JP2024083607A - Method for producing halogenated alkene compounds - Google Patents

Abstract

[Problem] To provide a method for efficiently obtaining a halogenated alkene compound. [Solution] A method for producing a halogenated alkene compound represented by general formula (1): R1-CR2=CR3-R4(1), comprising a step of subjecting a halogenated alkane compound represented by general formula (2): R1-CHR2-CXR3-R4(2) to a dehydrohalogenation reaction in the presence of a catalyst and an unsaturated compound, wherein the unsaturated compound is a compound represented by general formula (3): R5-CR6=CR7-R8(3) or general formula (4): R9-C≡C-R10(4), and the compound represented by general formula (1) and the unsaturated compound are different compounds. [Selected Figure] None

Description

The present disclosure relates to a method for producing a halogenated alkene compound.

As a method for producing a halogenated alkene compound, for example, Patent Document 1 discloses a method for dehydrohalogenating a specific halogenated alkane compound (see, for example, Patent Document 1).

International Publication No. 2020/171011

The present disclosure aims to provide a method for efficiently obtaining halogenated alkene compounds.

This disclosure includes the following:

Item 1. General formula (1):
R ¹ -CR ² ═CR ³ -R ⁴ (1)
In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom or a haloalkyl group, provided that one of R ² and R ³ is a hydrogen atom and the other is a halogen atom. It is an atom.
A method for producing a halogenated alkene compound represented by the following formula:
General formula (2):
R ¹ -CHR ² -CXR ³ -R ⁴ (2)
[In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as defined above. X represents a halogen atom.]
The method includes a step of subjecting a halogenated alkane compound represented by the following formula (1) to a dehydrohalogenation reaction in the presence of a catalyst and an unsaturated compound,
The unsaturated compound is represented by the general formula (3):
R ⁵ -CR ⁶ ═CR ⁷ -R ⁸ (3)
[wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or an organic group.], or general formula (4):
R ⁹ -C≡C-R ¹⁰ (4)
[In the formula, R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom or an organic group.]
and
The production method, wherein the compound represented by the general formula (1) and the unsaturated compound are different compounds.

Item 2. The method according to item 1, wherein in the general formulas (1) and (2), R ¹ and R ⁴ are a fluorine atom or a perfluoroalkyl group.

Item 3. The method according to item 1 or 2, wherein the energy level of the highest occupied molecular orbital (HOMO) of the unsaturated compound is higher than the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by the general formula (1).

Item 4. The method according to any one of items 1 to 3, wherein the amount of the unsaturated compound fed is 0.001 to 0.40 moles per mole of the halogenated alkane compound represented by the general formula (2).

Item 5. The method according to any one of items 1 to 4, in which the dehydrohalogenation reaction is carried out in a gas phase.

Item 6. General formula (1):
R ¹ -CR ² ═CR ³ -R ⁴ (1)
In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom or a haloalkyl group, provided that one of R ² and R ³ is a hydrogen atom and the other is a halogen atom. It is an atom.
and 50 to 80 mol % of a halogenated alkene compound represented by the following formula:
General formula (5):
R ¹ -CH=CH-R ⁴ (5)
[In the formula, R ¹ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom, or a haloalkyl group.]
and 12 to 40 mol % of a halogenated alkene compound represented by the formula:

Item 7. Furthermore, the general formula (6):
R ⁵ -CR ⁶ R ¹¹ -CR ⁷ R ¹² -R ⁸ (6)
[In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or an organic group. One of R ¹¹ and R ¹² is a hydrogen atom, and the other is a halogen atom.]
Item 7. The composition according to item 6, comprising a halogenated alkane compound represented by the formula:

Item 8. The composition according to item 7, in which the content of the halogenated alkane compound represented by the general formula (6) is 0.10 to 10.0 mol %.

Item 9. The composition according to any one of items 6 to 8, which is used as a cleaning gas, an etching gas, a refrigerant, a heat transfer medium, or a building block for organic synthesis.

According to the present disclosure, halogenated alkene compounds can be efficiently synthesized.

In this specification, "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of."

In addition, in this specification, when a numerical range is indicated as "A to B," it means A or more and B or less.

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

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

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

Halogenated butyne compounds, such as hexafluoro-2-butyne, are known to be synthesized by carrying out two dehydrohalogenation reactions using specific halogenated alkane compounds as starting materials.

Here, when a dehydrohalogenation reaction is carried out from a halogenated alkane compound, hydrogen halide is liberated. When the product halogenated alkene compound reacts with the liberated hydrogen halide, the raw material halogenated alkane compound is produced again. Therefore, to obtain a halogenated butyne compound, the yield can be improved by carrying out two dehydrohalogenation reactions using the halogenated alkane compound as the starting material instead of one dehydrohalogenation reaction.

On the other hand, in the present disclosure, the dehydrohalogenation reaction of a halogenated alkane compound is carried out in the presence of a specific unsaturated compound, so that the hydrogen halide produced by the dehydrohalogenation reaction can be trapped in the specific unsaturated compound. As a result, the halogenated alkane compound, which is the raw material, reacts almost quantitatively, and a halogenated alkene compound can be obtained with high selectivity and high yield.

1. Method for Producing a Halogenated Alkene Compound The method for producing a halogenated alkene compound according to the present disclosure includes the steps of:
General formula (1):
R ¹ -CR ² ═CR ³ -R ⁴ (1)
[In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom or a haloalkyl group, provided that one of R ² and R ³ is a hydrogen atom and the other is a halogen atom.]
A method for producing a halogenated alkene compound represented by the following formula:
General formula (2):
R ¹ -CHR ² -CXR ³ -R ⁴ (2)
[In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as defined above. X represents a halogen atom.]
The method includes a step of subjecting a halogenated alkane compound represented by the following formula (1) to a dehydrohalogenation reaction in the presence of a catalyst and an unsaturated compound,
The unsaturated compound is represented by the general formula (3):
R ⁵ -CR ⁶ ═CR ⁷ -R ⁸ (3)
[R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or an organic group.]
Or general formula (4):
R ⁹ -C≡C-R ¹⁰ (4)
[In the formula, R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom or an organic group.]
and
The compound represented by the general formula (1) and the unsaturated compound are different compounds.

According to the present disclosure, by carrying out the dehydrohalogenation reaction of the halogenated alkane compound represented by the above general formula (2) in the presence of a specific unsaturated compound, the hydrogen halide produced by the dehydrohalogenation reaction can be trapped in the specific unsaturated compound. Therefore, the halogenated alkane compound as the raw material reacts almost quantitatively, and a halogenated alkene compound represented by general formula (1) can be selectively obtained in which 1 mole of hydrogen halide is eliminated per 1 mole of the halogenated alkane compound represented by general formula (2).

(1-1) Raw material compound (halogenated alkane compound)
The halogenated alkane compound usable as a substrate in the production method of the present disclosure is represented by the general formula (2):
R ¹ -CHR ² -CXR ³ -R ⁴ (2)
[In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom or a haloalkyl group, provided that one of R ² and R ³ is a hydrogen atom and the other is a halogen atom, and X represents a halogen atom.]
It is a halogenated alkane compound represented by the formula:

In the general formula (2), examples of the halogen atom represented by R ¹ , R ² , R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (2), the haloalkyl group represented by R ¹ , R ² , R ³ and R ⁴ means an alkyl group in which at least one hydrogen atom is substituted with a halogen atom. Among the haloalkyl groups, an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom is called a fluoroalkyl group, and an alkyl group in which all hydrogen atoms are substituted with fluorine atoms is called a perfluoroalkyl group. Among the haloalkyl groups, an alkyl group in which at least one hydrogen atom is substituted with a chlorine atom is called a chloroalkyl group, and an alkyl group in which all hydrogen atoms are substituted with chlorine atoms is called a perchloroalkyl group. Among the haloalkyl groups, an alkyl group in which at least one hydrogen atom is substituted with a bromine atom is called a bromoalkyl group, and an alkyl group in which all hydrogen atoms are substituted with bromine atoms is called a perbromoalkyl group. Among them, from the viewpoint of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by the general formula (1), etc., a fluoroalkyl group is preferred, and a perfluoroalkyl group is more preferred.

The haloalkyl group may be linear, branched, or cyclic. Of these, linear haloalkyl groups are preferred from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), etc.

The number of carbon atoms in the haloalkyl group is not particularly limited, but from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), etc., it is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.

Specific examples of such fluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and heptafluoropropyl groups. Specific examples of chloroalkyl groups include trichloromethyl, pentachloroethyl, and heptachloropropyl groups. Specific examples of bromoalkyl groups include tribromomethyl, pentabromoethyl, and heptabromopropyl groups.

The halogenated alkene compound represented by the general formula (1) also functions as an intermediate for obtaining a halogenated alkyne compound by a dehydrohalogenation reaction thereafter. Therefore, in order to allow dehydrohalogenation of the halogenated alkene compound represented by the general formula (1), one of ^R2 and ^R3 in the general formula (2) is a hydrogen atom, and the other is a halogen atom.

In general formula (2), from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), and the like, ^R1 and ^R4 are preferably a fluorine atom or a fluoroalkyl group, more preferably a fluorine atom or a perfluoroalkyl group, and further preferably a perfluoroalkyl group.

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

_{Specific examples of halogenated alkane} compounds that can serve as a substrate and satisfy these conditions include _CF2HCF2H , _{CFH2CF3 , CCl2HCCl2H , CClH2CCl3 , CBr2HCBr2H , CBrH2CBr3 , CF3CFHCF2H , CF3CH2CF3 , CCl3CClHCCl2H , CCl3CH2CCl3 , CBr3CBrHCBr2H , CBr3CH2CBr3 , CF3CFHCFHCF3 , CF3CH2CF2CF3 , CCl3CClHCClHCCl3 , CCl 3CH2CCl2CCl3 , CBr3CBrHCBrHCBr3 , CBr3CH2CBr2CBr3 , CH3CF3 , CH3CCl3 , CH3CBr3 , CF3CF2CH3 , CCl3CCl2CH3 , CBr3CBr2CH3 , CF3CH2CF2CH3 , CF3CHFCF2CH3 , CCl3CH2CCl2CH3 , CCl3CHClCCl2CH3 , CBr3CH2CBr2CH3 , CBr3CHBrCBr ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 2CH3 ,} etc.

These halogenated alkane compounds can be used alone or in combination of two or more. Such halogenated alkane compounds can be publicly known or commercially available products.

(1-2) Dehydrofluorination Reaction In the process of dehydrofluorinating a halogenated alkane compound in the present disclosure, the reaction is carried out according to the following reaction formula:
R1 ^- CHR2 ^- CXR3 ^{-R4 →} R1 ^{- CR2} = ^CR3 - ^R4 +HX
The dehydrohalogenation reaction can be carried out according to the following procedure.

Among these, from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by the general formula (1), etc., it is preferable that R ¹ and R ^{4 are trifluoromethyl groups, R 2 is a fluorine atom, R 3 is a hydrogen atom, and X is a fluorine atom. That is, it is preferable that R 1 and R 4} are trifluoromethyl groups, R ² is a fluorine atom, R ³ is a hydrogen atom, and X is a fluorine atom.
_{CF3CFHCFHCF3 → CF3CF} = _CHCF3 + HF
It is preferable to carry out the dehydrofluorination reaction according to the following procedure.

(1-3) Catalyst The step of dehydrohalogenating a halogenated alkane compound in the present disclosure is carried out in the presence of a catalyst.

The catalyst used in the manufacturing method of the present disclosure is preferably an activated carbon catalyst, a zeolite catalyst, a chromium oxide catalyst, a silica-alumina catalyst, or the like. Both non-fluorinated and fluorinated catalysts can be used as these catalysts.

The activated carbon catalyst is not particularly limited, and examples include powdered activated carbon such as crushed carbon, shaped carbon, granular carbon, and spherical carbon. It is preferable to use powdered activated carbon that has a particle size of 4 mesh (4.75 mm) to 100 mesh (0.150 mm) in the JIS test (JIS Z8801).

These activated carbons can be used alone or in combination of two or more. These activated carbons can be publicly known or commercially available products.

Since activated carbon becomes more active when fluorinated, it is also possible to use fluorinated activated carbon, which is obtained by fluorinating activated carbon before use in a reaction, as an activated carbon catalyst. In other words, both non-fluorinated activated carbon and fluorinated activated carbon can be used as the activated carbon catalyst.

As the fluorinating agent for fluorinating activated carbon, for example, in addition to inorganic fluorinating agents such as _F2 and HF, organic fluorinating agents such as hydrofluorocarbons (HFCs) such as hexafluoropropene, chlorofluorocarbons (CFCs) such as chlorofluoromethane, and hydrochlorofluorocarbons (HCFCs) can also be used.

One method for fluorinating activated carbon is, for example, to pass the above-mentioned fluorinating agent through the carbon under atmospheric pressure at temperatures between room temperature (25°C) and about 400°C.

As the zeolite catalyst, a wide variety of known types of zeolite can be used. For example, crystalline hydrous aluminosilicates of alkali metals or alkaline earth metals are preferred. The crystal form of the zeolite is not particularly limited, and examples thereof include A-type, X-type, and LSX-type. The alkali metal or alkaline earth metal in the zeolite is not particularly limited, and examples thereof include potassium, sodium, calcium, and lithium.

Zeolite catalysts become more active when fluorinated, so they can be fluorinated before use in a reaction to become fluorinated zeolite catalysts.

As the fluorinating agent for fluorinating the zeolite catalyst, for example, inorganic fluorinating agents such as F ₂ and HF, and fluorocarbon-based organic fluorinating agents such as hexafluoropropene can be used.

One method for fluorinating a zeolite catalyst is, for example, to pass the above-mentioned fluorinating agent through the catalyst at atmospheric pressure and at temperatures between room temperature (25°C) and about 400°C.

The chromium oxide catalyst is not particularly limited, but when chromium oxide is expressed as CrO _m , it is preferable that m is 1.5<m<3.0, more preferably 2.0<m<2.75, and even more preferably 2.0<m<2.3. When chromium oxide is expressed as CrO _{m.nH 2} O, it may be hydrated so that the value of n is 3 or less, particularly 1.0 to 1.5.

The fluorinated chromium oxide catalyst can be prepared by fluorinating the above-mentioned chromium oxide catalyst. This fluorination can be carried out using, for example, HF, fluorocarbons, etc. Such a fluorinated chromium oxide catalyst can be synthesized, for example, according to the method described in JP-A-05-146680.

The silica-alumina catalyst is a composite oxide catalyst containing silica (SiO ₂ ) and alumina (Al ₂ O ₃ ). With the total amount of silica and alumina being 100 mass %, for example, a catalyst having a silica content of 20 to 90 mass %, particularly 50 to 80 mass %, can be used.

Since silica-alumina catalysts become more active when fluorinated, they can be fluorinated before use in the reaction to produce fluorinated silica-alumina catalysts.

As the fluorinating agent for fluorinating the silica-alumina catalyst, for example, inorganic fluorinating agents such as F ₂ and HF, and fluorocarbon-based organic fluorinating agents such as hexafluoropropene can be used.

One example of a method for fluorinating a silica-alumina catalyst is to pass the above-mentioned fluorinating agent through the catalyst at atmospheric pressure and at temperatures between room temperature (25°C) and about 400°C.

The above catalysts can be used alone or in combination of two or more. The above catalysts can be publicly known or commercially available products.

Among these, from the viewpoints of conversion rate, selectivity, and yield, activated carbon catalysts (activated carbon or fluorinated activated carbon), chromium oxide catalysts (chromium oxide or fluorinated chromium oxide), etc. are preferred, with activated carbon catalysts (activated carbon or fluorinated activated carbon) being more preferred.

In addition, when the above-mentioned zeolite catalyst, chromium oxide catalyst, silica alumina catalyst, etc. are used as the catalyst, it is possible to support them on a carrier. Examples of such carriers include carbon, alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), silica (SiO ₂ ), titania (TiO ₂ ), etc. Examples of carbon that can be used include activated carbon, amorphous carbon, graphite, diamond, etc.

In the manufacturing method of the present disclosure, when a halogenated alkane compound is dehydrohalogenated in the gas phase in the presence of a catalyst, it is preferable to contact the catalyst in a solid state (solid phase) with the halogenated alkane compound. In this case, the catalyst can be in the form of a powder, but a pellet shape is preferable when the catalyst is used in a gas phase continuous flow reaction.

The specific surface area of the catalyst measured by the BET method (hereinafter sometimes referred to as "BET specific surface area") is usually preferably 10 to 3000 m ² /g, more preferably 15 to 2500 m ² /g, further preferably 20 to 2000 m ² /g, and particularly preferably 30 to 1500 m ² /g. When the BET specific surface area of the catalyst is within such a range, the density of the catalyst particles is not too small, so that the halogenated alkene compound can be obtained with higher selectivity and yield. It is also possible to further improve the conversion rate of the halogenated alkane compound.

(1-4) Unsaturated Compound In the present disclosure, the step of dehydrohalogenating the above-mentioned halogenated alkane compound is carried out in the presence of an unsaturated compound.

Unsaturated compounds refer to compounds that have at least one unsaturated bond (double bond, triple bond, etc.).

This unsaturated compound can trap hydrogen halide generated by the dehydrohalogenation reaction of the halogenated alkane compound represented by general formula (2). When the unsaturated compound traps hydrogen halide, a hydrogen halide addition reaction occurs with the unsaturated compound.

For example, when CF ₃ CFHCFHCF ₃ is used as the halogenated alkane compound represented by the general formula (2) and CF ₃ CF═CFCF ₃ is used as the unsaturated compound, the reaction proceeds according to the following reaction formula:
_{CF3CFHCFHCF3 → CF3CF} = _CHCF3 + HF
Hydrogen fluoride is generated by the following reaction:
_CF3CF = _CFCF3 + _{HF → CF3CF2CFHCF3}
The hydrogen fluoride produced by this is trapped.

In this way, it is possible to prevent the hydrogen halide generated by the dehydrohalogenation reaction of the halogenated alkane compound represented by general formula (2) from reacting with the target halogenated alkene compound represented by general formula (1) to produce the raw material halogenated alkane compound represented by general formula (2).

By trapping the hydrogen halide with the unsaturated compound, the equilibrium of the dehydrohalogenation reaction shifts toward the product (the halogenated alkene compound represented by general formula (1)), and the raw material, the halogenated alkane compound represented by general formula (2), reacts almost quantitatively, allowing the halogenated alkene compound represented by general formula (1) to be obtained with high selectivity and high yield.

Here, the addition reaction between olefins, i.e. compounds with unsaturated bonds, and hydrogen halides occurs at the energy orbitals of the highest occupied molecular orbital (HOMO) of the olefin and the lowest unoccupied molecular orbital (LUMO) of the hydrogen halide. Therefore, the smaller the difference in energy levels between the highest occupied molecular orbital (HOMO) of the olefin and the lowest unoccupied molecular orbital (LUMO) of the hydrogen halide, the higher the reactivity.

The unsaturated compound to be added and the halogenated alkene compound represented by general formula (1) undergo an addition reaction with the same hydrogen halide, so the difference in energy level between the highest occupied molecular orbital (HOMO) of the halogenated alkene compound and the lowest unoccupied molecular orbital (LUMO) of the hydrogen halide is due to the difference in energy level of the highest occupied molecular orbital (HOMO) of the halogenated alkene compound.

When the highest occupied molecular orbital (HOMO) of the unsaturated compound is higher than the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by general formula (1), the reaction of trapping hydrogen fluoride by the unsaturated compound occurs preferentially over the reverse reaction between the halogenated alkene compound represented by general formula (1) and hydrogen fluoride.

Similarly, when the unsaturated compound is a compound represented by general formula (4) having a triple bond, if the highest occupied molecular orbital (HOMO) of the compound represented by general formula (4) having a triple bond is at a higher energy level than the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by general formula (1), the trapping reaction of hydrogen fluoride by the compound represented by general formula (4) having a triple bond occurs preferentially over the reverse reaction with hydrogen fluoride of the halogenated alkene compound represented by general formula (1).

In other words, it is preferable to select an unsaturated compound whose highest occupied molecular orbital (HOMO) is higher than the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by general formula (1).

For this reason, the unsaturated compound used in the present disclosure is specifically represented by the general formula (3):
R ⁵ -CR ⁶ ═CR ⁷ -R ⁸ (3)
[wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or an organic group.], or general formula (4):
R ⁹ -C≡C-R ¹⁰ (4)
[In the formula, R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or an organic group.]
A compound represented by the formula:
The highest occupied molecular orbital (HOMO) of the compounds represented by the general formulas (3) and (4) preferably has a higher energy level than the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by the general formula (1).

From this perspective, the highest occupied molecular orbital (HOMO) of the unsaturated compound is preferably 0.1 eV or more higher, more preferably 0.2 to 30 eV higher, and even more preferably 0.5 to 15 eV higher, than the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by general formula (1).

Examples of the organic groups represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ in general formula (3) and the organic groups represented by R ⁹ and R ¹⁰ in general formula (4), which are unsaturated compounds, include halogen atoms, cyano groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted amino groups, substituted or unsubstituted thiol groups, ester groups (-COOR), carbonyl groups (-COR), substituted or unsubstituted carboxyl groups, nitro groups, sulfo groups, amide groups (-CONR ₂ , -NRCOR), etc. R may be the same or different and may be a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, etc.

In general formula (3), the organic groups represented by ^R5 , ^R6 , ^R7 and ^R8 , and the halogen atoms represented by ^R9 and ^R10 in general formula (4) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl groups as the organic groups represented by ^R5 , ^R6 , ^R7 and ^R8 in general formula (3) and the organic groups represented by ^R9 and ^R10 in general formula (4) may be linear, branched or cyclic. Of these, linear alkyl groups are preferred from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), etc.

The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), etc., it is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.

Specific examples of such alkyl groups include methyl groups, ethyl groups, and n-propyl groups.

The alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a hydroxyl group, the halogen atom, a cyano group, an alkoxy group as described below, an aryl group as described below, an amino group as described below, a thiol group as described below, an ester group as described above, a carbonyl group as described above, a carboxyl group as described below, and an amide group as described above.

In general formula (3), the organic groups represented by ^R5 , ^R6 , ^R7 , and ^R8 , and the alkoxy groups represented by ^R9 and ^R10 in general formula (4) may be linear, branched, or cyclic. Of these, linear alkoxy groups are preferred from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), and the like.

The number of carbon atoms in the alkoxy group is not particularly limited, but from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), etc., it is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.

Specific examples of such alkoxy groups include methoxy groups, ethoxy groups, and n-propoxy groups.

The alkoxy group may have a substituent, such as a hydroxyl group, the above-mentioned halogen atom, a cyano group, the above-mentioned alkoxy group, an aryl group described below, an amino group described below, a thiol group described below, and the above-mentioned amide group.

The organic groups represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ in general formula (3) and the aryl group as the organic group represented by R ⁹ and R ¹⁰ in general formula (4) are not particularly limited, but from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), etc., those having a carbon number of 6 to 20 are preferred, those having a carbon number of 6 to 12 are more preferred, and those having a carbon number of 6 to 10 are even more preferred. The aryl group may be either monocyclic or polycyclic (e.g., bicyclic, tricyclic, etc.), but is preferably monocyclic.

Specific examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a pentalenyl group, an indenyl group, an anthranyl group, a tetracenyl group, a pentacenyl group, a pyrenyl group, a perylenyl group, a fluorenyl group, and a phenanthryl group.

The aryl group may have a substituent. Examples of the substituent that the aryl group may have include a hydroxyl group, the halogen atom, the cyano group, the alkyl group, the alkoxy group, the aryl group, the amino group described below, the thiol group described below, the ester group, the carbonyl group, the carboxyl group described below, and the amide group.

The amino group may have a substituent. Examples of the substituent that the amino group may have include a hydroxyl group, the halogen atom, the cyano group, the alkyl group, the alkoxy group, the aryl group, the amino group, the thiol group described below, the ester group, the carbonyl group, the carboxyl group described below, and the amide group.

The thiol group may have a substituent. Examples of the substituent that the thiol group may have include a hydroxyl group, the halogen atom, the cyano group, the alkyl group, the alkoxy group, the aryl group, the amino group, the thiol group, the ester group, the carbonyl group, the carboxyl group described below, and the amide group.

The carboxyl group may have a substituent. Examples of the substituent that the carboxyl group may have include a hydroxyl group, the halogen atom, the cyano group, the alkyl group, the alkoxy group, the aryl group, the amino group, the thiol group, the ester group, the carbonyl group, the carboxyl group, and the amide group.

Among these, from the viewpoints of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), etc., the organic group is preferably a halogen atom, a halogenated alkyl group, etc., more preferably a fluorine atom, a fluoroalkyl group, etc., and even more preferably a fluorine atom, a perfluoroalkyl group, etc.

However, the compound represented by general formula (3) is a different compound from the desired halogenated alkene compound represented by general formula (1).

In the present disclosure, the reaction temperature is preferably 300 to 450°C, as described below. At this reaction temperature, from the viewpoints of making it easier to trap hydrogen halide, making it less likely to decompose or ignite, and making it easier to improve the conversion rate of the reaction, and the selectivity and yield of the halogenated alkene compound represented by general formula (1), it is preferable that at least one of the decomposition temperature, ignition point, and critical point of the unsaturated compound is higher than the reaction temperature, regardless of whether or not a measured value is present, and it is more preferable that all of the decomposition temperature, ignition point, and critical point are higher than the reaction temperature.

The unsaturated compounds satisfying the above conditions are compounds represented by the general formula (3), such as _CF3CF = _CFCF3 , _CCl3CCl = _CClCCl3 , _CBr3CBr =CBrCBr3, CF2= _CH2 , CHF=CHF, CHCl= _CHCl , _CHBr =CHBr, _CF2 =CFH, CBr2=CBrH, _CCl2 = _CCl2 , _{CBr2 =} CBr2, CHF=CHCF3 _{, CHCl} =CHCCl3, CF3CF ₌ CHCl, _{CCl3CCl =} CHCl, CF3CH ₌ CHCl, CCl3CH=CHCl _{, CCl3CCl} = _CH2 , _CH2 =CClCN, _CH2 =CBrCN, CH _{Examples of} the _{compound represented by the general formula (4) include CF3C≡CCF3 and CH≡CCH2COOCH3. Examples of the compound represented by the general formula ( 5 ) include CF3C≡CCF3 and CH≡CCH2COOCH3 . Examples of the compound represented by the general formula ( 6} ) include _{CF3C≡CCF3 and CH≡CCH2COOCH3} . Examples of the compound represented by _the general formula ( _{7 )} include _{CF3C≡CCF3 and CH≡CCH2COOCH3} .

It is preferable to adjust the energy level of the highest occupied molecular orbital (HOMO) of these unsaturated compounds as follows. It is preferable to select an unsaturated compound so that the highest occupied molecular orbital (HOMO) of the unsaturated compound has a higher energy level than the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by general formula (1) produced by dehydrohalogenation of the halogenated alkane compound represented by general formula (2). For this reason, the energy level of the highest occupied molecular orbital (HOMO) of the unsaturated compound is preferably -15 eV to 40 eV, more preferably -14 eV to 35 eV, and even more preferably -13 eV to 30 eV.

The energy level of the highest occupied molecular orbital (HOMO) is calculated by optimizing the structure using MM2 calculations and then calculating the electronic structure using the extended Hückel method. The results are shown in Table 1.

これらの不飽和化合物は、単独で用いることもでき、２種以上を組合せて用いることも
できる。このような不飽和化合物は、公知又は市販品を採用することができる。

These unsaturated compounds may be used alone or in combination of two or more. Such unsaturated compounds may be publicly known or commercially available products.

In the production method of the present disclosure, the amount of the unsaturated compound used is not particularly limited, but from the viewpoint of the conversion rate of the reaction, the selectivity and yield of the halogenated alkene compound represented by general formula (1), etc., the amount is preferably 0.001 to 0.40 mol, more preferably 0.01 to 0.40 mol, and even more preferably 0.05 to 0.20 mol per mol of the halogenated alkane compound represented by general formula (2) which is the raw material compound.

(1-5) Examples of dehydrohalogenation reactions The dehydrohalogenation reaction of the halogenated alkane compound in the present disclosure is preferably carried out in a gas phase, particularly from the viewpoint of productivity. When the step of dehydrohalogenating the halogenated alkane compound in the present disclosure is carried out in a gas phase, there are advantages in that it is not necessary to use a solvent, no industrial waste is generated, and productivity is excellent.

The dehydrohalogenation reaction of the halogenated alkane compound in the present disclosure can be carried out by either a flow system or a batch system in which the halogenated alkane compound, which is the raw material compound, is continuously charged into a reactor and the halogenated alkene compound, which is the target compound, is continuously withdrawn from the reactor. In the present disclosure, it is preferable to carry out the dehydrohalogenation reaction in a gas phase continuous flow system in order to further suppress the reverse reaction.

When the dehydrohalogenation reaction of the halogenated alkane compound in the present disclosure is carried out in a gas-phase continuous flow system, the equipment and operation can be simplified and it is economically advantageous.

In the present disclosure, the dehydrohalogenation reaction of the halogenated alkane compound is preferably carried out in an inert gas atmosphere in order to prevent deterioration of the catalyst. Examples of the inert gas include nitrogen, helium, and argon. Among these inert gases, nitrogen is preferred in terms of reducing costs.

(1-6) Reaction Temperature In the step of dehydrohalogenating a halogenated alkane compound in the present disclosure, the reaction temperature is preferably 300 to 450° C., more preferably 350 to 450° C., and even more preferably 350 to 400° C., from the viewpoint of more efficiently progressing the dehydrohalogenation reaction to further improve the conversion rate and obtaining the target compound, that is, the halogenated alkene compound, with higher selectivity and higher yield.

(1-7) Reaction Time In the present disclosure, the reaction time for dehydrohalogenating the halogenated alkane compound is, for example, when a gas-phase flow system is employed, the contact time of the raw material compound to the catalyst (W/F) [W: weight of catalyst (g), F: flow rate of raw material compound (cc/sec)] is preferably 12 to 45 g·sec/cc, more preferably 15 to 40 g·sec/cc, and even more preferably 20 to 30 g·sec/cc, from the viewpoint of a particularly high conversion rate of the reaction and a higher yield and higher selectivity of the halogenated alkane compound. The contact time means the time during which the raw material compound and the catalyst are in contact. Here, the flow rate of the raw material compound means the flow rate of the halogenated alkane compound represented by the general formula (2) that does not contain the above-mentioned unsaturated compound.

(1-8) Reaction Pressure The reaction pressure for dehydrohalogenating a halogenated alkane compound in the present disclosure is preferably 0 kPa or more, more preferably 10 kPa or more, even more preferably 20 kPa or more, and particularly preferably 30 kPa or more, from the viewpoint of more efficiently proceeding with the dehydrohalogenation reaction to further improve the conversion rate and obtaining the target compound, that is, a halogenated alkene compound, with higher selectivity and higher yield. There is no particular upper limit to the reaction pressure, and it is usually about 2 MPa. In the present disclosure, the pressure is referred to as gauge pressure unless otherwise specified.

In the dehydrohalogenation reaction of a halogenated alkane compound in the present disclosure, the reactor into which the halogenated alkane compound, catalyst, and unsaturated compound are introduced and reacted is not particularly limited in shape and structure as long as it can withstand the above-mentioned temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multi-tube reactor. Examples of the material of the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloys.

After the dehydrohalogenation reaction is completed, purification can be carried out according to conventional methods as necessary to obtain the halogenated alkene compound represented by general formula (1).

(1-9) Target compound (halogenated alkene compound)
The target compound of the present disclosure thus obtained is represented by the general formula (1):
R ¹ -CR ² ═CR ³ -R ⁴ (1)
[In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom or a haloalkyl group, provided that one of R ² and R ³ is a hydrogen atom and the other is a halogen atom.]
It is a halogenated alkene compound represented by the formula:

R ¹ , R ² , R ³ and R ⁴ in the general formula (1) correspond to R ¹ , R ² , R ³ and R ⁴ in the above-mentioned general formula (2). For this reason, the halogenated alkene compounds represented by the general formula (1) to be produced are, for example, specifically CFH= _CF2 , _CClH = _CCl2 , CBrH= _CBr2 , _CF3CH = _CF2 , CF3CF=CFH, _{CCl3CH =} CCl2, CCl3CCl ₌ CClH, CBr3CH= _CBr2 , _{CBr3CBr = CBrH} , CF3CF=CHCF3, _{CCl3CCl = CHCCl3} , _CBr3CBr = _CHCBr3 , _CH2 = _CF2 , _CH2 = _CCl2 , CH2= _{CBr2 , CF3CF} = _CH2 , _CCl3CCl = _CH2 , _CBr3 CBr= _CH2 , _{CF3CH2CF = CH2} , _{CF3CH = CFCH3} , CF3CHFCF= _CH2 , _{CF3CF2CH = CF2} , CH3CF2CH _{= CF2} , _{CCl3CH2CCl = CH2} , _{CCl3CH = CClCH3 ,} CCl3CHClCCl ₌ CH2, _{CCl3CCl2CH = CCl2} , _{CH3CCl2CH = CCl2 , CBr3CH2CBr = CH2} , _{CBr3CH = CBrCH3 ,} CBr3CHBrCBr= _CH2 , CBr3CBr2CH= _CBr2 , CH ₃ CBr ₂ CH═CBr ₂ , etc. These compounds include both Z and E forms.

As described above, it is preferable to select an unsaturated compound such that the highest occupied molecular orbital (HOMO) of the unsaturated compound has a higher energy level than the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by general formula (1) produced by dehydrohalogenation of the halogenated alkane compound represented by general formula (2). Therefore, the energy level of the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by general formula (1) is preferably -25 eV to 10 eV, more preferably -20 eV to 5 eV, and even more preferably -15 eV to -5 eV.

The energy level of the highest occupied molecular orbital (HOMO) is calculated by optimizing the structure using MM2 calculations and then calculating the electronic structure using the extended Hückel method. The results are shown in Table 2.

このようにして得られたハロゲン化アルケン化合物は、クリーニングガス；半導体、液
晶等の最先端の微細構造を形成するためのエッチングガス；デポジットガス；冷媒；熱移動媒体；有機合成用ビルディングブロック等の各種用途に有効利用できる。デポジットガス及び有機合成用ビルディングブロックについては後述する。

The halogenated alkene compounds thus obtained can be effectively used for various purposes such as cleaning gases, etching gases for forming cutting-edge fine structures in semiconductors, liquid crystals, etc., deposit gases, refrigerants, heat transfer media, building blocks for organic synthesis, etc. Deposit gases and building blocks for organic synthesis will be described later.

2. Composition The halogenated alkene compound can be obtained as described above, but it may also be obtained in the form of a composition containing the target compound.

According to the production method of the present disclosure, for example, a composition containing a halogenated alkene compound represented by general formula (1) and a halogenated alkene compound as an impurity may be obtained. In this case, the halogenated alkene compound as an impurity may be a halogenated alkene compound represented by general formula (5):
R ¹ -CH=CH-R ⁴ (5)
[In the formula, R ¹ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom, or a haloalkyl group.]
The halogenated alkene compound may be represented by the formula:

In the general formula (5), the halogen atom and haloalkyl group represented by ^R1 and ^R4 may be those explained above.

In other words, examples of the compound represented by the general formula (5) include CFH=CFH, CClH ₌ CClH, CBrH ₌ CBrH, CH2=CFH, _CH2 =CClH, _CH2 = _CBrH , _CF3CH = _CFH , _CCl3CH =CClH, _CBr3CH =CBrH, CF3CH= _CHCF3 , _{CCl3CH = CHCCl3} , CBr3CH=CHCBr3, _CF3CH = _CH2 , CCl3CH= _{CH2 , CBr3CH = CH2} , _{CF3CH2CH = CH2} , CF3CH= _CHCH3 , _{CF3CHFCH=CH2 , CF3CF2CH} = _CHF , _CH3 Examples of such compounds include _CF2CH =CHF, _{CCl3CH2CH = CH2} , _{CCl3CH = CHCH3} , _{CCl3CHClCH = CH2} , _CCl3CCl2CH= CHCl, CH3CCl2CH _{= CHCl, CBr3CH2CH=CH2, CBr3CH=CHCH3, CBr3CHBrCH=CH2 , CBr3CBr2CH = CHBr , CH3CBr2CH = CHBr ,} etc. These compounds include both Z _and E forms.

The composition further comprises a compound represented by the general formula (6) obtained by addition reaction of hydrogen halide generated in the dehydrohalogenation reaction of a halogenated alkane represented by the general formula (1) with an unsaturated compound represented by the general formula (3) or (4):
R ⁵ -CR ⁶ R ¹¹ -CR ⁷ R ¹² -R ⁸ (6)
[In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or an organic group. One of R ¹¹ and R ¹² is a hydrogen atom, and the other is a halogen atom.]
The halogenated alkane compound may also include a halogenated alkane compound represented by the formula:

In the general formula (6), the organic groups represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ and the halogen atoms represented by R ¹¹ and R ¹² may be those explained above.

The compound represented by the general formula (6) is one or two kinds of compounds in which hydrogen halide is added to the added unsaturated compound, that is, the compound represented by the general formula (3) or the general formula (4). That is, the compound represented by the general formula (6) is a compound in which hydrogen halide removed from the halogenated alkane (2) is added to the corresponding unsaturated compound, and examples of the compound represented by the general formula (6) include [CF ₃ CFHCF ₂ CF ₃ (HF added to the added unsaturated compound CF ₃ CF=CFCF ₃ )], [CCl ₃ CClHCCl ₂ CCl ₃ (HCl added to the added unsaturated compound CCl ₃ CCl=CClCCl ₃ )], [CBr ₃ CBrHCBr ₂ CBr ₃ (HBr added to the added unsaturated compound CBr ₃ CBr=CBrCBr ₃ )], [CF ₃ CH ₃ , CHF ₂ CH ₂ F, CH
F ₂ CH ₂ Cl, CF ₂ ClCH ₃ , CHF ₂ CH ₂ Br or CF ₂ BrCH ₃ (additional unsaturated compound CF ₂ ═CH ₂ with HF, HCl or HBr added) , [CHF ₂ CH ₂ F or CFClCFH ₂ (additional unsaturated compound CFH═CFH with HF or HCl added) , [CHCl ₂ CH ₂ Cl or CHFCICH ₂ Cl (additional unsaturated compound CHCl═CHCl
to HF or HCl)], CHClBrCH ₂ Br, or CHBr ₂ CH ₂ Br (addition of the added unsaturated compound CHBr=CHBr with HCl or HBr)], [CF ₃ CH ₂ F, CF ₂ ClCH ₂ F, CF ₂ HCHF ₂ , or CF ₂ HCHFCl (addition of the added unsaturated compound CF ₂ =CHF with HF or HCl)], [CHBr ₂ CHBr ₂ (addition of the added unsaturated compound CBr ₂ =CHBr with HBr)], [CFCl ₂ CHCl ₂ , or CCl ₃ CHCl ₂ (addition of the added unsaturated compound CCl ₂ =CCl ₂ with HF or HCl)], [CBr ₃ CHBr ₂ (addition of the added unsaturated compound CBr ₂ =CBr ₂ with HBr added)], [CH ₂ FCHFCF ₃ , CHF ₂ CH ₂ CF ₃ , CHFClCH ₂ CF ₃ , or CH ₂ FCHClCF ₃ (addition of unsaturated compound CHF═CHCF ₃ with HF or HCl added)], [CH ₂ ClCHClCCl ₃ , CHCl ₂ CH ₂ CCl ₃ , CHFClCH ₂ CCl ₃ , or CH ₂ ClCHFCCCl ₃ (addition of unsaturated compound CHCl═CHCCl ₃ with HF or HCl added)], [CF ₃ CF ₂ CH ₂ Cl, CF ₃ CHFCHFCl, or CF ₃ CFClCH ₂ Cl (addition of unsaturated compound CF ₃ CF═CHCl with HF or HCl added)], [CCl ₃ CCl ₂ CH ₂ Cl, or CCl ₃ CHClCHCl ₂ (addition of HCl to added unsaturated compound CCl ₃ CCl=CHCl)], [CCl ₃ CHClCH ₂ Cl, CCl ₃ CCl ₂ CH ₃ , or CCl ₃ CFClCH ₃ (addition of HF or HCl to added unsaturated compound CCl ₃ CCl=CH ₂ )], [CF ₃ CH ₂ CHFCl, CF ₃ CHFCH ₂ Cl, CF ₃ CH ₂ CHClBr, CF ₃ CH ₂ CHCl ₂ , CF ₃ CHClCH ₂ Cl, or CF ₃ CHBrCH ₂ Cl (addition of HF, HCl or HBr to added unsaturated compound CF ₃ CH=CHCl)], [CCl ₃ CH ₂ CHCl ₂ , CCl ₃ CHClCH ₂ Cl, or CCl _3CH2CHFCl (HF or HCl _added to added unsaturated compound _CCl3CH =CHCl) , [ _CH3CCl2CN , or _CH2ClCHClCN (HCl added to added unsaturated compound _CH2 = _{CClCN )} , [ _CH2BrCHBrCN (HBr added to added unsaturated compound _CH2 =CBrCN) , [ _CH3CHFCOOCH3 , _{CH3CHClCOOCH3 , CH3CHBrCOOCH3 , CH2ClCH2COOCH3 , or CH2BrCH2COOCH3} ( _HF , _HCl or _HBr added to added unsaturated compound _CH2 = _{CHCOOCH3 )} , _{[ CH3OCH2CHClCOOCH3} , or _CH3OCH2 CHBrCOOCH ₃ (additional unsaturated compound CH ₃ OCH═CHCOOCH ₃ with HCl or HBr added) , [CH ₃ CH ₂ CH ₂ CHClCOOCH ₃ , or CH ₃ CH ₂ CH ₂ CHBrCOOCH ₃ (additional unsaturated compound CH ₃ CH ₂ CH═CHCOOCH ₃ with HCl or HBr added) , [CH ₃ CBr(CH ₂ CH ₃ )COOCH ₃ (additional unsaturated compound CH ₂ ═C(C ₂ H ₅ )COOCH ₃ with HBr added) , [(CH ₃ ) ₂ CHCHClCOOCH ₃ , (CH ₃ ) ₂ CHCHBrCOOCH ₃ , or (CH ₃ ) ₂ CBrCH ₂ COOCH ₃ (additional unsaturated compound (CH ₃ ) ₂ C=CHCOOCH with _HCl or _HBr added)], _{[ CH3CHFCH2OH , CH3CHClCH2OH , CH3CHBrCH2OH , CH2FCH2CH2OH , CH2ClCH2CH2OH} , or _{CH2BrCH2CH2OH} (addition _of unsaturated compound _CH2 = _CHCH2OH with _HF , HCl or HBr _added )], [CH3CH2CHFCH2OH _{, CH3CH2CHClCH2OH} , or _{CH3CH2CHBrCH2OH} ( _addition of _{unsaturated compound CH3CH2CH = CHOH with HF} , _HCl or _HBr added)], _{[ CH3CHFCH2CH2OH , CH3CHClCH2CH2OH , CH3 CHBrCH2CH2OH , CH3CH2CFHCH2OH , CH3CH2CClHCH2OH , or CH3CH2CBrHCH2OH} (HF, HCl, or HBr added to the added unsaturated compound _CH3CH = _CHCH2OH ) , [ _{CH3CHClCH2OCH3} , or _{CH3CHBrCH2OCH3} ( _HCl or HBr added to the added unsaturated compound _CH3CH = _CHOCH3 ) , [ _{CH2ClCH2CH2N (CH3)2, or CH2BrCH2CH2N(CH3)2 ( HCl or HBr added to the added unsaturated compound CH2 = CHCH2N} ( _{CH3 ) 2 )} ], _{[ CH3 CCl2CH2COOC ​
H3} , _{or CHCl2CH2CH2COOCH3} ( _HCl added to _the added _unsaturated compound _{CH≡CCH2COOCH3} )
etc.

When the total amount of the composition of this disclosure is 100 mol%, the content of the halogenated alkene compound represented by general formula (1) is 50 to 80 mol%, and can also be 54 to 79 mol%, 58 to 78 mol%, 62 to 77 mol%, 65 to 76 mol%, etc.

In addition, the content of the halogenated alkene compound represented by general formula (5) is 12 to 40 mol%, and can also be 13 to 37 mol%, 14 to 34 mol%, 15 to 30 mol%, 16 to 27 mol%, etc., with the total amount of the composition disclosed herein being 100 mol%.

In addition, the content of the halogenated alkene compound represented by general formula (6) is preferably 0.10 to 10.0 mol%, and can also be 0.15 to 9.5 mol%, 0.20 to 9.0 mol%, 0.25 to 8.5 mol%, 0.30 to 8.0 mol%, etc., with the total amount of the composition disclosed herein being 100 mol%.

In addition, according to the production method of the present disclosure, even if a halogenated alkene composition is obtained, the halogenated alkene compound represented by general formula (1) can be obtained with a high reaction conversion rate, high yield, and high selectivity as described above. Therefore, it is possible to reduce the amount of components other than the halogenated alkene compound represented by general formula (1) in the composition of the present disclosure, thereby reducing the purification effort required to obtain the halogenated alkene compound represented by general formula (1).

According to the manufacturing method of the present disclosure, even when a composition containing a halogenated alkene compound represented by general formula (1) is obtained, the halogenated alkene compound represented by general formula (1) can be obtained with a high reaction conversion rate, high yield, and high selectivity, and as a result, it is possible to reduce components other than the halogenated alkene compound represented by general formula (1) in the composition. According to the manufacturing method of the present disclosure, it is possible to reduce the purification effort required to obtain the halogenated alkene compound represented by general formula (1).

Compositions containing the halogenated alkene compounds of the present disclosure, like the halogenated alkene compounds alone, can be effectively used for a variety of applications, including cleaning gases; etching gases for forming cutting-edge microstructures in semiconductors, liquid crystals, etc.; as well as deposit gases, refrigerants, heat transfer media, building blocks for organic synthesis, etc.

The deposition gas is a gas that deposits an etch-resistant polymer layer.

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 can be introduced to convert the compound into a substance that can be a cleaning agent or a fluorine-containing pharmaceutical intermediate.

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

The following examples are presented to clarify the features of the present disclosure. The present disclosure is not limited to these examples.

In the methods for producing halogenated alkene compounds in Examples 1 to 3, the raw material compound is a halogenated alkane compound represented by general formula (2), in which R ¹ and R ⁴ are trifluoromethyl groups, R ² is a fluorine atom, R ³ is a hydrogen atom, and X is a fluorine atom, and the compound is reacted with the following reaction formula:
_{CF3CFHCFHCF3 → CF3CF} = _CHCF3 + HF
According to the procedure described above, a halogenated alkene compound was obtained by dehydrofluorination reaction.

Examples 1 to 3 and Comparative Example 1
10 g of an activated carbon catalyst (manufactured by Osaka Gas Chemicals Co., Ltd.; specific surface area: 1200 ^m2 /g) was added as a catalyst to a SUS pipe (outer diameter: 1/2 inch) serving as a reaction tube. After drying at 200°C for 2 hours under a nitrogen atmosphere, _CF3CFHCFHCF3 (raw material compound) _was circulated through the reaction tube at normal pressure so that the contact time between _CF3CFHCFHCF3 (raw material compound) and the activated carbon catalyst, W/F [W: weight of catalyst (g), F: flow rate (cc/sec) of _CF3CFHCFHCF3 as raw material compound], was ₂₃ g·sec/cc or ₄₇ g·sec/cc. Thereafter, in Examples 1 to 3, 0.01 to 0.20 moles (1 to 20 mole %) of CF ₃ CF═CFCF ₃ (raw material compound) was passed through per mole of CF ₃ CFHCFHCF ₃ (raw material compound).

The reaction was carried out in a continuous gas phase flow system.

The reaction tube was heated to 350°C to initiate the dehydrofluorination reaction.

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

Thereafter, mass analysis was performed by gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, product name "GC-2014"), and structural analysis was performed by NMR spectroscopy using an NMR (manufactured by JEOL, product name "400YH"). From the results of mass analysis and structural analysis, it was confirmed that CF ₃ CF═CHCF ₃ was produced as the target compound. The results are shown in Table 3.

Claims (9)

General formula (1):
R ¹ -CR ² ═CR ³ -R ⁴ (1)
[In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom or a haloalkyl group, provided that one of R ² and R ³ is a hydrogen atom and the other is a halogen atom.]
A method for producing a halogenated alkene compound represented by the following formula:
General formula (2):
R ¹ -CHR ² -CXR ³ -R ⁴ (2)
[In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as defined above. X represents a halogen atom.]
The method includes a step of subjecting a halogenated alkane compound represented by the following formula (1) to a dehydrohalogenation reaction in the presence of a catalyst and an unsaturated compound,
The unsaturated compound is represented by the general formula (3):
R ⁵ -CR ⁶ ═CR ⁷ -R ⁸ (3)
[wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or an organic group.], or general formula (4):
R ⁹ -C≡C-R ¹⁰ (4)
[In the formula, R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom or an organic group.]
and
The production method, wherein the compound represented by the general formula (1) and the unsaturated compound are different compounds. The method according to claim 1 , wherein in the general formulas (1) and (2), R ¹ and R ⁴ each represent a fluorine atom or a perfluoroalkyl group. The method according to claim 1 or 2, wherein the energy level of the highest occupied molecular orbital (HOMO) of the unsaturated compound is higher than the highest occupied molecular orbital (HOMO) of the halogenated alkene compound represented by the general formula (1). The method according to claim 1 or 2, wherein the amount of the unsaturated compound supplied is 0.001 to 0.40 moles per mole of the halogenated alkane compound represented by the general formula (2). The method according to claim 1 or 2, wherein the dehydrohalogenation reaction is carried out in a gas phase. General formula (1):
R ¹ -CR ² ═CR ³ -R ⁴ (1)
[In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom or a haloalkyl group, provided that one of R ² and R ³ is a hydrogen atom and the other is a halogen atom.]
and 50 to 80 mol % of a halogenated alkene compound represented by the following formula:
General formula (5):
R ¹ -CH=CH-R ⁴ (5)
[In the formula, R ¹ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom, or a haloalkyl group.]
and 12 to 40 mol % of a halogenated alkene compound represented by the formula: Furthermore, the general formula (6):
R ⁵ -CR ⁶ R ¹¹ -CR ⁷ R ¹² -R ⁸ (6)
[In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or an organic group. One of R ¹¹ and R ¹² is a hydrogen atom, and the other is a halogen atom.]
The composition according to claim 6, comprising a halogenated alkane compound represented by the formula: The composition according to claim 7, wherein the content of the halogenated alkane compound represented by the general formula (6) is 0.10 to 10.0 mol %. The composition according to any one of claims 6 to 8, which is used as a cleaning gas, an etching gas, a refrigerant, a heat transfer medium, or a building block for organic synthesis.