high, and there are by-products, so steps such as purification are required, and the equipment is laborious and expensive. It was a thing.
However, according to the production method of the present disclosure, an unsaturated halide containing HFO-1132 and a saturated halide containing HFC-134 can be produced safely, efficiently and economically.

Although the embodiments have been described above, it will be understood that various modifications of the embodiments and details are possible without departing from the purpose and scope of the claims.

Hereinafter, examples will be described in more detail. However, the present disclosure is not limited to these examples.

Reference example: Production of acetylene In a pre-nitrogen-substituted reactor, acetone was used as the reaction solvent, and acetylene was generated by the reaction of calcium carbide with water. The generated gas is passed through a cooled superficial, by further preferably under the water, acetone and by-product H _{2 S} in a solvent, after removing the PH ₃ or the like, through a drying tower packed with granular calcium chloride Moisture was removed and collected in a cylinder at atmospheric pressure to obtain acetylene.
In the following examples, nitrogen-diluted acetylene was used as needed.

As the fluorine gas, 15.5% by volume F ₂ / N ₂ gas manufactured by Kanto Chemical Co., Inc. was used as it was (described as "15.5% by volume fluorine gas" in the following examples) or further diluted with nitrogen gas. ..
The gas obtained in each example was directly collected in a gas tight syringe, and the components were analyzed by gas chromatography using GCMS (gas chromatography-mass spectrometer) or FID (hydrogen flame ionization detector) as a detector. .. For gas chromatography, GCMS-QP2020 manufactured by SHIMADZU was used, and for the column, GS-GASPRO 60 m manufactured by Agilent Technologies, an inner diameter of 0.32 μm, and a film pressure of 0 (MPa) were used.
In each of the following examples, the pressure is also described as a gauge pressure.

Example 1
A fluororesin tube having an internal volume of about 10 cc was charged with acetylene gas diluted to 50% by volume at atmospheric pressure (0 MPa), and fluorine gas diluted to 15.5% by volume with nitrogen gas was charged over 10 seconds for reaction. .. At this time, the amount of fluorine gas was 10 mol% with respect to 100 mol% of acetylene (the molar ratio of fluorine gas to acetylene present in the reaction field was 0.1). About 20% of HFC-134 was observed as the gas produced, and it was confirmed that HFO-1132 produced a trace amount because peaks of m / z = 64 and 45 were simultaneously present by the SIM method.

Example 2
A PFA tube was inserted into the four-necked flask, and the outside of the tube and the inside of the flask were filled with 50% by volume acetylene. When 15.5% by volume fluorine gas was charged into the PFA tube at atmospheric pressure (0 MPa), both ends were closed, and after standing for 24 hours, the acetylene gas outside the tube and inside the flask was analyzed. I was not able to admit. After standing for 21 days, the generated gas outside the tube and inside the flask was analyzed. As a result, 0.5% of HFO-1132 and 0.1% of HFC-134 were detected.

Example 3
A PFA tube was passed through the SUS tube, 15.5% by volume of fluorine gas was supplied to the PFA tube, and the outside of the PFA tube and the inside of the SUS tube were filled with 100% by volume of acetylene gas. As shown in FIG. 1, these tubes are installed (the PFA tube corresponds to the molded product 1 made of a material capable of transmitting the fluorine gas of FIG. 1, and the SUS tube corresponds to the pressure resistant tube 2 of FIG. 1). The whole was cooled with cold water at 20 ° C. The gas after the reaction was extracted from the lower part, passed through an adsorption tower 4 filled with activated carbon as an adsorbent, and connected to the upper part of the reaction tube through an empty tower heated to 30 ° C. The gas inside is naturally convected due to the difference in specific gravity and temperature. It was operated for several days in this state. At this time, the amount of fluorine gas was 1 mol% with respect to 100 mol% of acetylene (the molar ratio of fluorine gas to acetylene present in the reaction field was 0.01).
The adsorption tower was removed, the adsorption tower was connected to a recovery cylinder under vacuum, the suction tower was heated, and the recovery cylinder was cooled with liquid nitrogen to recover the adsorbed components. The recovered gas was 37% for HFO-1132, 1% for HFC-134, and 60% for unreacted acetylene.

Example 4
0.26 g of CoF ₃ was charged into the autoclave under nitrogen, cooled to −20 ° C., and 50% by volume acetylene gas was introduced to atmospheric pressure (0 MPa). At this time, CoF ₃ was 100 mol% with respect to 100 mol% of acetylene (the molar ratio of CoF ₃ to acetylene present in the reaction field was 1). After that, the temperature was adjusted to room temperature (10 to 20 ° C.), the pressure was increased to 0.05 MPa with nitrogen, the gas inside was sampled, and measured by GCMS. As a result, HFC-134 was 0.17% and hydrofluorocarbon having 1 carbon atom ( It was observed that CH ₄ , CH ₃ F, CH ₂ F ₂ , CHF ₃ , CF ₄ ) were produced in an amount of about 0.01%. However, no formation of HFO-1132 was observed.

Example 5
The SUS tube was filled with 2.6 g of CoF ₃ and 50% by volume acetylene gas was supplied at 4 ml / min for 10 minutes while cooling to 10 ° C. When the gas that passed through the SUS tube was recovered with liquid nitrogen and measured by GCMS, hydrofluorocarbon having 62% acetylene, 34% HFC-134, and 1 carbon number (CH ₄ , CH ₃ F, CH ₂ F ₂ , CHF ₃ , CF ₄ ) was detected in 4%. However, no formation of HFO-1132 was observed.

1: Molded product made of a material that can permeate fluorine gas 2: Pressure-resistant tube 3: Temperature control cylinder 4: Adsorption tower (adsorption and recovery of target object)

Claims (15)

General formula (1)
(In the formula, X and Y independently represent H, F or CF ₃ , respectively.)
A method for producing a halide, which comprises reacting a compound of the above with a halogen. The compound of the general formula (1) is
The production method according to claim 1, which is at least one compound selected from the group consisting of. The production method according to claim 1 or 2, wherein the halogen is a fluorine gas. The production method according to claim 3, wherein the molar ratio of the fluorine gas to the compound of the general formula (1) present in the reaction field (fluorine gas / compound of the general formula (1)) is 0.04 or less. The production method according to claim 3 or 4, wherein the fluorine gas is diluted with an inert gas and used. The production method according to any one of claims 3 to 5, wherein the fluorine gas is permeated through a molded product made of a material capable of permeating the fluorine gas and reacted with the compound of the general formula (1). .. The production method according to claim 6, wherein the molded product made of a material capable of transmitting fluorine gas is a film or a tube. The production method according to any one of claims 1 to 7, wherein the halide is an unsaturated halide. The production method according to claim 8, wherein the obtained unsaturated halide is immediately separated. The production method according to claim 9, wherein the adsorbent is used for separation. Claimed that the unsaturated halide is at least one compound selected from the group consisting of CHF = CHF, CF ₂ = CFH, CF ₃ CF = CFH, CF ₃ CF = CF ₂ and CF ₃ CF = CFCF _3. Item 8. The production method according to any one of Items 8 to 10. The production method according to any one of claims 1 to 3, wherein the halide is a saturated halide. The production method according to claim 12, wherein the halogen is supplied from at least one solid fluorine source selected from the group consisting of CoF ₃ , WF ₆ , VF ₆ , MoF ₆ and UF ₆ . The production method according to claim 13, wherein the solid fluorine source is CoF ₃ . The saturated halide is at least one selected from the group consisting of CHF ₂ CHF ₂ , CF ₃ CF ₂ H, CF ₃ CF ₂ CF ₂ H, CF ₃ CF ₂ CF ₃ and CF ₃ CF ₂ CF ₂ CF ₃ . The production method according to any one of claims 12 to 14, which is a compound.