WO2019230456A1

WO2019230456A1 - Method for producing fluorine-containing propene

Info

Publication number: WO2019230456A1
Application number: PCT/JP2019/019762
Authority: WO
Inventors: 敏史仁平; 慎哉民辻; 優竹内
Original assignee: Ａｇｃ株式会社
Priority date: 2018-05-28
Filing date: 2019-05-17
Publication date: 2019-12-05
Also published as: JP7287391B2; JPWO2019230456A1

Abstract

The present invention provides a production method for efficiently obtaining a fluorine-containing propene having a -CF= structure with high yield with use of a fluorine-containing propane that has a -CF₂- structure in each molecule as a starting material. A method for producing a fluorine-containing propene, by which a fluorine-containing propene represented by formula (B) is obtained by subjecting a fluorine-containing chlorine-containing propane represented by formula (A) to a defluorination dechlorination reaction in the presence of a reducing agent that is composed of at least one element selected from among alkaline earth metals and transition metals. Formula (A): CY₃-CF₂-CClX₂ Formula (B): CY₃-CF=CX₂ In formula (A), each one of two X moieties independently represents F, Cl or H; and each one of three Y moieties independently represents F or H, excluding the cases where both of the two X moieties represent H. In formula (B), the X and Y moieties are as defined in formula (A).

Description

Method for producing fluorine-containing propene

The present invention relates to a method for efficiently producing a fluorine-containing propene.

Recently, hydrofluorocarbons (HFCs) and hydrochlorofluorocarbons (HCFCs) have been used for cleaning agents, refrigerants, foaming agents, solvents, aerosols and the like. However, it has been pointed out that these compounds may cause global warming. Therefore, fluorine-containing olefins such as hydrofluoroolefin (HFO) and hydrochlorofluoroolefin (HCFO) are attracting attention as compounds having a low global warming potential.

HFO and HCFO are known to have both low ozone depletion potential (ODP) and global warming potential (GWP). ing.

In particular, for use as a refrigerant or a solvent, a C3 unsaturated compound (hereinafter also referred to as fluorine-containing propene) that is HFO or HCFO and has three carbons in its structure is preferable. Further, among the fluorinated propenes, the fluorinated propene having a structure represented by —CF═ in the molecule has low toxicity and is particularly suitable for refrigerants and solvents. In addition, the fluorine-containing propene having a structure represented by —CF═CX ₂ (in the molecule, two X's are each independently F, Cl or H, and both X are H) is Compared with fluorine-containing propene having a structure represented by —CF═CH ₂ in the molecule, it has high nonflammability and excellent detergency, and is more suitable for refrigerants and solvents. Examples include 1-chloro-2,3,3,3-tetrafluoropropene (CF ₃ —CF═CClH, HCFO-1224yd), 1-chloro-2,3,3 trifluoropropene (CF ₂ H—CF═ CClH) and the like.

On the other hand, a fluorinated propene having —CF═ is produced, for example, by dechlorinating a fluorinated propane having —CFCl— as a precursor. However, since fluorinated propane having —CFCl— as a precursor is energetically unstable, it is difficult to obtain a fluorinated propene having —CF═ in a high yield. In addition, in the synthesis of fluorine-containing propane starting from tetrafluoroethylene (TFE), which is a key raw material in the fluorine chemical industry, a compound having —CF ₂ — is easily synthesized.

For these reasons, as a method for producing a fluorine-containing propene having —CF═, it is generally synthesized by dehydrohalogenation (see, for example, Patent Document 1). However, in order to obtain a precursor of dehydrohalogenation, a plurality of steps such as H ₂ reduction and halogenation are required as necessary, and the efficiency of the process is a problem.

In contrast, Patent Document 2 discloses a method of directly synthesizing a fluorinated propene having —CF═ by using a fluorinated propane having —CF ₂ — as a raw material and defluorinating and dechlorinating in an H ₂ reducing atmosphere. It is being considered. However, in the method of Patent Document 2, the target fluorine-containing propene having —CF═ is not obtained in high yield.

Further, in Non-Patent Document 1, a method of defluorinating and dechlorinating in the presence of metallic zinc has been attempted in the same manner as in Patent Document 2, but the same reaction system contains a substrate on which dechlorination proceeds, and the same. Since there are two defluorination and dechlorination routes in the substrate, the target fluorine-containing propene having —CF═ cannot be obtained in high yield.

International Publication No. 2017/110851 International Publication No. 1994/005611

An object of the present invention is to provide a production method for efficiently obtaining a fluorine-containing propene having a —CF═structure in a high yield by using a fluorine-containing propane having a —CF ₂ — structure as a raw material. To do. More particularly, a fluorine-containing propene having a structure represented by —CF═CX ₂ (X is independently F, Cl or H, except when both X are H) in the molecule, It aims at providing the manufacturing method obtained efficiently and with a high yield.

The present invention has the following aspects.
[1] A fluorine-containing chlorine-containing propane represented by the following formula (A) is defluorinated and dechlorinated in the presence of at least one reducing agent selected from alkaline earth metals and transition metals, and the following formula ( A method for producing a fluorinated propene, which obtains the fluorinated propene represented by B).
CY ₃ —CF ₂ —CClX ₂ formula (A)
CY ₃ -CF = CX Formula ₂ (B)
In formula (A), two Xs are each independently F, Cl or H, and three Ys are each independently F or H. However, the case where both X are H is excluded. X and Y in the formula (B) are the same as X and Y in the formula (A).
[2] The fluorine-containing chlorine-containing propane is 3,3-dichloro-1,1,1,2,2-pentafluoropropane, and the fluorine-containing propene is 1-chloro-2,3,3,3-tetra The production method of [1], which is fluoropropene.
[3] The production method of [1], wherein the fluorine-containing chlorine-containing propane is 1-chloro-1,1,2,2-tetrafluoropropane, and the fluorine-containing propene is 1,1,2-trifluoropropene .
[4] The fluorine-containing chlorine-containing propane is 1-chloro-1,1,2,2,3-pentafluoropropane, and the fluorine-containing propene is 1,1,2,3-tetrafluoropropene [1] ] The manufacturing method of description.
[5] The method according to any one of [1] to [4], wherein the reducing agent includes at least one selected from the group consisting of zinc, magnesium, copper, and nickel.
[6] The method according to any one of [1] to [5], wherein the reducing agent contains zinc.
[7] The method according to any one of [1] to [6], wherein the reducing agent is a reducing agent activated with an activating agent.
[8] The reducing agent has a particle size _{D 50} is a powder of 0.05 ~ 1000 .mu.m [1] one of the production method to [7].
[9] The production method of any one of [1] to [8], wherein the fluorine-containing chlorine-containing propane is defluorinated and dechlorinated in a liquid phase.
[10] The method according to [9], wherein the liquid phase contains a solvent that dissolves the fluorine-containing chlorine-containing propane.
[11] The solvent is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, N, N-dimethylformamide, acetonitrile, [10] A process for producing [10] comprising at least one selected from the group consisting of acetone, methyl ethyl ketone, diethyl ketone, and tetrahydrofuran.
[12] The production method according to any one of [1] to [11], wherein the reducing agent is used in a ratio of 0.6 to 3.0 mol with respect to 1.0 mol of the fluorine-containing chlorine-containing propane.
[13] The production method of any one of [1] to [12], wherein the defluorination dechlorination reaction is carried out in the presence of a catalyst containing copper halide.
[14] The production method according to [13], wherein 1 to 50 mol of the catalyst containing copper halide is used with respect to 1 mol of the fluorine-containing chlorine-containing propane.
[15] The production method according to any one of [1] to [14], wherein a reaction temperature of the defluorination dechlorination reaction is 0 ° C. or higher and 250 ° C. or lower.

According to the present invention, fluorine-containing propane having a —CF ₂ — structure in the molecule is used as a raw material, —CF═structure, in particular, —CF═CX ₂ (wherein X is independently F, Cl Or a fluorine-containing propene having a structure represented by the formula (except for the case where both X and H are both H), can be produced efficiently and in high yield under mild conditions.

Definitions of terms and how to describe them in the present specification are as follows.
“Halogenated hydrocarbon” is an abbreviation of the compound in parentheses after the compound name, and the abbreviation is used instead of the compound name as necessary. In addition, as an abbreviation, only the number after the hyphen (-) and the lowercase alphabet part (for example, HCFO-1224yd may be represented by 1224yd. (E) represents E form (trans form), and (Z) represents Z form (cis form) .If the E form or Z form is not specified in the name or abbreviation of the compound, the name or abbreviation is used. Means a generic name including E-form, Z-form, and a mixture of E-form and Z-form.

The “reaction represented by reaction formula (F)” is referred to as reaction (F). Reactions represented by other formulas are also expressed accordingly. The “compound represented by the formula (A)” is referred to as the compound (A). Compounds represented by other formulas are also represented accordingly.
“˜” representing a numerical range includes the upper limit value and the lower limit value thereof. When the lower limit value and the upper limit value of the numerical range are the same unit, one of the descriptions may be omitted for the sake of brevity.
The particle size D ₅₀ represents the particle size when the cumulative amount occupies 50% on the volume basis in the cumulative particle size curve of the particle size distribution measured using a laser diffraction / scattering type particle size distribution measuring apparatus.

(Production method of the present invention)
In the production method of the present invention, the fluorine-containing chlorine-containing propane represented by the formula (A) is a reducing agent composed of at least one selected from alkaline earth metals and transition metals (hereinafter also referred to as a reducing agent (M)). To obtain a fluorinated propene represented by the formula (B). The defluorination dechlorination reaction (hereinafter also referred to as deClF reaction) according to the present invention is represented by the following reaction formula (F).

In the reaction formula (F), two Xs in the compound (A) are each independently F, Cl or H, and three Ys are each independently F or H. However, the compound (A) does not include the case where both X are H. X and Y in the compound (B) are the same as X and Y in the compound (A).

In the deClF reaction, the present inventors obtain a fluorine-containing propene having a —CF═ structure in the molecule in the presence of a reducing agent from a fluorine-containing chlorine-containing propane having a —CF ₂ — structure in the molecule. It was found that the compound (B) as a product can be obtained in high yield by limiting the raw material to the compound (A) and combining the reducing agent with the reducing agent (M).

As described above, the de-ClF reaction has hitherto been recognized as being a simple method with a small number of reaction steps, but is not suitable as a method for producing a fluorinated propene with a very low yield. For example, in Patent Document 2, compound (A) is subjected to deClF reaction using hydrogen as a reducing agent to obtain compound (B), but the yield is less than 50%. In Non-Patent Document 1, for example, CClF ₂ —CF ₂ —CCl ₂ H having a structure different from that of the compound (A) is used as a raw material, and the compound (B) is subjected to a deClF reaction using a reducing agent (M). Although several types are obtained, the yield of the compound (B) is several percent or less in total. Thus, it has been said that the compound (B) cannot be obtained in a high yield by the deClF reaction proposed so far.

The present inventors first focused on the raw material of the deClF reaction using a reducing agent, and limited the structure of the raw material to the structure of the compound (A), that is, in CY ₃ —CF ₂ —CClX ₂ , It was thought that by using a raw material limited to F, Cl or H and Y limited to F or H, side reactions were suppressed as follows.
In the deClF reaction using a reducing agent from a fluorine-containing chlorine-containing propane having a —CF ₂ — structure in the molecule, F is extracted from —CF ₂ — by the reducing agent, and at the same time, out of carbon atoms at both ends. Cl bonded to one of the carbon atoms is extracted. Here, when Cl is present at both of the terminal carbon atoms, there are two reaction routes, and as a result, it is considered that a fluorine-containing propene having a —CF═ structure cannot be obtained in a high yield. Therefore, in the present invention, the raw material compound (A) has a configuration in which Cl is bonded to only one of the terminal carbon atoms so that unnecessary side reactions do not occur.

As a dehalogenation route from CY ₃ —CF ₂ —CClX ₂ (compound (A)), only a deClF route from —CF ₂ —CClX ₂ substantially exists. In the case where one or more of Y in the compound (A) is F, de-F ₂ from CY ₃ —CF ₂ — is also considered in principle as a dehalogenation route. However, since the C—F bond energy is extremely high, the reaction rate is extremely low, and even in that case, practically no de-F ₂ form is obtained. Therefore, it can be assumed that the compound (B) can be obtained in high yield by selecting the compound (A) as a raw material.

Even when the compound (A) is selected as a raw material, as in Patent Document 1, when hydrogen that is generally used is used as a reducing agent, a fluorine-containing propene having a —CF═ structure can be obtained in a high yield. I can't. The reason is not clear, but it is considered that the olefin produced is polymerized or decomposed because the hydrogen reducing ability is low and a higher temperature is required for the reduction. Therefore, by selecting the reducing agent (M), which is a reducing agent consisting of at least one selected from alkaline earth metals and transition metals, and using it in combination with the compound (A), the compound (B) can be obtained in a high yield. The present invention obtained in the above has been completed.

Specifically, in the deClF reaction (F) according to the production method of the present invention, the compound (B) can be produced in a high yield of 60% or more. Furthermore, in the deClF reaction (F) according to the production method of the present invention, the compound (B) can be obtained in a higher yield under milder conditions such as lowering the reaction temperature.

(Reaction to which the production method of the present invention can be applied)
Specific examples of the reaction to which the present invention is applied include deClF reactions represented by the following formulas (1) to (20).

CH ₃ —CF ₂ —CCl ₃ → CH ₃ —CF═CCl ₂ (1)
CFH ₂ —CF ₂ —CCl ₃ → CFH ₂ —CF═CCl ₂ (2)
CF ₂ H—CF ₂ —CCl ₃ → CF ₂ H—CF═CCl ₂ (3)
CF ₃ —CF ₂ —CCl ₃ → CF ₃ —CF═CCl ₂ (4)
CH ₃ —CF ₂ —CCl ₂ H → CH ₃ —CF═CClH (5)
CFH ₂ —CF ₂ —CCl ₂ H → CFH ₂ —CF═CClH (6)
CF ₂ H—CF ₂ —CCl ₂ H → CF ₂ H—CF═CClH (7)
CF ₃ —CF ₂ —CCl ₂ H → CF ₃ —CF═CClH (8)
CH ₃ —CF ₂ —CCl ₂ F → CH ₃ —CF═CClF (9)
CFH ₂ —CF ₂ —CCl ₂ F → CFH ₂ —CF═CClF (10)
CF ₂ H—CF ₂ —CCl ₂ F → CF ₂ H—CF═CClF (11)
CF ₃ —CF ₂ —CCl ₂ F → CF ₃ —CF═CClF (12)
CH ₃ —CF ₂ —CClFH → CH ₃ —CF═CFH (13)
_{_{_{CFH 2 -CF 2 -CClFH → CFH 2}}} -CF = CFH ... (14)
CF ₂ H—CF ₂ —CClFH → CF ₂ H—CF═CFH (15)
CF ₃ —CF ₂ —CClFH → CF ₃ —CF═CFH (16)
_{_{_{CH 3 -CF 2 -CClF 2 → CH}}} 3 -CF = CF 2 ... (17)
_{_{_{CFH 2 -CF 2 -CClF 2 → CFH}}} 2 -CF = CF 2 ... (18)
_{_{_{CF 2 H-CF 2 -CClF 2}}} → CF 2 H-CF = CF 2 ... (19)
_{_{_{CF 3 -CF 2 -CClF 2 → CF}}} 3 -CF = CF 2 ... (20)

In the deClF reaction represented by the above formulas (1) to (20), considering the availability of the compound (A) as a raw material and the usefulness of the compound (B) as a product, the present invention is suitable. As the reaction used, the deClF reaction (3), (4), (7), (8), (10), (11), (11), wherein the total number of fluorine atoms contained in the compound (A) is 4-6. 12), (14) to (19). Among these, it is particularly suitable for deClF reactions (8), (17) and (18).

The deClF reaction (8) is performed from 3,3-dichloro-1,1,1,2,2-pentafluoropropane (CF ₃ —CF ₂ —CCl ₂ H, HCFC-225ca; hereinafter also referred to as 225ca). , 1-chloro-2,3,3,3-tetrafluoropropene (CF ₃ —CF═CClH, HCFO-1224yd; hereinafter also referred to as 1224yd).

1224yd is a compound that is expected to be used particularly for refrigerants and solvents. For example, Patent Document 1 also proposes a production route from 225ca. However, in the method described in Patent Document 1, dehydrofluorination, H ₂ reduction, chlorination and dehydrochlorination are necessary, and there are problems that the number of steps is large and the production cost is high. However, by applying the production method of the present invention, it is possible to produce 1224yd in a single step and in a high yield by deClF reaction using a 225ca reducing agent (M). The effect is more remarkable.

The deClF reaction (17) is carried out from 1-chloro-1,1,2,2-tetrafluoropropane (CH ₃ —CF ₂ —CCIF ₂ , HCFC-244cc, hereinafter also referred to as 244 cc) to 1,1,1, This is a reaction for obtaining 2-trifluoropropene (CH ₃ —CF═CF ₂ , HFO-1243yc, hereinafter also referred to as 1243yc).
1243yc is a compound that has not been described in the literature regarding production so far, but according to the production method of the present invention, it is possible to carry out in one step by deClF reaction using 244 cc of reducing agent (M), which is an easily available raw material. In addition, it can be produced in a high yield. 1243yc is useful for applications such as refrigerants, foaming agents, aerosol propellants, resin raw materials for car air conditioners and vending machines, for example.

The deClF reaction (18) is carried out from 1-chloro-1,1,2,2,3-pentafluoropropane (CH ₂ F—CF ₂ —CClF ₂ , HCFC-235 cc, hereinafter also referred to as 235 cc) to 1 , 1,2,3-tetrafluoropropene (CH ₂ F—CF═CF ₂ , HFO-1234yc, hereinafter also referred to as 1234yc).
1234yc is a compound that has not been described in the literature with respect to production so far, but according to the production method of the present invention, it can be obtained in one step by deClF reaction using 235 cc of a reducing agent (M), which is an easily available raw material. In addition, it can be produced in a high yield. 1234yc is useful, for example, for applications such as refrigerants, foaming agents, aerosol propellants, resin raw materials for car air conditioners and vending machines.

(DeClF reaction)
In the production method of the present invention, the deClF reaction for obtaining the compound (B) from the compound (A) represented by the deClF reaction formulas (1) to (20) is performed at least selected from alkaline earth metals and transition metals. It is characterized in that it is carried out in the presence of one reducing agent (M).

<Compound (A)>
The method for obtaining the compound (A) is not particularly limited. You may manufacture by a well-known method and may use a commercial item. In the reaction of formula (8) to which the present invention is preferably applied, 225ca is, for example, a reaction between tetrafluoroethylene (TFE) and dichlorofluoromethane (CCl ₂ FH) in the presence of a Lewis acid catalyst such as aluminum chloride. Can be manufactured.
In this case, 225ca is 1,3-dichloro-1,1,2,2,3-pentafluoropropane (CClF ₂ -CF ₂ -CClFH, HCFC-225cb), 2,2-dichloro-1,1,3 , 3,3-pentafluoropropane (CHF ₂ —CCl ₂ —CF ₃ , HCFC-225aa), 2,3-dichloro-1,1,2,3,3-pentafluoropropane (CHF ₂ —CClF—CClF ₂₎ , HCFC-225bb) and the like in a dichloropentafluoropropane (HCFC-225) isomer mixture. Therefore, 225ca is separated from the HCFC-225 isomer mixture by a known method such as distillation and used as the compound (A).

Also, 225ca is distilled from a commercially available HCFC-225 isomer mixture containing 225ca, such as Asahiklin AK225 (AGC brand name, a mixture of 48 mol% of 225ca and 52 mol% of HCFC-225cb), etc. The compound (A) may be used after being separated by the above method.

Further, 244 cc in the reaction of the formula (17) to which the present invention is preferably applied can be produced, for example, by the following method (A) or method (B).
Method (A): TFE is reacted with at least one selected from CCl ₄ , CHCl ₃ and CH ₂ Cl _{2 in} the presence of a Lewis acid catalyst such as aluminum chloride to give CF ₂ Cl—CF ₂ —CClAB ( Wherein A and B are each independently H or Cl.), And the resulting compound is hydrogenated by reacting with hydrogen in the presence of a palladium catalyst or the like to yield 244 cc. How to get.
Method (B): A method in which 244 cc is obtained by reacting TFE and CH ₃ Cl in the presence of a Lewis acid catalyst such as aluminum chloride.

In method (A) or method (B), 244 cc is obtained as a reaction product containing unreacted raw materials, by-products and the like together with 244 cc. Therefore, 244 cc is separated and used as the compound (A) by a known purification process such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-layer separation, and adsorption.

Further, 235 cc in the reaction of the formula (18) to which the present invention is preferably applied can be produced by, for example, the method described in US Pat. No. 5,756,869. That is, it can be produced by hydrogenating 225cb by reacting with hydrogen in the presence of a bismuth-palladium catalyst supported on activated carbon. When the reaction product contains an isomer such as 225ca and HCFC in which the isomer is hydrogenated, 235 cc is separated and used as the compound (A) by a known purification step such as distillation.

In the production method of the present invention, compound (A) may be used for deClF reaction (F) in the form of a mixture containing compound (A) and impurities. The amount of impurities in the mixture is preferably set so as not to affect the effect of the production method of the present invention. Specifically, the compound (A) may be used together with by-products and unreacted raw materials that are by-produced during the production of the compound (A). For example, the composition containing the compound (A) having a purity of 85% by mass or more, preferably 90% by mass or more, and particularly preferably 95% by mass or more can be used in the present invention.

<Reducing agent (M)>
The reducing agent (M) used in the present invention is at least one selected from alkaline earth metals and transition metals. Specifically, the alkaline earth metal is beryllium, magnesium, calcium, strontium, barium, or radium. Specifically, the transition metal is a Group 3 element to a Group 12 element. The reducing agent (M) is preferably zinc, magnesium, copper, or nickel from the viewpoint of reactivity, more preferably zinc or magnesium, and particularly preferably zinc from the viewpoint of handling properties.
A reducing agent (M) may consist of 1 type of the said metal, and may consist of 2 or more types. In the case of 2 or more types, it may be a mixture or an alloy.

Although the form of a reducing agent (M) is not specifically limited, From a viewpoint of contact efficiency with a compound (A), it is preferable that it is a powder form, and the more nearly spherical powder form is preferable. The particle size is selected from the contact efficiency with the compound (A) and the ease of handling. When the reducing agent (M) is in powder form, the particle size D ₅₀ is preferably 0.05 to 1000 μm. The smaller the particle size, the better the contact efficiency between the compound (A) and the reducing agent (M), and the reaction proceeds, preferably 500 μm or less, more preferably 200 μm or less. Moreover, since the handling at the time of manufacture becomes easy so that a particle size is large, 0.1 micrometer or more is more preferable, and 0.5 micrometer or more is further more preferable.

In addition, the surface of the metal constituting the reducing agent (M) is easily oxidized by exposure to oxygen in the air. Therefore, the reducing agent (M) usually has a constituent metal oxide film on its surface. When it has an oxide film, the reducing ability of a reducing agent (M) may fall and reaction rate may fall. Therefore, the reducing agent (M) is preferably subjected to a pretreatment for removing the oxide film before being used in the present invention.

In order to remove the oxide film from the reducing agent (M), an activator is usually used. As the activator, an activator generally used for removing the oxide film on the metal surface can be used without particular limitation, and zinc chloride is suitable industrially. This is because, for example, when the deClF reaction according to the present invention is carried out in the liquid phase, the solubility of zinc chloride in a polar solvent is high, and particularly when zinc is used as the reducing agent (M), Since zinc chloride is produced as a by-product, there is no need to newly add an activator.

It is thought that the reason that zinc chloride functions as an activator is that hydrogen chloride generated due to moisture contained in a trace amount in the reaction system removes the oxide film on the metal surface. In addition to zinc chloride, dibromoethane can also be used as an activator.

In addition, you may perform the process of the reducing agent (M) by an activator in the reactor in which the deClF reaction (F) of a compound (A) is performed as mentioned later. Further, the compound (A), the reducing agent (M), and other components used for the deClF reaction (F) and the activating agent are charged into the reactor, and the reducing agent (M) is treated with the activating agent. A deClF reaction (F) may be performed. The amount of the activator is preferably 1 to 100 mol%, more preferably 10 to 50 mol%, and further preferably 20 to 50 mol% from the viewpoints of economy and reactivity with respect to the reducing agent (M). preferable. In the case of a batch reaction in which the reducing agent (M) is initially charged all at once, the reducing agent (M) decreases during the reaction. In that case, the amount is preferably from 1 to 100 mol%, more preferably from 10 to 50 mol% from the viewpoint of economy and reactivity, with respect to the maximum molar amount of the reducing agent (M) during the reaction. In the case of a liquid phase reaction, it is preferable to use the activator in a state in which the activator is dissolved in the solvent for ease of handling, and the saturated solubility in the solvent or less is preferable.

The amount of the reducing agent (M) used in the present invention is preferably 0.6 to 3.0 mol with respect to 1.0 mol of the compound (A). By making the usage-amount of a reducing agent (M) into the said range, while being able to obtain sufficient reaction rate, a compound (B) can be manufactured with a sufficiently high yield. However, when the amount of the reducing agent (M) used increases, the production cost increases. Therefore, the amount used is more preferably 0.6 to 1.5 mol, particularly preferably 0.8 to 1.2 mol, and 1.0 to 1.2 mol, relative to 1.0 mol of compound (A). Is most preferred. Further, even in the case of a fixed bed flow reactor type in which the compound (A) is continuously circulated through the reactor filled with the reducing agent (M), the reduction is performed with respect to 1.0 mol of the total amount of the compound (A) used. By setting the usage-amount of an agent (M) to the said range, while being able to obtain sufficient reaction rate, a compound (B) can be manufactured with a sufficiently high yield.

In the present invention, depending on the type of the compound (A), the reaction rate of the deClF reaction is low, and the production efficiency of the compound (B) may be low. In that case, the reaction rate can be increased by increasing the reaction temperature, but the reaction rate can be increased by using a catalyst to improve the production efficiency of the compound (B).
For example, when 1243yc is obtained using 244cc as the compound (A) by the deClF reaction of the above formula (17), the reaction rate is lower than the deClF reaction using 225ca according to the above formula (8). High temperature is required. Therefore, by using a catalyst, deClF reaction proceeds under milder conditions, and it is possible to obtain 1243yc as compound (B).

As the catalyst, copper halide is preferred. As the copper halide, copper (I) chloride, copper (I) bromide, or copper (I) iodide is preferable, and copper bromide (I) is more preferable. Furthermore, a catalyst obtained by complexing copper halide, particularly copper (I) bromide, with triphenylphosphine or the like is more preferable. By using the catalyst thus complexed, it becomes possible to obtain the compound (B) which is a deClF form with higher yield.
When a catalyst is used, the amount used is preferably 1 mol% to 50 mol%, more preferably 5 mol% to 20 mol%, relative to compound (A).

The deClF reaction in the present invention may be performed in the liquid phase or in the gas phase. The deClF reaction (F) is preferably carried out in a liquid phase from the viewpoint that it is easy to remove the halide of the reducing agent (M) by-produced in the deClF reaction represented by the above reaction formula (F).
For example, in the deClF reaction (F), when zinc (Zn) is used as the reducing agent (M), the reaction formula (F) is shown as follows. Here, Y and X are the same as in reaction formula (F).
CY ₃ —CF ₂ —CClX ₂ + Zn →
CY ₃ -CF = CX ₂ + 0.5ZnF ₂ + 0.5ZnCl ₂
Zinc, which is the reducing agent (M) in the above reaction formula, reacts with F and Cl generated by the deClF reaction of the compound (A), respectively, to generate zinc fluoride and zinc chloride. Therefore, the product after the reaction is compound (B), zinc fluoride and zinc chloride.

When the production method of the present invention is performed in a liquid phase, the liquid phase preferably contains a solvent. The solvent is preferably a solvent that is non-reactive with the compound (A) and the resulting compound (B) and that dissolves the compound (A). In addition, that a solvent melt | dissolves a compound (A) means that when a solvent and a compound (A) are mixed in arbitrary mixing ratios at 25 degreeC, it will melt | dissolve uniformly, without causing phase separation or turbidity.

It is preferable that the solvent further dissolves the chloride and fluoride of the reducing agent (M) by-produced in the deClF reaction (F). From this viewpoint, the solvent used for the deClF reaction (F) is preferably a polar solvent. The polar solvent is preferably at least one selected from the group consisting of alcohols, ethers, ketones, amide compounds, and nitrile compounds.

Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol and the like. Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone. Examples of the ether include chain ethers such as tetraethylene glycol dimethyl ether, dimethyl ether, ethyl methyl ether, diethyl ether, and ethylene oxide, and cyclic ethers such as tetrahydrofuran, furan, and crown ethers. Examples of the amide compound include N, N-dimethylformamide, and examples of the nitrile compound include acetonitrile.

Among these solvents, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, N, N-dimethylformamide, acetonitrile, Acetone, methyl ethyl ketone, diethyl ketone, or tetrahydrofuran is preferred. Furthermore, methanol, ethanol, tetrahydrofuran, acetone, N, N-dimethylformamide, or acetonitrile is used from the viewpoint of promoting the deClF reaction (F), availability, and ease of separation from the compound (B) after the deClF reaction. It is particularly preferable that an appropriate solvent can be selected from these in consideration of the reaction temperature and the degree of progress of side reactions. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
When the production method of the present invention is carried out in a liquid phase containing a solvent, the amount of the solvent used is preferably 10 to 2000 parts by mass, more preferably 20 to 1500 parts by mass with respect to 100 parts by mass of the compound (A), and 50 More preferred is ~ 500 parts by mass.

The reaction temperature of the deClF reaction (F) in the present invention depends on the type of the compound (A), but it is 0 to 250 ° C. from the viewpoint of increasing the reaction rate and the yield of the compound (B) regardless of the liquid phase or the gas phase. Is preferred. If the reaction temperature is too low, the reaction rate decreases and productivity decreases. Moreover, since decomposition | disassembly of a compound (A) and progress of a side reaction will advance when reaction temperature is too high, there exists a possibility that a yield may fall. In addition, there is a problem that the solvent that can be selected is limited and there is a problem that energy costs are required. For these reasons, the reaction temperature is more preferably 20 to 220 ° C, particularly preferably 50 to 180 ° C.

More specifically, when the deClF reaction (F) for obtaining 225ca to 1224yd is performed, the reaction temperature is preferably 20 to 150 ° C, more preferably 50 to 100 ° C. The reaction pressure is the pressure in the reactor for carrying out the reaction, and the gauge pressure is preferably 0 to 1 MPa, more preferably 0 to 0.5 MPa.

Further, when the deClF reaction (F) to obtain 1243yc from 244 cc is performed, the reaction temperature is preferably 50 to 250 ° C., more preferably 100 to 200 ° C. The reaction pressure is the pressure in the reactor for carrying out the reaction, and the gauge pressure is preferably 0 to 1 MPa, more preferably 0 to 0.5 MPa.
Further, when the deClF reaction (F) for obtaining 235 cc to 1234yc is performed, the reaction temperature is preferably 50 to 250 ° C, more preferably 100 to 200 ° C. The reaction pressure is the pressure in the reactor for carrying out the reaction, and the gauge pressure is preferably 0 to 1 MPa, more preferably 0 to 0.5 MPa.

The reaction time for the deClF reaction (F) in the present invention is selected from the viewpoint of the yield of the compound (B) and the reaction rate, and the time with the highest productivity is selected. 10 hours is more preferable, and 2 to 5 hours is particularly preferable.

The production method of the present invention may be carried out by any of batch, semi-continuous or continuous methods. The semi-continuous type can be exemplified by a fixed bed flow reactor type in which the compound (A) is continuously passed through the reactor filled with the reducing agent (M). From the viewpoint of industrially producing a target compound (B) in large quantities, a de-ClF reaction (F) is carried out by installing a stirring blade in a batch, semi-continuous or continuous reactor and stirring it. It is preferable. The reactor is not particularly limited as long as it can withstand the temperature and pressure in the reactor described above. For example, a flask, an autoclave, or a cylindrical vertical reactor can be used. Examples of the stirring blade include a 2-paddle blade, a 4-paddle blade, an anchor blade, a gate blade, a 3-propeller, a ribbon blade, and a 6-turbine blade. Further, the reactor may be provided with an electric heater for heating the inside of the reactor.

When the production method of the present invention is carried out in the liquid phase, it is usually carried out by introducing a predetermined amount of the compound (A), the solvent, the reducing agent (M) and, if necessary, the activator and catalyst into the reactor. . The material of the reactor is a material that is inert to the reaction liquid component containing the compound (A), the solvent, the reducing agent (M), the catalyst, the compound (B), and the halide of the reducing agent (M), and is corrosion resistant. If it is, it will not be restrict | limited. For example, glass or an alloy such as stainless steel mainly containing iron, nickel, iron, or the like can be given.

In the present invention, the reaction product obtained by performing the deClF reaction (F) in the reactor includes, in addition to the target product compound (B), unreacted compound (A), by-product, solvent, reduction Agent (M), activator, catalyst may be included. When recovering the compound (B) from the reaction product containing these, it is preferable to employ a separation and purification method such as filtration or distillation. A reactive distillation format in which distillation is performed simultaneously with the deClF reaction can also be employed.
For example, 1224yd obtained by deClF reaction from 225ca is obtained as a mixture of 1224yd (E) and 1224yd (Z). If necessary, 1224yd (E) and 1224yd (Z) may be separated and used by a general method such as distillation.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these descriptions.

Example 1 Production of 1224yd by DeClF Reaction of 225ca [Production of 225ca]
A product mainly composed of 225 ca and 225 cb obtained by reacting tetrafluoroethylene (TFE) and dichlorofluoromethane (CCl ₂ FH) in the presence of Lewis acid aluminum chloride (AlCl ₃ ) is separated by distillation. As a result, 225ca having a purity of 99% or more was obtained.

[Production of 1224yd]
In a 0.5 L autoclave (hereinafter referred to as A / C), 238 g of methanol (dehydrated product: manufactured by Kanto Chemical Co., Inc.) as a solvent, zinc powder (D ₅₀ ; 6-9 μm) as a reducing agent (M), organic For synthesis: 47 g (0.72 mol) of Fuji Film Wako Pure Chemical Industries, Ltd.), 9.8 g (0.072 mol) of zinc chloride as an activator, and 122 g (0.60 mol) of 225ca as compound (A) And sealed.

Subsequently, A / C was installed in the water bath, and it heated up to 75 degreeC which is reaction temperature. The temperature was raised in less than 1 hour, and the stirring blade was rotated at 300 rpm during the temperature rise and during the reaction. The stirring blades used were two paddle blades.
After the temperature was raised to 75 ° C., the temperature was controlled at ± 1 ° C., and the mixture was stirred for 4 hours. During the reaction, the deClF form is a low-boiling compound (boiling point of about 15 ° C.), so the reaction pressure gradually increases, but the reaction was carried out in a sealed state without purging.

After completion of the reaction, the temperature of the water bath was lowered and cooled to room temperature. After cooling to room temperature, the reaction solution was sampled from the insertion tube into a high pressure syringe and analyzed by gas chromatography (manufactured by Shimadzu Corporation, hereinafter referred to as GC).
By GC analysis, composition analysis of 225ca and 1224yd, which is a de-ClF form, was performed to calculate the conversion and selectivity. As a result, the conversion rate of 225ca was 99.6%, the selectivity of 1224yd was 88.5%, and 1224yd was obtained in a very high yield of 88.2%.

(Example 2) Production of 1243yc by 244cc deClF [production of 244cc]
Tetrafluoroethylene (TFE) and chloroform (CHCl ₃ ) are reacted in the presence of a Lewis acid, and 1,1,3-trichloro-2,2,3,3-tetrafluoropropane ( HCFC-224ca (hereinafter also referred to as 224ca) was produced, and 244 cc was produced from the obtained 224ca by the second step.

(1) Production of 224ca (first step)
According to the following reaction formula, 224ca was produced by the following procedure.
CHCl ₃ + TFE → 224ca
First, anhydrous aluminum chloride (25 g, 0.19 mol), CHCl ₃ (500 g, 4.19 mol) and 224ca (100 g, 0.45 mol) were put into 500 mL stainless steel A / C and degassed under reduced pressure while stirring. TFE was supplied until the inside of A / C reached 0.05 MPa, and the inside of A / C was heated to 80 ° C. Thereafter, TFE was further supplied while maintaining the pressure in A / C at 0.8 MPa. The total amount of TFE supplied to A / C was 0.17 kg (1.65 mol).

After further stirring for 1 hour, the reaction solution was cooled to room temperature and analyzed by GC. As a result, the conversion rate of CHCl ₃ was 33%, and the selectivity of 224ca was 84%. To the crude liquid obtained by filtering the liquid after the reaction, 102 g of molecular sieve 4A was added and stirred overnight to dehydrate. The crude liquid after stirring was separated by filtration, and the obtained crude product was purified by distillation to produce 224ca (230 g, 1.05 mol).

(2) Manufacture of 244cc (second process)
Using 224ca obtained by the above method as a raw material, 244cc was obtained by the following method.
First, a gas phase reactor (made of SUS316, diameter 25 mm, length 30 cm) composed of a cylindrical reaction tube equipped with an electric furnace was charged with activated carbon pellets (15 g) supporting palladium at a ratio of 2.0 mass%, The temperature was raised to 130 ° C. while flowing nitrogen (N ₂ ) gas (500 NmL / min). While maintaining the reaction tube at atmospheric pressure (1 atm), the catalyst was dried until the moisture in the gas obtained from the outlet of the reaction tube became 20 ppm or less. After the drying of the catalyst was completed, the supply of nitrogen was stopped, the reaction tube was heated to 200 ° C. while supplying hydrogen (180 mL / min), and then 224ca (0.44 g / min) was supplied.

The crude gas obtained from the outlet of the reaction tube was washed with water, acid and moisture were removed through an alkali washing tower and molecular sieve 5A, and then collected in a cold trap. When the collected crude product was analyzed by GC, the conversion of 224ca was 98%, and 1,3-dichloro-1,1,2,2-tetrafluoropropane (HCFC-234cc) had a selectivity of 24%. 244 cc was obtained with a selectivity of 70%. A total of 500 g (2.27 mol) of 224ca was reacted above to give 298 g of crude product.
The obtained crude product was subjected to normal pressure rectification in a 25-stage rectification column to obtain a total of 200 g of 244 cc.

[Production of 1243yc]
0.2 L of A / C, 47 g of N, N-dimethylformamide (dehydrated product: manufactured by Junsei Co., Ltd.) as the solvent, zinc powder (D ₅₀ ; 6-9 μm as the reducing agent (M), for organic synthesis: Fuji Film 11 g (0.17 mol) manufactured by Wako Pure Chemical Industries, Ltd., 2.3 g (0.017 mol) zinc chloride (manufactured by Junsei Chemical) as an activator, and 21 g (0.14 mol) 244 cc as compound (A) , Sealed.

Next, A / C was placed in an oil bath and the temperature was raised to 180 ° C., which is the reaction temperature. The temperature was raised for just over 1 hour, and the stirring blade was rotated at 300 rpm during the temperature rise and during the reaction. The stirring blades used were two paddle blades.
After maintaining at 180 ° C. for several hours, the temperature of the oil bath was lowered and cooled to room temperature. During the reaction, the reaction was carried out in a sealed state without purging.

After the temperature dropped to room temperature, the reaction solution was sampled from the insertion tube into a high pressure syringe and analyzed by GC.
The composition analysis of 244cc and 1243yc which is a de-ClF form was performed by GC analysis, and the conversion and selectivity were calculated. As a result, the conversion rate of 244 cc was 79.2%, the selectivity of 1243yc was 98.6%, and 1243yc could be obtained in a very high yield of 78.1%.

Comparative Example 1 Production of 3-chloro-1,2,3,3-tetrafluoropropene (CCIF ₂ —CF═CFH, HCFO-1224ye, hereinafter referred to as “1224ye”) by deClF reaction of 225cb In this manner, 225cb not corresponding to the compound (A) was subjected to deClF reaction in the presence of the reducing agent (M) to produce 1224ye.

[Manufacture of 225cb]
A commercially available product containing 99% or more of 225cb, Asahiklin AK225G (manufactured by AGC), was used as the compound (A).

[Production of 1224ye]
In a 20 cc reaction tube, 1.4 g of N, N-dimethylformamide (dehydrated product: manufactured by Junsei Co., Ltd.) as the solvent, zinc powder (D ₅₀ ; 6-9 μm) as the reducing agent (M), for organic synthesis: Fuji Film Kogyo Pharmaceutical Co., Ltd.) 0.3 g (4.5 mmol), 0.06 g (0.45 mmol) of zinc chloride as an activator, and 0.6 g (3.0 mmol) of 225cb not corresponding to compound (A) were charged. , Sealed.

The reaction tube was installed in a water bath, and the temperature was raised to 75 ° C., which is the reaction temperature. The temperature was raised in less than 10 minutes.
After raising the temperature to 75 ° C., the temperature was controlled at ± 1 ° C. and mixed for 4 hours. During the reaction, since the deClF form is a low boiling point compound, the reaction pressure gradually increases, but the reaction was carried out in a sealed state without purging.
After completion of the reaction, the temperature of the water bath was lowered and cooled to room temperature. After the temperature dropped to room temperature, the reaction solution was sampled from the insertion tube into a high pressure syringe and analyzed by GC.

The composition analysis of 224cb and 1224ye which is a de-ClF form was performed by GC analysis, and the conversion and selectivity were calculated. As a result, the conversion rate of 225cb was 19.2%, the selectivity of 1224ye was 1.70%, and the yield was as low as 0.33%. It is considered that the conversion rate did not increase because it was a reaction tube test without a stirring mechanism. However, the selectivity was very low, there were two or more deClF routes, and in the reaction test, solvent-derived desorption as a reaction byproduct. As a result, a large amount of Cl—H substitution product such as 1-chloro-1,2,2,3,3-pentafluoropropane (CF ₂ H—CF ₂ —CClFH, HCFC-235ca) was produced.

(Comparative Example 2)
1224ye was produced in the same manner as Comparative Example 1 except that the production method of 1224ye was changed to the following.
[Production of 1224ye]
Methanol (dehydrated product: manufactured by Kanto Chemical Co., Inc.) as a solvent in 0.2 L of A / C, zinc powder (D ₅₀ ; 6-9 μm as a reducing agent (M), for organic synthesis: Fuji Film Wako Pure Chemicals 15.7 g (0.24 mol), zinc chloride (made by Junsei) 32.7 g (0.24 mol) as activator, and 40.5 g (0.20 mol) 225cb as compound (A) And sealed.

Subsequently, A / C was installed in the water bath, and it heated up to 75 degreeC which is reaction temperature. The temperature was raised in less than 1 hour, and the stirring blade was rotated at 300 rpm during the temperature rise and during the reaction. The stirring blades used were two paddle blades.
After the temperature was raised to 75 ° C., the temperature was controlled at ± 1 ° C. and stirred for 5 hours. During the reaction, the deClF form is a low-boiling compound (boiling point of about 15 ° C.), so the reaction pressure gradually increases, but the reaction was carried out in a sealed state without purging.

The composition of 225cb and 1224ye which is a de-ClF form was analyzed by GC analysis, and the conversion and selectivity were calculated. As a result, the conversion rate of 225cb was 3.6%, the selectivity of 1224ye was 30.8%, and the yield was 1.1%, which was a very low yield.

(Examples 3 to 9)
In Examples 3 to 9, 1224yd was produced in the same manner as in Example 1 except that the conditions described in Tables 1 and 2 below were changed.

Example 10: Production of 1234yc (1,1,2,3-tetrafluoropropene) by de-ClF of 235 cc (1-chloro-1,1,2,2,3-pentafluoropropane) [Production of 235 cc ]
According to the method described in US Pat. No. 5,756,869, 1550 g of a crude product containing 16.4% by mass of 235 cc was obtained. The obtained crude product was subjected to normal pressure rectification in a 25-stage rectification column to obtain a total of 200 g of 235 cc.

[Production of 1234yc]
In 0.2 L of A / C, 55 g of N, N-dimethylformamide (dehydrated product: manufactured by Junsei Co., Ltd.) as a solvent, zinc powder (D ₅₀ ; 6-9 μm as a reducing agent (M), for organic synthesis: Fuji Film Wako Pure Chemical Industries, Ltd.) 12 g (0.18 mol), zinc chloride (manufactured by Junsei) as activator, 8.3 g (0.061 mol), and compound (A) 235 cc as 20 g (0.12 mol) are charged. And sealed.
Next, A / C was placed in an oil bath and the temperature was raised to 170 ° C., which is the reaction temperature. The temperature was raised for just over 1 hour, and the stirring blade was rotated at 300 rpm during the temperature rise and during the reaction. The stirring blades used were two paddle blades.

After maintaining at 170 ° C. for 2 hours, the temperature of the oil bath was lowered and cooled to room temperature. During the reaction, the reaction was carried out in a sealed state without purging.
After the temperature dropped to room temperature, the reaction solution was sampled from the insertion tube into a high pressure syringe and analyzed by GC.
By GC analysis, composition analysis of 235 cc and 1234yc which is a de-ClF form was performed to calculate conversion and selectivity. As a result, the conversion rate of 235 cc was 78.2%, the selectivity of 1234yc was 89.3%, and 1234yc could be obtained in a high yield of 69.8%.

From Examples 1 and 3 to 9, it was found that 1224yd was obtained with high selectivity and high selectivity. Moreover, it was found from a comparison between Example 1 and Example 7 that the selectivity of 225ca tends to be higher by increasing the amount of zinc chloride that is an activator. Moreover, it turned out from the comparison with Example 4 and Example 9 that the conversion rate of 225ca tends to become high by increasing the usage-amount of zinc which is a reducing agent.
From Example 2, it was found that 1243yc can be obtained with high selectivity and high selectivity. From Example 10, it was found that according to the production method of the present invention, 1234yc can be obtained with high selectivity and high selectivity.

The specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-101495 filed on May 28, 2018 and Japanese Patent Application No. 2018-177771 filed on September 20, 2018. The entire contents of this document are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

The fluorine-containing chlorine-containing propane represented by the following formula (A) is defluorinated and dechlorinated in the presence of at least one reducing agent selected from alkaline earth metals and transition metals, and the following formula (B) A method for producing a fluorine-containing propene, which obtains the fluorine-containing propene shown.
CY 3 —CF 2 —CClX 2 formula (A)
CY 3 -CF = CX Formula 2 (B)
However, in the formula (A), two Xs are each independently F, Cl or H, and three Ys are each independently F or H. However, the case where both X are H is excluded. X and Y in the formula (B) are the same as X and Y in the formula (A).
The fluorine-containing chlorine-containing propane is 3,3-dichloro-1,1,1,2,2-pentafluoropropane, and the fluorine-containing propene is 1-chloro-2,3,3,3-tetrafluoropropene. The manufacturing method according to claim 1.
The production method according to claim 1, wherein the fluorine-containing chlorine-containing propane is 1-chloro-1,1,2,2-tetrafluoropropane, and the fluorine-containing propene is 1,1,2-trifluoropropene.
2. The fluorine-containing chlorine-containing propane is 1-chloro-1,1,2,2,3-pentafluoropropane, and the fluorine-containing propene is 1,1,2,3-tetrafluoropropene. Manufacturing method.
The production method according to any one of claims 1 to 4, wherein the reducing agent includes at least one selected from the group consisting of zinc, magnesium, copper, and nickel.
The production method according to any one of claims 1 to 5, wherein the reducing agent contains zinc.
The production method according to any one of claims 1 to 6, wherein the reducing agent is a reducing agent activated by an activating agent.
The reducing agent is a powder having a particle size D 50 of 0.05 ~ 1000 .mu.m, the production method according to any one of claims 1 to 7.
The production method according to any one of claims 1 to 8, wherein the fluorine-containing chlorine-containing propane is defluorinated and dechlorinated in a liquid phase.
The method according to claim 9, wherein the liquid phase contains a solvent that dissolves the fluorine-containing chlorine-containing propane.
The solvent is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, N, N-dimethylformamide, acetonitrile, acetone, methyl ethyl ketone. The manufacturing method of Claim 10 containing at least 1 sort (s) chosen from the group which consists of, diethyl ketone, and tetrahydrofuran.
The production method according to any one of claims 1 to 11, wherein the reducing agent is used in a ratio of 0.6 to 3.0 mol with respect to 1.0 mol of the fluorine-containing chlorine-containing propane.
The production method according to any one of claims 1 to 12, wherein the defluorination and dechlorination reaction is carried out in the presence of a catalyst containing copper halide.
The production method according to claim 13, wherein the catalyst containing copper halide is used in an amount of 1 to 50 mol per 1 mol of the fluorine-containing chlorine-containing propane.
The production method according to any one of claims 1 to 14, wherein a reaction temperature of the defluorination dechlorination reaction is 0 to 250 ° C.