RU2793785C2 - Method for producing halogenated alkene compound and fluorinated alkyne compound - Google Patents

Abstract

FIELD: production of a halogenated butene.

SUBSTANCE: invention relates to variants of a method for the production of a halogenated butene compound represented by formula (2A) CX¹ X² X³ CX⁴ = CHCX⁵ X⁶ X⁷ (2A), in which X¹, X², X³, X⁴, X⁵, X⁶ and X⁷ are the same or different and each represents a halogen atom. In one embodiment, the method includes introducing a halogenated butane compound represented by formula (1A) CX¹ X² X³ CHX⁴ CFHCX⁵ X⁶ X⁷, in which X¹, X², X³, X⁴, X⁵, X⁶ and X⁷ have the meanings defined above, in the gas phase or liquid phase dehydrofluorination reaction, where the dehydrofluorination reaction is carried out in the presence of at least one catalyst, selected from the group consisting of an activated carbon catalyst, a chromium oxide catalyst, and an aluminosilicate catalyst when the dehydrofluorination reaction is carried out in the gas phase. The invention also relates to options for the production of a halogenated butyne compound.

EFFECT: use of the present invention makes it possible to obtain target compounds with a high degree of conversion and high selectivity.

14 cl, 2 dwg, 6 tbl, 20 ex

Description

Technical field

[0001]

The present invention relates to processes for the production of a halogenated alkene compound and a fluorinated alkyne compound.

Technical field

[0002]

As a method for producing a halogenated alkene compound, for example, in a patent document (PD (PTL)) 1 starting material such as CF ₃ CHClCHClCCl ₃ , CF ₃ CCl ₂ CH ₂ CCl ₃ , CF ₃ CClHCHFCCl ₃ or CF ₃ CClFCH ₂ CCl ₃ , is reacted with hydrogen fluoride in the presence of a chromium oxyfluoride catalyst, and dehydrofluorination is carried out during fluorination, resulting in CF ₃ CF=CHCF _3.

Citation list

patent document

[0003]

PD 1: WO 2012/067864.

The essence of the invention

Technical task

[0004]

The purpose of the present invention is to provide processes in which a halogenated alkene compound and a fluorinated alkyne compound can be produced with high conversion and high selectivity.

The solution of the problem

[0005]

The present invention includes the following configurations.

Item 1. Method for the production of a halogenated butene compound represented by the formula (2A):

CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom,

and this method includes introducing a halogenated butane compound represented by formula (1A):

CX ¹ X ² X ³ CHX ⁴ CFHCX ⁵ X ⁶ X ⁷ (1A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, in the dehydrofluorination reaction.

Item 2. Process for the production of a halogenated butyne compound represented by the formula (3A):

CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom,

and this method includes introducing a halogenated butene compound represented by formula (2A):

CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, and X ⁴ represents a halogen atom, in the dehydrohalogenation reaction.

Item 3. Method for the production of a halogenated butyne compound represented by the formula (3A):

CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom,

and this way includes:

(IA) introducing a halogenated butane compound represented by formula (1A):

CX ¹ X ² X ³ CHX ⁴ CFHCX ⁵ X ⁶ X ⁷ (1A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, and X ⁴ represents a halogen atom, in the dehydrofluorination reaction to obtain a halogenated butene compound represented by formula (2A):

CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are as defined above;

(IIA) after step (IA) removal of hydrogen fluoride; And

(IIIA) after step (IIA), introducing the resulting halogenated butene compound represented by formula (2A):

CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are as defined above, in a dehydrohalogenation reaction to obtain a halogenated butyne compound represented by formula (3A):

CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above.

Item 4. The production method according to any one of items 1 to 3, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in the presence of a catalyst and/or a base.

Item 5. The production method according to any of items 1 to 4, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in liquid phase.

Item 6. The production method according to item 5, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in a closed reaction process.

Item 7. The production method according to any of items 1 to 4, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in the gas phase.

Item 8. The production method according to item 7, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in the presence of at least one catalyst selected from the group consisting of an activated carbon catalyst, a chromium oxide catalyst, a zeolite catalyst and aluminosilicate catalyst.

Item 9. Process for the production of a halogenated alkene compound represented by the formula (2B):

CX ⁸ A ¹ = CHA ² (2B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group, and X ⁸ represents a halogen atom,

and this method includes introducing a halogenated alkane compound represented by formula (1B):

CHX ⁸ A ¹ CHX ⁹ A ² (1B),

where A ¹ and A ² have the meanings defined above, and X ⁸ and X ⁹ are the same or different and each represents a halogen atom, in the dehydrohalogenation reaction in the presence of a catalyst in the gas phase.

Item 10 A method for producing a fluorinated alkyne compound represented by the formula (3B):

CA ¹ ≡ ^{CA 2} (3B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group,

and this method includes introducing a halogenated alkene compound represented by formula (2B):

CX ⁸ A ¹ = CHA ² (2B),

where A ¹ and A ² have the meanings defined above, and X ⁸ represents a halogen atom, in the dehydrohalogenation reaction in the presence of a catalyst.

Item 11. The production method according to item 10, wherein the dehydrohalogenation reaction step is carried out in the gas phase.

Item 12 A method for producing a fluorinated alkyne compound represented by the formula (3B):

CA ¹ ≡ ^{CA 2} (3B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group,

and this way includes:

(IB) introducing a halogenated alkane compound represented by formula (1B):

CHX ⁸ A ¹ CHX ⁹ A ² (1B),

where A ¹ and A ² are as defined above, and X ⁸ and X ⁹ are the same or different and each represents a halogen atom, in a dehydrohalogenation reaction in the presence of a gas phase catalyst to obtain a halogenated alkene compound represented by formula (2B):

CX ⁸ A ¹ = CHA ² (2B),

where A ¹ , A ² and X ⁸ have the meanings defined above;

(IIB) after step (IB) removing the hydrogen halide; And

(IIIB) after step (IIB), introducing the resulting halogenated alkene compound represented by formula (2B):

CX ⁸ A ¹ = CHA ² (2B),

where A ¹ , A ² and X ⁸ have the meanings defined above, in the reaction of dehydrohalogenation in the presence of a catalyst in the gas phase to obtain a fluorinated alkyne compound represented by formula (3B):

CA ¹ ≡ ^{CA 2} (3B),

where A ¹ and A ² have the meanings defined above.

Item 13. The production method according to any one of items 1 to 12, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out by a gas-phase continuous flow process.

Item 14. The production method according to any one of items 1 to 13, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in the presence of a cyclic halocarbide compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound are replaced by halogen atoms _.

Item 15 A composition containing a halogenated butene compound represented by formula (1A):

CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (1A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom,

moreover, the halogenated butene compound represented by formula (1A) is contained in an amount of from 80.00 to 99.99 mol%. based on the total amount of the composition, which is taken as 100 mol%.

Item 16. The composition in accordance with item 15, containing as a halogenated butene compound represented by formula (1A), (E)-halogenated butene compound in an amount of from 85.00 to 99.98 mol%. based on the total amount of the composition, which is taken as 100 mol%.

Clause 17. Composition containing:

a halogenated alkene compound represented by the formula (2B):

CX ⁸ A ¹ = CHA ² (2B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group, and X ⁸ represents a halogen atom; And,

at least one hydrofluorocarbon (HFC) compound, excluding the halogenated alkene compound represented by formula (2B).

Item 18. The composition in accordance with item 17, where the halogenated alkene compound represented by formula (2B) is contained in an amount of 80 mol%. or more, and hydrofluorocarbon (HFC) compound is contained in an amount of 20 mol%. or less based on the total amount of the composition, which is taken as 100 mol%.

Item 19 A composition according to item 17 or 18, wherein the hydrofluorocarbon (HFC) compound is at least one selected from the group consisting of hexafluorobutene, hexafluorobutane and octafluorobutane.

Clause 20. Composition containing:

the fluorinated alkyne compound represented by the formula (3B):

CA ¹ ≡ ^{CA 2} (3B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group; And,

at least one hydrofluorocarbon (HFC) compound except for the fluorinated alkyne compound represented by formula (3B).

Clause 21. Composition containing:

a halogenated butyne compound represented by the formula (3A):

CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom; And

at least one hydrofluorocarbon (HFC) compound except for the halogenated butyne compound represented by formula (3A).

Item 22. The composition in accordance with item 20 or 21, where the fluorinated alkyne compound represented by formula (3B) or halogenated butyne compound represented by formula (3A) is contained in an amount of 80 mol%. or more, and hydrofluorocarbon (HFC) compound is contained in an amount of 20 mol%. or less based on the total amount of the composition, which is taken as 100 mol%.

Item 23 A composition according to any one of items 20-22, wherein the hydrofluorocarbon (HFC) compound is at least one selected from the group consisting of trifluoromethane, difluoromethane, tetrafluoromethane, and monofluoromethane.

Item 24 A composition according to any one of items 15-23 that is used as a cleaning gas, pickling gas, refrigerant, heat transfer medium, or building block for organic synthesis.

Positive effects of the invention

[0006]

According to the present invention, a halogenated alkene compound and a fluorinated alkyne compound can be synthesized with high conversion and high selectivity.

Brief description of the drawings

[0007]

FIG. 1 is a view schematically showing the production method of an alkene (halogenated butene compound or halogenated alkene compound) and an alkyne (halogenated butene compound or fluorinated alkyne compound) of the present invention. FIG. 1 the resulting hydrogen fluoride can be separated in a distillation column.

FIG. 2 is a view schematically showing the production method of an alkene (halogenated butene compound or halogenated alkene compound) and an alkyne (halogenated butene compound or fluorinated alkyne compound) of the present invention. FIG. 2, the generated hydrogen halide can be removed using a hydrogen halide removal agent (removal column).

Description of Embodiments

[0008]

In this description, the term "comprises" is a concept that includes "comprising", "consisting essentially of" and "consisting of". In the present description, the numerical range indicated "from A to B" means A or more and B or less.

[0009]

As used herein, "selectivity" means the total molar amount (mol %) of the target compound in the outlet gas from the reactor outlet, based on the total molar amount of compounds other than the feed compound in the outlet gas.

[0010]

In the present description, "conversion rate" means the total molar amount of compounds other than the feed compound present in the outlet gas from the reactor outlet, based on the molar amount of the feed compound fed to the reactor.

[0011]

Conventionally (see AP 1), a feed material such as CF ₃ CHClCHClCCl ₃ , CF ₃ CCl ₂ CH ₂ CCl ₃ , CF ₃ CClHCHFCCl _{3 ,} or CF ₃ CClFCH ₂ CCl ₃ is reacted with hydrogen fluoride in the presence of an oxyfluoride-based catalyst chromium, and dehydrofluorination is carried out simultaneously with fluorination, resulting in CF ₃ CF=CHCF ₃ . However, its yield is only 14.8%.

[0012]

Based on the foregoing, in the traditional method, the yield is only 14.8%. According to the production method of the present invention, a halogenated alkene compound and a fluorinated alkyne compound can be synthesized with higher conversion and higher selectivity compared to the conventional method.

[0013]

1. Methods for the production of a halogenated butene compound and a halogenated butene compound

1-1: Process for producing a halogenated butene compound from a halogenated butane compound

The method for producing a halogenated butene compound of the present invention is a method for producing a halogenated butene compound represented by the formula (2A):

CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom,

and this method includes introducing a halogenated butane compound represented by formula (1A):

CX ¹ X ² X ³ CHX ⁴ CFHCX ⁵ X ⁶ X ⁷ (1A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, in the dehydrofluorination reaction.

[0014]

According to the present invention, when the halogenated butane compound represented by the formula (1A) is introduced into the dehydrofluorination reaction, the halogenated butene compound represented by the formula (2A) in which 1 mol of hydrogen fluoride is eliminated per 1 mol of the halogenated butane compound can be selectively obtained, represented by formula (1A). In addition, the reaction of abstraction of a hydrogen halide represented as HX ⁴ from a halogenated butene compound represented by formula (2A) is unlikely to proceed continuously. Further, according to the present invention, as the halogenated butene compound represented by the formula (2A), the E isomer among the geometric isomers can be selectively synthesized. The reason for this is as follows. Since the α-carbon of trihalogenated methyl groups such as the CF ₃ group becomes electron-deficient due to the electron attraction effect of trihalogenated methyl groups such as the CF ₃ group, halogenated anions such as fluorine anions are less prone to desorption. The result is halogenated butene instead of halogenated butyne. In addition, selective synthesis of the E isomer occurs because the trans configuration is energetically more stable due to steric hindrance from trihalogenated methyl groups such as the CF ₃ group.

[0015]

(1-1-1) Raw material compound (Halogenated butane compound).

The halogenated butane compound as a substrate that can be used in the production method of the present invention is, as described above, the halogenated butane compound represented by the formula (1A):

CX ¹ X ² X ³ CHX ⁴ CFHCX ⁵ X ⁶ X ⁷ (1A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom.

[0016]

In the formula (1A), examples of the halogen atom represented by X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0017]

In the halogenated butane compound which is the substrate, all of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are preferably fluorine atoms or chlorine atoms, and more preferably fluorine atoms, from that point of view that the halogenated butene compound can be obtained especially with high conversion, high yield and high selectivity.

[0018]

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ may be the same or different.

[0019]

Specific examples of the halogenated butane compound as a substrate that satisfies the above conditions include CF ₃ CFHCFHCF ₃ , CCl ₃ CClHCFHCCl ₃ , CBr ₃ CBrHCFHCBr ₃ and the like. These halogenated butane compounds may be used singly or in combination of two or more. Such halogenated butane compounds may be known or commercially available.

[0020]

(1-1-2) Dehydrofluorination reaction

In the step of introducing the halogenated butane compound into the dehydrofluorination reaction in the present invention, for example, in the halogenated butane compound represented by the formula (1A) as ^the substrate X ¹ , X 2 , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ more preferably represent fluorine atoms.

[0021]

That is, this reaction is preferably a dehydrofluorination reaction according to the following reaction equation:

CF ₃ CFHCFHCF ₃ → CF ₃ CF=CHCF ₃ +HF

[0022]

The step of introducing the halogenated butane compound into the dehydrofluorination reaction in the present invention may be carried out in liquid phase or gas phase. Particularly from a performance point of view, it is preferable to carry out this step in the gas phase.

[0023]

The step of introducing a halogenated butane compound into the dehydrofluorination reaction in the present invention is preferably carried out in the presence of a catalyst and/or a base from the viewpoint that the target compound can be obtained with higher selectivity and higher conversion. More specifically, when a liquid phase reaction is used, this step is preferably carried out in the presence of a base and optionally a catalyst, and when a gas phase reaction is used, this step is preferably carried out in the presence of a catalyst. Detailed information on the catalyst and the base in each case is described later.

[0024]

(1-1-2-1) Liquid phase reaction

When the step of introducing a halogenated butane compound into the dehydrofluorination reaction in the present invention is carried out in the liquid phase, the yield of the target compound can be further improved, for example, by using a metal container and increasing the liquid component by applying pressure and raising the boiling point of the starting material.

[0025]

When the step of introducing the halogenated butane compound into the dehydrofluorination reaction in the present invention is carried out in the liquid phase, it is preferable to first prepare a solution of the halogenated butane compound represented by the formula (1A) and then proceed to the reaction in the presence of a base.

[0026]

Solvent

As a solvent in a solution of a halogenated butane compound, both aqueous and non-aqueous solvents can be used. Preferred examples of non-aqueous solvents include carbonate esters such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate and ethyl propyl carbonate; esters such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate and butyl propionate; ketones such as acetone, ethyl methyl ketone and diethyl ketone; lactones such as γ-butyrolactone, γ-valerolactone, tetrahydrofuran and tetrahydropyran; ethers such as diethyl ether, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane and tetrahydrofuran; nitriles such as acetonitrile, propionitrile and benzonitrile; amides such as N,N-dimethylformamide; sulfones such as dimethyl sulfoxide and sulfolane; and so on. These aqueous and non-aqueous solvents may be used alone or in combination of two or more. Of these, it is preferable to use solvents which have a high boiling point and which do not readily decompose the bases described later. More specifically, a non-aqueous solvent is preferred, an ether is more preferred, and dibutyl ether is particularly preferred.

[0027]

Base

When the step of introducing a halogenated butane compound into the dehydrofluorination reaction in the present invention is carried out in a liquid phase, this step is preferably carried out in the presence of a base as described above.

[0028]

From the standpoint of reaction conversion rate and selectivity and yield of halogenated butene compound, the base is preferably an alkali metal or alkaline earth metal hydroxide or alkoxide, and more preferably an alkali metal or alkaline earth metal alkoxide. Specific examples include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium t-butoxide, and the like; and preferably sodium methoxide, potassium t-butoxide and the like. In this step, it is preferable to use an aqueous solution of an alkali metal or alkaline earth metal hydroxide or alkoxide, and more preferably an aqueous solution of an alkali metal or alkaline earth metal alkoxide. More specifically, an aqueous solution of sodium methoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide or the like is particularly preferred. By using such a base, the target compound can be obtained with higher selectivity and higher conversion.

[0029]

The content of the base in the reaction solution is not limited, but is preferably from 20 to 60 wt%. and more preferably from 40 to 55% of the mass. based on the entire reaction solution, which is taken as 100 wt%. When the content of the base in the reaction solution is within these ranges, the target compound can be obtained with higher selectivity and higher conversion.

[0030]

Catalyst

A catalyst may be used at this stage, if necessary. The catalyst used in this step is preferably a hydrocarbon-based alkoxide. Примеры алкоксидов на основе углеводорода включают тетраметиламмонийфторид, тетраметиламмонийхлорид, тетраметил-аммонийбромид, тетраметиламмониййодид, тетраэтиламмонийфторид, тетраэтиламмонийхлорид, тетраэтиламмонийбромид, тетраэтил-аммониййодид, тетрапропиламмонийфторид, тетрапропиламмоний-хлорид, тетрапропиламмонийбромид, тетрапропиламмониййодид, тетрабутиламмонийфторид, тетрабутиламмонийхлорид, тетрабутил-аммонийбромид, тетрабутиламмониййодид, бензилтриэтиламмоний-фторид, бензилтриэтиламмонийхлорид, бензилтриэтиламмонийбромид, бензилтриэтиламмониййодид, бензилтрибутиламмонийфторид, бензил-трибутиламмонийхлорид, бензилтрибутиламмонийбромид, бензил-трибутиламмониййодид, метилтрибутиламмонийфторид, метилтрибутил-аммонийхлорид, метилтрибутиламмонийбромид, метилтрибутиламмоний-йодид, метилтриоктиламмонийфторид, метилтриоктиламмонийхлорид (товарный знак: Aliquat 336), метилтриоктиламмонийбромид, метилтриоктиламмониййодид и т.п. The catalysts may be used singly or in combination of two or more. By using such a catalyst, the target compound can be obtained with higher selectivity and higher conversion.

[0031]

Cyclic halocarbide compound

In the present invention, the step of introducing a halogenated butane compound into the dehydrofluorination reaction may be carried out in the presence of a cyclic halocarbide compound. A cyclic halocarbide compound refers to a cyclic halocarbide compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound are replaced by halogen atoms. In other words, this compound refers to a cyclic halocarbide compound composed of carbon atoms and halogen atoms and containing no hydrogen atoms.

[0032]

When the step of introducing a halogenated butane compound into the dehydrofluorination reaction is carried out in the presence of such a cyclic halocarbide compound, the reaction equilibrium can be shifted towards the product, and the halogenated butene compound, which is the desired product, can be obtained with higher conversion and higher yield.

[0033]

Examples of the halogen atom in a suitable cyclic halocarbide compound include any of fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Of these, from the point of view of reaction efficiency, it is preferable that the same type of halogen atom is present as the halogen atom (X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ ) present in the halogenated butane compound, which is a compound of the starting material. When the halogenated butane compound has a plurality of halogen atoms (when not all of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are the same), it is preferred that the cyclic halocarbide compound contains one, or two, or more of the halogen atoms present in the halogenated butane compound, and more preferably one of the halogen atoms present in the halogenated butane compound.

[0034]

The number of carbon atoms in a suitable cyclic halocarbide compound is not limited. In terms of conversion rate, selectivity and yield of the halogenated butene compound as the target product, the number of carbon atoms in the cyclic halocarbide compound is preferably 1 to 10, more preferably 2 to 7, and even more preferably 3 to 5.

[0035]

A suitable cyclic halocarbide compound may be a saturated cyclic halocarbide compound without an unsaturated bond or an unsaturated cyclic halocarbide compound with an unsaturated bond. Of these, the saturated cyclic halogen carbide compound is preferable in terms of conversion rate, selectivity, and yield of the halogenated butene compound as an end product.

[0036]

Based on the foregoing, the cyclic halocarbide compound is preferably a saturated cyclic halocarbide compound. Such a saturated cyclic halocarbide compound is preferably a saturated cyclic halocarbide compound represented by the formula (4):

[0037]

[0038]

where A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ and A ¹⁰ are the same or different and each represents a fluorine atom or a perfluoroalkyl group.

[0039]

In the formula (4), the perfluoroalkyl group denoted as A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ and A ¹⁰ refers to an alkyl group in which all hydrogen atoms are replaced by fluorine atoms. Such a perfluoroalkyl group, for example, is a perfluoroalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 up to 3 carbon atoms. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. Such a perfluoroalkyl group is preferably a trifluoromethyl group (CF ₃ -) or a pentafluoroethyl group (C ₂ F ₅ -).

[0040]

Specific examples of the cyclic halocarbide compound that satisfies the above conditions include:

[0041]

[0042]

[0043]

In the production method of the present invention, when the halogenated butane compound is introduced into a liquid phase dehydrofluorination reaction, for example, in the presence of a cyclic halocarbide compound, the cyclic halocarbide compound may be blown in a gaseous state into a solution of the halogenated butane compound, or it may be fed liquid phase (for example, liquefied gas).

[0044]

In the production method of the present invention, when the halogenated butane compound is introduced into the dehydrofluorination reaction in the presence of the cyclic halocarbide compound, the amount of the cyclic halocarbide compound used is not limited. From the viewpoints of the degree of conversion, selectivity and yield of the halogenated butene compound as the target product, the amount of the cyclic halocarbide compound is preferably an excess amount based on the halogenated butane compound, which is the compound of the raw material, and more specifically, 1 to 20 moles are preferably used, more preferably 2 to 10 moles and even more preferably 3 to 5 moles per mole of the halogenated butane compound which is the starting material compound.

[0045]

Closed reaction process

In the present invention, the halogenated butene compound represented by the formula (2A) as the target compound has a low boiling point and exists as a gas at room temperature. Accordingly, in the present invention, in the step of carrying out the dehydrofluorination reaction, when the closed reaction process is used as the reaction system, the pressure inside the closed reaction process rises naturally, and the reaction can be carried out under pressurized conditions. Therefore, the halogenated butene compound represented by the formula (2A) as the target compound can be obtained with higher selectivity and higher conversion.

[0046]

Thus, the closed reaction process is under pressure due to the low boiling point of the target compound, and the concentration of the substrate (raw material compound) in the reaction solution (base solution) is increased, which can improve the reactivity. In a closed reaction process, it is preferable to carry out the reaction while sealing the reaction system using a pressure-resistant batch reaction vessel. When the reaction is carried out in a batch process, it is preferable, for example, to put the starting material compound, base solution (alkaline aqueous solution), catalyst, etc. into a pressure vessel such as an autoclave, raise the temperature to the appropriate reaction temperature with a heater, and carry out the reaction while stirring for some period of time. As for the reaction atmosphere, it is preferable to carry out the reaction under an inert gas atmosphere such as nitrogen, helium or carbon dioxide.

[0047]

In the present invention, in the step of carrying out the dehydrofluorination reaction, the reaction temperature in the closed reaction process is generally preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 15°C or higher from the viewpoint that the elimination reaction can proceed more effectively, and the target compound can be obtained with a higher selectivity, and from the viewpoint of suppressing the decrease in the conversion rate.

[0048]

In the dehydrofluorination reaction step of the present invention, the reaction temperature in the closed reaction process is generally preferably 100°C or lower, and more preferably 80°C or lower, from the viewpoint that the dehydrofluorination reaction can proceed more efficiently and the target compound can be obtained with higher selectivity, and in terms of further suppressing the drop in selectivity due to decomposition or polymerization of the reaction product.

[0049]

Reaction process at elevated pressure

In the step of carrying out the dehydrofluorination reaction in the present invention, the reaction can be carried out in the reaction process at an elevated pressure by setting the reaction temperature to 10°C or more and the reaction pressure to 0 kPa or more. As a result, the halogenated butene compound represented by the formula (2A) as the target compound can be obtained with higher selectivity and higher conversion. When the reaction system is pressurized in this way, the concentration of the substrate (raw material compound) in the reaction solution (base solution, alkaline aqueous solution) rises, which can improve the reactivity. In the pressurized reaction process, it is preferable to carry out the reaction while sealing the reaction system using a batch-type pressure-resistant reaction vessel. When the reaction is carried out in a batch process, it is preferable, for example, to put the starting material compound, the base solution (alkaline aqueous solution), the catalyst, etc. into a reaction vessel such as an autoclave, raise the temperature to the appropriate reaction temperature with a heater, and carry out the reaction while stirring for some period of time.

[0050]

In the step of carrying out the cleavage reaction in the present invention, the pressurization conditions are preferably such that the reaction pressure is 0 kPa or more. The reaction pressure is the pressure inside the reaction vessel used in the case of a pressurized reaction process. In the dehydrofluorination reaction step of the present invention, the reaction pressure is preferably 0 kPa or more, more preferably 5 kPa or more, even more preferably 10 kPa or more, and particularly preferably 15 kPa or more. The upper limit of the reaction pressure is not limited, and, as a rule, is approximately 2 MPa. In the present invention, the pressure is overpressure, unless otherwise indicated.

[0051]

In the case of pressurizing the reaction system, the pressure can be increased by supplying an inert gas such as nitrogen, helium or carbon dioxide to the reaction system.

[0052]

In the dehydrofluorination reaction step of the present invention, the reaction temperature in the pressurized reaction process is generally preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 15°C or higher from the viewpoint that the elimination reaction can proceed more efficiently, and the target compound can be obtained with higher selectivity, and from the viewpoint of suppressing the decrease in the conversion rate.

[0053]

In the dehydrofluorination reaction step of the present invention, the reaction temperature in the closed reaction process is generally preferably 100°C or lower, and more preferably 80°C or lower, from the viewpoint that the dehydrofluorination reaction can proceed more efficiently and the target compound can be obtained with more high selectivity, as well as from the point of view of additional suppression of the decrease in selectivity due to decomposition or polymerization of the reaction product.

[0054]

Combination of a closed reaction process and a reaction process at elevated pressure

In the dehydrofluorination reaction step of the present invention, it is also possible to carry out the reaction in a pressure continuous reaction format while recovering a liquid or recovering a gasified product by connecting a back pressure valve to a continuously stirred reactor (CSTR).

[0055]

After the completion of the dehydrofluorination reaction, purification may optionally be carried out according to conventional methods, resulting in a halogenated butene compound represented by formula (2A).

[0056]

(1-1-2-2) Gas phase reaction

When the step of introducing the halogenated butane compound into the dehydrofluorination reaction is carried out in the gas phase in the present invention, it is advantageous in that the use of a solvent is not required, industrial waste is not generated, and the productivity is excellent.

[0057]

The step of introducing the halogenated butane compound into the dehydrofluorination reaction in the present invention is preferably carried out in the gas phase, especially by a gas phase continuous flow process using a fixed bed reactor. When using a gas-phase continuous flow process, the device, work, etc. can be simplified, which is cost-effective.

[0058]

Catalyst

The step of introducing the halogenated butane compound into the dehydrofluorination reaction in the present invention is preferably carried out in the presence of a catalyst.

[0059]

Preferred catalysts used in the production process of the present invention include activated carbon catalysts, chromium oxide catalysts, zeolite catalysts, aluminosilicate catalysts, and the like. Such catalysts can be both non-fluorinated catalysts and fluorinated catalysts.

[0060]

Activated carbon catalysts are not limited, and examples include powdered activated carbon such as pulverized carbon, molded carbon, granular carbon, and spherical carbon. As the powdered activated carbon, it is preferable to use powdered activated carbon which exhibits a particle size of 4 mesh (4.75 mm) to 100 mesh (0.150 mm) according to JIS test (JIS Z8801). Such activated carbons may be known or commercially available products.

[0061]

Since activated carbon exhibits higher fluorination activity, it is also possible to use, as an activated carbon-based catalyst, a fluorinated activated carbon obtained by pre-fluorinating activated carbon before using it in the reaction. That is, both non-fluorinated activated carbon and fluorinated activated carbon can be used as the activated carbon-based catalyst.

[0062]

Suitable examples of fluorinating agents for fluorinating activated carbon include HF and similar inorganic fluorinating agents, as well as hydrofluorocarbon (HFC) such as hexafluoropropene, chlorofluorocarbon (CFC) such as chlorofluoromethane, hydrochlorofluorocarbon (HCFC), and similar organic fluorinating agents.

[0063]

The method for fluorination of activated carbon is, for example, fluorination by circulating the above-mentioned fluorinating agent at atmospheric pressure at a temperature from room temperature (25°C) to about 400°C.

[0064]

Chromium oxide catalysts are not limited; however, when the chromium oxide is represented by the formula CrO _m , it is preferable that it satisfies the condition 1.5<m<3, more preferably the condition 2<m<2.75, and even more preferably the condition 2<m<2.3. In addition, when the chromium oxide is represented by the formula CrO _m ⋅nH ₂ O, it can be hydrogenated so that the value of n is 3 or less, especially 1 to 1.5.

[0065]

The fluorinated chromium oxide catalyst can be prepared by fluorinating the above-mentioned chromium oxide catalyst. Such fluorination can be performed with, for example, HF or fluorocarbon. Such a fluorinated chromium oxide catalyst can be synthesized, for example, according to the method described in JPH 05-146680A.

[0066]

The following is an example of a method for synthesizing a chromium oxide catalyst and a fluorinated chromium oxide catalyst.

[0067]

Initially, a precipitate of chromium hydroxide can be obtained by mixing an aqueous solution of a chromium salt (chromium nitrate, chromium chloride, chromium alum, chromium sulfate, etc.) with aqueous ammonia. At this time, the physical properties of chromium hydroxide can be controlled by the reaction rate for the precipitation reaction. The reaction rate is preferably high. The reaction rate depends on the temperature of the reaction solution, the mixing method of aqueous ammonia (mixing speed), mixing level, etc.

[0068]

The precipitate can be filtered and washed and then dried. Drying can be carried out, for example, in air at 70 to 200° C. for 1 to 100 hours. The catalyst at this stage is sometimes referred to as the "chromium hydroxide state". Then this catalyst can be crushed. In terms of pellet strength, catalyst activity, etc. it is preferable to control the precipitation reaction rate so that the powder density of the pulverized powder (for example, 95% of the powder having a particle size of 1000 µm or less, especially 46 to 1000 µm) is from 0.6 to 1.1 g/ml and preferably from 0 .6 to 1.0 g/ml. The specific surface area of the powder (BET specific surface area) is preferably 100 m ² /g or more, and more preferably 120 m ² /g or more, for example, under degassing conditions at 200°C for 80 minutes. The upper limit of the specific surface area is, for example, 220 m ² /g.

[0069]

If necessary, this chromium hydroxide powder can be mixed with 3 wt. or less graphite, and granules can be formed using a tablet machine. The size and strength of the granules can be adjusted accordingly.

[0070]

The shaped catalyst can be calcined in an inert atmosphere (eg, under a stream of nitrogen) to form amorphous chromium oxide. The calcination temperature is preferably 360°C or higher, and preferably 380 to 460°C from the viewpoint of suppressing crystallization. The calcination time can be set, for example, to a period of 1 to 5 hours.

[0071]

The specific surface area of the calcined catalyst is preferably, for example, 170 m ² /g or more, more preferably 180 m ² /g or more, and even more preferably 200 m ² /g or more in terms of catalyst activity. The upper limit of the specific surface area is usually preferably about 240 m ² /g and more preferably about 220 m ² /g.

[0072]

The chromium oxide may then be fluorinated to form fluorinated chromium oxide. The fluorination temperature may be in the temperature range in which the resulting water does not condense, and the upper limit may be the temperature at which the catalyst does not crystallize due to the heat of reaction. The fluorination temperature can be set to, for example, 100-460°C. Although the pressure during the fluorination is not limited, it is preferable to carry out the fluorination under pressure during the introduction into the catalytic reaction.

[0073]

Known types of zeolite can be widely used as zeolite catalysts. For example, crystalline hydrated alkali metal or alkaline earth metal aluminosilicates are preferred. The crystal form of the zeolite is not limited, and examples include A type, X type, LSX type, and the like. The alkali metal or alkaline earth metal in the zeolite is not limited, and examples include potassium, sodium, calcium, lithium, and the like.

[0074]

Since the zeolite catalyst shows higher activity due to fluorination, the zeolite catalyst can be prefluorinated before being used in the reaction and used as a fluorinated zeolite catalyst.

[0075]

Suitable examples of fluorinating agents for fluorinating zeolite catalysts include inorganic fluorinating agents such as F ₂ and HF; fluorocarbon-based organic fluorinating agents such as hexafluoropropene, and the like.

[0076]

The zeolite catalyst fluorination method is, for example, fluorination by circulating the above fluorinating agent at atmospheric pressure at room temperature (25°C) to about 400°C.

[0077]

The aluminosilicate catalyst is a complex oxide catalyst containing silica (SiO ₂ ) and alumina (Al ₂ O ₃ ). When the total amount of silica and alumina is taken as 100 wt. -%, a suitable catalyst has, for example, a silica content of from 20 to 90 wt. and especially from 50 to 80% of the mass.

[0078]

Since the aluminosilicate catalyst shows higher activity due to fluorination, the aluminosilicate catalyst can be prefluorinated before being used in the reaction and used as a fluorinated aluminosilicate catalyst.

[0079]

Suitable examples of fluorinating agents for fluorinating aluminosilicate catalysts include inorganic fluorinating agents such as F ₂ and HF; fluorocarbon-based organic fluorinating agents such as hexafluoropropene, and the like.

[0080]

The method for fluorinating an aluminosilicate catalyst is, for example, fluorinating by circulating the above-mentioned fluorinating agent at atmospheric pressure at a temperature from room temperature (25°C) to about 400°C.

[0081]

The catalysts described above may be used singly or in combination of two or more. In terms of conversion rate, selectivity and yield, among them, activated carbon catalysts (activated carbon or fluorinated activated carbon), chromium oxide catalysts (chromium oxide or fluorinated chromium oxide), etc. are preferable; and more preferred are activated carbon catalysts (activated carbon or fluorinated activated carbon).

[0082]

When the above-mentioned chromium oxide catalyst, zeolite catalyst, aluminosilicate catalyst or the like is used as a catalyst, it may also be supported. Suitable examples of such carriers include carbon, alumina (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), silicon dioxide (SiO ₂ ), titanium oxide (TiO ₂ ), and the like. As carbon, activated carbon, amorphous carbon, graphite, diamond, etc. can be used.

[0083]

In the production method of the present invention, when the halogenated butane compound is introduced into the gas phase dehydrofluorination reaction in the presence of a catalyst, for example, it is preferable to contact the catalyst in the solid state (solid phase) with the halogenated butane compound. In this case, the form of the catalyst may be a powder; however, the pellet shape is preferred when the catalyst is used in a gas phase continuous flow process reaction.

[0084]

The specific surface area of the catalyst (hereinafter also referred to as "BET specific surface area") measured by the BET method is generally preferably 10 to 3000 m ² /g, more preferably 10 to 2500 m ² /g, even more 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 these ranges, the particle density of the catalyst is not too small. Therefore, the halogenated butene compound can be produced with higher selectivity. In addition, the conversion rate of the halogenated butane compound can be further improved.

[0085]

Cyclic halocarbide compound

In the present invention, the steps of introducing a halogenated butane compound into the dehydrofluorination reaction can also be carried out in the presence of a cyclic halocarbide compound. A cyclic halocarbide compound refers to a cyclic halocarbide compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound are replaced by halogen atoms. In other words, this compound refers to a cyclic halocarbide compound composed of carbon atoms and halogen atoms and containing no hydrogen atoms.

[0086]

When the step of introducing a halogenated butane compound into the dehydrofluorination reaction is carried out in the presence of such a cyclic halocarbide compound, the reaction equilibrium can be shifted towards the product, and the halogenated butene compound, which is the desired product, can be obtained with higher conversion and higher yield.

[0087]

As such a cyclic halocarbide compound, the compounds described in "(1-1-2-1) Liquid Phase Reaction" may be approved. The same applies to the preferred specific examples and the amounts used.

[0088]

In the production method of the present invention, when a halogenated butane compound is subjected to a gas phase dehydrofluorination reaction in the presence of a cyclic halocarbide compound, for example, it is preferable to contact the halogenated butane compound in the form of a gas (gas phase).

[0089]

Reaction temperature

In the step of introducing the halogenated butane compound into the dehydrofluorination reaction in the present invention, the reaction temperature is usually preferably 230°C or higher, more preferably 280°C or higher, and even more preferably 320°C or higher from the viewpoint that the dehydrofluorination reaction can proceed more effectively, the conversion rate can be further improved, and the halogenated butene compound as the target compound can be obtained with higher selectivity. When activated carbon is used as a catalyst and when a cyclic halogen carbide compound is not used, the reaction temperature is preferably higher to promote the dehydrofluorination reaction more efficiently, and is preferably 400°C or higher, and more preferably 420°C or higher. Even when activated carbon is used as a catalyst and when a halogenated butane compound is subjected to a gas phase dehydrofluorination reaction in the presence of a cyclic halocarbide compound, the dehydrofluorination reaction can proceed more efficiently; thus, the reaction temperature can be set slightly lower, and is generally preferably 230°C or higher, more preferably 280°C or higher, and even more preferably 320°C or higher.

[0090]

The reaction temperature for introducing the halogenated butane compound into the dehydrofluorination reaction in the present invention is generally preferably 500°C or lower, and more preferably 450°C or lower from the viewpoint that the dehydrofluorination reaction can proceed more efficiently, the conversion rate can be further improved, and a halogenated butene compound as a target compound can be obtained with higher selectivity.

[0091]

Reaction time

As for the reaction time in the case of introducing a halogenated butane compound into the dehydrofluorination reaction in the present invention, for example, when a gas-phase flow process is used, contact time of the raw material compound with the catalyst (W/F) [W: mass (g) of catalyst, F: flow rate ( cc/sec) of the starting material compound] is preferably 5 to 100 gs/cc, more preferably 10 to 90 gs/cc, and even more preferably 15 to 80 gs/cc .cm, from the point of view that the conversion rate of the reaction is particularly high, and the halogenated butene compound can be obtained in higher yield and higher selectivity. When the halogenated butane compound is subjected to a gas phase dehydrofluorination reaction in the presence of a cyclic halocarbide compound, the dehydrofluorination reaction can proceed more efficiently; therefore, the lower limit of the contact time can be further lowered, and the contact time is preferably 1 to 100 gsec/cc, more preferably 2 to 90 gsec/cc, and even more preferably 3 to 80 g .sec/cc The contact time refers to the contact time between the feedstock compound and the catalyst.

[0092]

Reaction pressure

The reaction pressure when introducing the halogenated butane compound into the dehydrofluorination reaction in the present invention 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 that the dehydrofluorination reaction can proceed more efficiently, the conversion rate can be further improved, and the halogenated butene compound as the target compound can be obtained with higher selectivity. The upper limit of the reaction pressure is not limited and is usually about 2 MPa. In the present invention, the pressure is overpressure, unless otherwise indicated.

[0093]

In the dehydrofluorination reaction of the halogenated butane compound in the present invention, the reactor for reacting the halogenated butane compound and preferably the catalyst and the cyclic halocarbide compound is not limited in its shape and structure as long as it can withstand the above-described temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, a multitube reactor, and the like. Examples of the reactor material include glass, stainless steel, iron, nickel, iron-nickel alloys, and the like.

[0094]

Examples of the dehydrofluorination reaction

The dehydrofluorination reaction of the halogenated butane compound in the present invention can be carried out in a batch process or a flow process in which a halogenated butane compound as a raw material compound is continuously supplied to the reactor and a halogenated butene compound as a target compound is continuously withdrawn from the reactor. If the halogenated butene compound remains in the reactor as the target compound, the cleavage reaction can proceed further; therefore, it is preferable to carry out the reaction in an on-line process. The step of introducing the halogenated butane compound into the dehydrofluorination reaction in the present invention is preferably carried out in the gas phase, especially by a gas phase continuous flow process using a fixed bed reactor. When using a gas-phase continuous flow process, the device, work, etc. can be simplified, which is cost-effective. When using a batch process, you can also use a closed reaction process or a reaction process at elevated pressure, discussed above in the section "Liquid phase reaction".

[0095]

The atmosphere when introducing the halogenated butane compound into the dehydrofluorination reaction in the present invention is preferably an inert gas atmosphere, a hydrogen fluoride gas atmosphere or the like from the viewpoint of suppressing catalyst degradation. Examples of the inert gas include nitrogen, helium, argon, and the like. Of these inert gases, nitrogen is preferred in terms of cost reduction. The concentration of the inert gas is preferably from 0 to 50 mol%. gas component introduced into the reactor.

[0096]

After the completion of the dehydrofluorination reaction, purification may optionally be carried out according to conventional methods, resulting in a halogenated butene compound represented by formula (2A).

[0097]

(1-1-3) Target compound (Halogenated butene compound)

The target compound of the present invention obtained as described above is a halogenated butene compound represented by the formula (2A):

CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom.

[0098]

In formula (2A), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are the same as X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ in formula (1A), respectively. Therefore, specific examples of the resulting halogenated butene compound represented by formula (2A) include CF ₃ CF=CHCF ₃ , CCl ₃ CCl=CHCCl ₃ , CBr ₃ CBr=CHCBr ₃ and the like. These compounds contain both Z and E isomers.

[0099]

The halogenated butene compound thus obtained can be effectively used for various applications, such as pickling gases for the formation of advanced microstructures in semiconductors, liquid crystals, etc., as well as cleaning gases, precipitating gases, coolants, heat transfer media and building materials. blocks for organic synthesis. The precipitating gas and building block for organic synthesis are described below.

[0100]

1-2: Method for producing a halogenated butene compound from a halogenated butene compound

The method for producing a halogenated butyne compound of the present invention is a method for producing a halogenated butyne compound represented by the formula (3A):

CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom,

and this method includes introducing a halogenated butene compound represented by formula (2A):

CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, and X ⁴ represents a halogen atom, in the dehydrohalogenation reaction.

[0101]

According to the present invention, when the halogenated butene compound represented by the formula (2A) is subjected to a dehydrohalogenation reaction, a selectively halogenated butene compound represented by the formula (3A) in which 1 mol of hydrogen halide per mol of the halogenated butene compound represented by the formula (2A).

[0102]

(1-2-1) Raw material compound (Halogenated butene compound)

The halogenated butene compound as a substrate that can be used in the production method of the present invention is, as described above, the halogenated butene compound represented by the formula (2A):

CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom, and corresponds to the target compound in section "1-1: Method for the production of a halogenated butene compound from a halogenated butane compound.

[0103]

In the formula (2A), as the halogen atom represented by X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ , the halogen atoms mentioned above can be used. The same applies to preferred types.

[0104]

Specific examples of the halogenated butene compound as a substrate that satisfies the above conditions include CF ₃ CF=CHCF ₃ , CCl ₃ CCl=CHCCl ₃ , CBr ₃ CBr=CHCBr ₃ and the like. These compounds contain both Z- and E-isomers. These halogenated butene compounds may be used singly or in combination of two or more. Such halogenated butene compounds may represent known or commercially available products.

[0105]

(1-2-2) Dehydrohalogenation reaction

In the step of introducing the halogenated butene compound into the dehydrohalogenation reaction in the present invention, for example, in the halogenated butene compound ^represented by formula (2A) as the substrate X ¹ , X ² , X 3 , X ⁴ , X ⁵ , X ⁶ and X ⁷ more preferably represent fluorine atoms.

[0106]

That is, this reaction is preferably a dehydrofluorination reaction according to the following reaction equation:

CF ₃ CF=CHCF ₃ → CF ₃ C≡CCF ₃ +HF.

[0107]

The step of introducing the halogenated butene compound into the dehydrohalogenation reaction in the present invention may be carried out in liquid phase or gas phase. Particularly from a performance point of view, it is preferable to carry out this step in the gas phase.

[0108]

The step of introducing the halogenated butene compound into the dehydrohalogenation reaction in the present invention is preferably carried out in the presence of a catalyst and/or a base from the viewpoint of obtaining a target compound with higher selectivity and higher conversion. More specifically, when a liquid phase reaction is used, this step is preferably carried out in the presence of a base and optionally a catalyst, and when a gas phase reaction is used, this step is preferably carried out in the presence of a catalyst. For liquid phase reaction details (solvent, base, catalyst, cyclic halocarbide compound, closed reaction process and pressurized reaction conditions, etc.) and gas phase reaction details (catalyst, cyclic halocarbide compound, reaction temperature, reaction time, reaction pressure, etc.) the explanation of "1-1: Method for producing a halogenated butene compound from a halogenated butane compound" can be applied, except that the expression "reaction for producing a halogenated butene compound from a halogenated butane compound by the reaction dehydrofluorination" is read as "a reaction to obtain a halogenated butene compound from a halogenated butene compound by a dehydrohalogenation reaction". The same applies to preferred types and contents.

[0109]

After completion of the dehydrohalogenation reaction, purification may optionally be carried out according to conventional methods, resulting in a halogenated butyne compound represented by formula (3A).

[0110]

(1-2-3) Target compound (Halogenated butyne compound)

The target compound of the present invention obtained as described above is a halogenated butyne compound represented by the formula (3A):

CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom.

[0111]

In formula (3A), X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are the same as X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ in formula (2A), respectively. Thus, specific examples of the halogenated butyne compound represented by the formula (3A) which are produced include CF ₃ C≡CCF ₃ , CCl ₃ C≡CCCl ₃ , CBr ₃ C≡CCBr ₃ and the like.

[0112]

The halogenated butyne compound thus obtained can be effectively used for various applications, such as pickling gases for the formation of advanced microstructures in semiconductors, liquid crystals, etc., as well as cleaning gases, precipitating gases, coolants, heat transfer media and building materials. blocks for organic synthesis. The precipitating gas and building block for organic synthesis are described later.

[0113]

1-3: Method for producing a halogenated butene compound from a halogenated butane compound via a halogenated butene compound

The method for producing a halogenated butyne compound of the present invention is a method for producing a halogenated butyne compound represented by the formula (3A):

CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom,

and this way includes:

(IA) introducing a halogenated butane compound represented by formula (1A):

CX ¹ X ² X ³ CHX ⁴ CFHCX ⁵ X ⁶ X ⁷ (1A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, and X ⁴ represents a halogen atom, in the dehydrofluorination reaction to obtain a halogenated butene compound represented by formula (2A):

CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are as defined above;

(IIA) after step (IA) removal of hydrogen fluoride; And

(IIIA) after step (IIA), introducing the resulting halogenated butene compound represented by formula (2A):

CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A),

where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are as defined above, in a dehydrohalogenation reaction to obtain a halogenated butyne compound represented by formula (3A):

CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above.

[0114]

(1-3-1) Stage (IA)

In the process for producing a halogenated butene compound of the present invention, the explanation of "1-1: Method for producing a halogenated butene compound from a halogenated butane compound" can be applied to step (IA) as it is.

[0115]

(1-3-2) Stage (IIA)

The method for producing a halogenated butene compound of the present invention includes introducing a halogenated butane compound represented by formula (1A) into a dehydrofluorination reaction to obtain a halogenated butene compound represented by formula (2A) (step (IA)), and then removing hydrogen fluoride from a mixture containing a halogenated butene compound; and hydrogen fluoride (step (IIA)).

[0116]

In the process for producing a halogenated butyne compound of the present invention, after step (IA), hydrogen fluoride generated from the dehydrofluorination reaction in step (IA) is separated and/or removed, followed by production of a halogenated butyne compound in the next step (IIIA), whereby a halogenated butyne compound, which is a target compound, can be obtained by dehydrofluorination with high conversion (yield) and high selectivity.

[0117]

Hydrogen fluoride can be removed from the mixture containing the halogenated butene compound and hydrogen fluoride obtained in step (IA), preferably by separating hydrogen fluoride in a distillation column (FIG. 1) or by removing hydrogen fluoride using a hydrogen halide removal agent (column for removal), such as alkali, Secard, aluminum or silicon dioxide (FIG. 2).

[0118]

In the process for producing a halogenated butyne compound of the present invention, unreacted raw materials (halogenated butane compound, etc.) separated by rectification are preferably reused. In the process for producing a halogenated butane compound of the present invention, the unreacted halogenated butane compound separated by distillation can be returned (reused) to the reactor and used for dehydrofluorination.

[0119]

Method for separating hydrogen fluoride in a distillation column

The boiling point of hydrogen fluoride (HF) to be separated is 19.54°C.

[0120]

In order to remove hydrogen fluoride from the mixture containing the halogenated butene compound and hydrogen fluoride, which is obtained in step (IA), the halogenated butene compound and hydrogen fluoride are separated in a distillation column based on the boiling points of both compounds and based on the difference of boiling points of both compounds. The halogenated butene compound is then collected and the hydrogen fluoride can be separated. In the production of the halogenated butyne compound in the next step (IIIA), the content of hydrogen fluoride can be reduced, and the halogenated butyne compound as the target compound can be produced with high conversion (yield) and high selectivity.

[0121]

Method for Removing Hydrogen Fluoride Using a Hydrogen Halide Removal Agent

The hydrogen fluoride to be separated can be removed with a hydrogen fluoride removal agent. As the hydrogen fluoride removing agent, it is preferable to use alkali, alumina, silicon dioxide, zeolite, Secard and the like hydrogen fluoride removing agents. Secard is an adsorbent (synthetic zeolite) that uses an amorphous clay mineraloid (alumina/silica gel) called "allophane" as the main raw material and is composed of amorphous to weakly crystalline hydrated aluminosilicate.

[0122]

In order to remove hydrogen fluoride from the mixture containing the halogenated butene compound and hydrogen fluoride, which is obtained in step (IA), hydrogen fluoride is removed using a hydrogen fluoride removing agent, and the halogenated butene compound can be collected. In the production of the halogenated butyne compound in the next step (IIIA), the content of hydrogen fluoride can be reduced, and the halogenated butyne compound as the target compound can be produced with high conversion (yield) and high selectivity.

[0123]

Hydrogen fluoride concentration

In the process for producing a halogenated butyne compound of the present invention, after step (IA), the hydrogen fluoride generated by dehydrofluorination in step (IA) is separated and/or removed, followed by the production of a halogenated butyne compound in the next step (IIIA), whereby a halogenated butyne compound, which is a target compound, can be obtained by dehydrofluorination with high conversion (yield) and high selectivity.

[0124]

In the production of a halogenated butene compound in the next step (IIIA), a halogenated butene compound represented by formula (2A) is used as a starting material compound. In this case, in addition to the halogenated butene compound represented by the formula (2A), the mixture containing hydrogen fluoride generated by dehydrofluorination can be introduced into the production of the halogenated butene compound in the next step (IIIA).

[0125]

In the process for producing a halogenated butyne compound of the present invention, in terms that in the production of a halogenated butyne compound in the next step (IIIA), a halogenated butyne compound, which is a target compound, is produced by dehydrofluorination with high conversion (yield) and high selectivity, in of the composition used as the raw material in the next step (IIIA), based on the mixture containing the halogenated butene compound represented by the formula (2A) and hydrogen fluoride (100 mol %), the hydrogen fluoride content (concentration) is preferably 50% they say or less, more preferably 20 mol%. or less, even more preferably 3 mol%. or less, and particularly preferably 0.1 mol%. or less. When the mixture containing the halogenated butene compound represented by the formula (2A) and hydrogen fluoride has a low content of hydrogen fluoride, the halogenated butene compound, which is the target compound, can be produced with high conversion (yield) and high selectivity.

[0126]

(1-3-3) Stage (IIIA)

In the process for producing a halogenated butene compound of the present invention, the explanation of "1-2: Method for producing a halogenated butene compound from a halogenated butene compound" applies to step (IIIA) as it is.

[0127]

(1-3-4) Examples of dehydrofluorination

In the dehydrofluorination step of the present invention, the reaction can be carried out in a batch process or in-line process in which the feed compound (halogenated butane compound) is continuously fed into the reactor and the target compound (halogenated butene compound) is continuously withdrawn from the reactor in the step (IA ). Then, hydrogen fluoride is removed from the mixture containing the halogenated butene compound or hydrogen fluoride (step (IIA)). Step (IIIA) can be carried out in a batch process or a flow process in which the feed compound (halogenated butene compound) is continuously fed into the reactor and the target compound (halogenated butene compound) is continuously withdrawn from the reactor. At each stage, the target compound (halogenated butene compound or halogenated butine compound) does not remain in the reactor, and the dehydrofluorination can proceed further; therefore, it is preferable to carry out the reaction in an on-line process.

[0128]

In the dehydrofluorination step of the present invention, the reaction is preferably carried out in the gas phase, especially by a gas phase continuous flow process using a fixed bed reactor. When using a gas-phase continuous flow process, the device, work, etc. can be simplified, which is cost-effective.

[0129]

In the dehydrofluorination step of the present invention, the reaction atmosphere is preferably an inert gas atmosphere from the viewpoint of suppressing degradation of the catalyst (activated carbon, metal catalyst, etc.). In the present invention, the inert gas is preferably at least one gas selected from the group consisting of nitrogen, helium, argon and carbon dioxide. Of these inert gases, nitrogen is more preferable in terms of cost reduction. The concentration of the inert gas is preferably from 0 to 50 mol%. gas component introduced into the reactor.

[0130]

In the dehydrofluorination step of the present invention, after the completion of the reaction as described above, purification may optionally be carried out according to conventional methods to obtain the target compound (halogenated butene compound or halogenated butine compound).

[0131]

2. Methods for the production of a halogenated alkene compound and a fluorinated alkyne compound

2-1: Process for producing a halogenated alkene compound from a halogenated alkane compound

The method for producing a halogenated alkene compound of the present invention is a method for producing a halogenated alkene compound represented by the formula (2B):

CX ⁸ A ¹ = CHA ² (2B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group, and X ⁸ represents a halogen atom,

and this method includes introducing a halogenated alkane compound represented by formula (1B):

CHX ⁸ A ¹ CHX ⁹ A ² (1B),

where A ¹ and A ² have the meanings defined above, and X ⁸ and X ⁹ are the same or different and each represents a halogen atom, in the dehydrohalogenation reaction in the presence of a catalyst in the gas phase.

[0132]

According to the present invention, when a halogenated alkane compound represented by formula (1B) is subjected to a dehydrohalogenation reaction in the presence of a gas phase catalyst, a selectively halogenated alkene compound represented by formula (2B) in which 1 mol of hydrogen halide is eliminated per mol a halogenated alkane compound represented by formula (1B). Moreover, the abstraction reaction of a hydrogen halide represented as HX ⁸ from a halogenated alkene compound represented by formula (2B) is unlikely to proceed continuously. Furthermore, according to the present invention, as the halogenated alkene compound represented by the formula (2B), the E-isomer can be synthesized selectively among other geometrical isomers. This effect is more pronounced when A ¹ and A ² are perfluoroalkyl groups. Since the α-carbon of trihalogenated methyl groups such as the CF ₃ group becomes electron-deficient due to the electron attraction effect of trihalogenated methyl groups such as the CF ₃ group, halogenated anions such as fluorine anions are less likely to be desorbed. As a result, halogenated butene should be more likely to form than halogenated butyne. In addition, the selective synthesis of the E-isomer is more pronounced when A ¹ and A ² are trifluoromethyl groups. This is because the trans configuration is energetically more stable due to the steric hindrance of trihalogenated methyl groups such as the CF ₃ group.

[0133]

(2-1-1) Raw material compound (Halogenated alkane compound)

In the present invention, the starting material compound in the process for producing a halogenated alkene compound from a halogenated alkane compound is a halogenated alkane compound represented by the formula (1B):

CHX ⁸ A ¹ CHX ⁹ A ² (1B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group, and X ⁸ and X ⁹ are the same or different and each represents a halogen atom.

[0134]

In the formula (1B), as the perfluoroalkyl group denoted as A ¹ and A ² and the halogen atom denoted as X ⁸ and X ⁹ , those mentioned above can be used. The same applies to the preferred specific examples.

[0135]

Examples of the halogenated alkane compound as the starting material compound that satisfies the above conditions include CF ₃ CHClCHClCF ₃ (336mdd), CF ₃ CHClCHFCl, CHFClCHFCl, CF ₃ CHFCHFCF ₃ (338mee), CF ₃ CHFCHF ₂ , CHF ₂ CHF ₂ , CF ₃ CHClCHClC ₂ F ₅ , C ₂ F ₅ CHClCHClC ₂ F ₅ , C ₂ F ₅ CHClCHFCl, CF ₃ CHFCHFC ₂ F ₅ , C ₂ F ₅ CHFCHFC ₂ F ₅ , C ₂ F ₅ CHFCHF ₂ etc. These halogenated alkane compounds may be used singly or in combination of two or more. Such halogenated alkane compounds may represent known or commercially available products.

[0136]

(2-1-2) Dehydrohalogenation reaction

In the step of introducing the halogenated alkane compound into the dehydrohalogenation reaction in the present invention, in terms of the ability to produce a halogenated alkane compound from a halogenated alkane compound with high conversion (yield) and high selectivity, for example, in the halogenated alkane compound represented by formula (1B) as substrate A ¹ and A ² are preferably both trifluoromethyl groups (CF ₃ -), and X ⁸ and X ⁹ are more preferably fluorine atoms or chlorine atoms.

[0137]

That is, this reaction is preferably a dehydrofluorination or dehydrochlorination reaction according to the following reaction equations:

CF ₃ CHClCHClCF ₃ (336mdd) → CF ₃ CCl=CHCF ₃ ((Z) or (E)-1326mxz) + HCl

CF ₃ CHFCHFCF ₃ (338mee) → CF ₃ CF=CHCF ₃ ((Z) or (E)-1327myz) + HF

[0138]

Catalyst

The step of introducing a halogenated alkane compound into a dehydrohalogenation reaction to obtain a halogenated alkene compound in the present invention is carried out in the presence of a gas phase catalyst.

[0139]

The catalyst used in this step is preferably at least one selected from the group consisting of activated carbon and a metal catalyst in terms of conversion, selectivity and yield.

[0140]

When a metal catalyst is used as the catalyst used in this step, the metal catalyst is preferably at least one selected from the group consisting of chromium oxide, fluorinated chromium oxide, chromium fluoride, alumina, fluorinated alumina, aluminum fluoride, iron oxide, fluorinated iron oxide, iron fluoride, nickel oxide, fluorinated nickel oxide, nickel fluoride, magnesium oxide, fluorinated magnesium oxide and magnesium fluoride.

[0141]

At this stage, in terms of the ability to react with a halogenated alkane compound, as a raw material compound, with a high conversion (yield) and give a halogenated alkene compound, as a target compound, with high selectivity, of these catalysts, activated carbon, chromium oxide are more preferable. , fluorinated chromium oxide, alumina, fluorinated alumina, etc.

[0142]

At this stage, when the raw material compound is contacted with the catalyst in the gas phase, it is preferable to contact the catalyst in the solid state (solid phase) with the raw material compound.

[0143]

At this stage, the catalyst may be in powder form; however, the shape of the granules is preferred in the case of a gas phase continuous flow process reaction.

[0144]

The specific surface area of the catalyst (hereinafter referred to as "BET specific surface area") measured by the BET method is generally preferably 10 to 3000 m ² /g, more preferably 100 to 2000 m ² /g, even more preferably 500 to 1500 m ² /g and particularly preferably 1000 to 1300 m ² /g. When the BET specific surface area of the catalyst is within this range, the particle density of the catalyst is not too low. Therefore, the target compound can be obtained with higher selectivity. In addition, the conversion rate of the raw material compound can be further improved.

[0145]

When activated carbon is used as a catalyst, it is preferable to use powdered activated carbon such as pulverized carbon, molded carbon, granular carbon and spherical carbon. As the powdered activated carbon, it is preferable to use powdered activated carbon which exhibits a particle size of 4 mesh (4.76 mm) to 100 mesh (0.149 mm) according to the JIS test.

[0146]

When activated carbon is used as a catalyst, as a form of activated carbon (for example, specific surface area of about 1200 m ² /g), it is preferable to use either powdered or granular activated carbon, and more preferably use granular activated carbon.

[0147]

When a metal catalyst is used as a catalyst, it is preferably supported. As the carrier, for example, carbon, alumina (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), silicon dioxide (SiO ₂ ), titanium oxide (TiO ₂ ) and the like can be preferably used. In addition, activated carbon, amorphous carbon, graphite, diamond, and the like can preferably be used as the carbon.

[0148]

Chromium oxide and fluorinated chromium oxide are described in the present invention as examples of the catalyst. For example, when chromium oxide is represented as Cr ₂ O ₃ .nH ₂ O, n is preferably 3 or less, and more preferably 1 to 1.5. In addition, in the case of chromium oxide, it is preferable that in the formula for the composition of CrO _m, the value of m satisfies the condition 1.5<m<3. As a catalyst, fluorinated chromium oxide can be prepared by fluorination of chromium oxide. Examples of fluorination include fluorination with hydrogen fluoride (HF), fluorination with fluorocarbon, and others.

[0149]

Chromium oxide as a catalyst can be obtained according to the method described in JP 3412165B, for example. Chromium oxide can be fluorinated with hydrogen fluoride (HF treatment) to give fluorinated chromium oxide. The fluorination temperature, for example, is preferably 100 to 460°C. The fluorination pressure is preferably the pressure during the catalytic reaction. In the present invention, it is particularly preferable to use a highly fluorinated chromium oxide catalyst with a high fluorine content. The highly fluorinated chromium oxide catalyst can be obtained by fluorinating chromium oxide at a higher temperature than usual for a long period of time.

[0150]

The highly fluorinated chromium oxide catalyst preferably has a fluorine content of 30% by weight. or more and more preferably from 30 to 45% of the mass. The fluorine content can be measured by the change in mass of the catalyst or by using the method of conventional quantitative analysis of chromium oxide.

[0151]

Cyclic halocarbide compound

In the present invention, the step of introducing a halogenated alkane compound into the dehydrohalogenation reaction may be carried out in the presence of a cyclic halocarbide compound. A cyclic halocarbide compound refers to a cyclic halocarbide compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound are replaced by halogen atoms. In other words, this compound refers to a cyclic halocarbide compound consisting of carbon atoms and halogen atoms and not containing hydrogen atoms.

[0152]

When the step of introducing a halogenated alkane compound into a dehydrohalogenation reaction is carried out in the presence of such a cyclic halocarbide compound, a halogenated alkene compound as a target product can be obtained with higher conversion and higher yield.

[0153]

As the cyclic halocarbide compound, the compounds mentioned above can be used. The same applies to the preferred specific examples, the amounts used, methods of incorporation into the liquid phase reaction and the gas phase reaction, and the like.

[0154]

Reaction temperature

In the step of carrying out the dehydrohalogenation reaction in the present invention, the lower limit of the reaction temperature is usually 50°C, preferably 70°C, and more preferably 100°C from the viewpoint of more effectively promoting the dehydrohalogenation reaction and obtaining the target compound (halogenated alkene compound) with higher selectivity, and also from the viewpoint of suppressing the decrease in the conversion rate from the raw material compound (halogenated alkane compound).

[0155]

In the step of carrying out the dehydrohalogenation reaction in the present invention, the upper limit of the reaction temperature is usually 500°C, preferably 450°C, and more preferably 400°C from the viewpoint that the dehydrohalogenation reaction can proceed more efficiently, and the target compound (halogenated alkene compound) can be obtained with higher selectivity, as well as in terms of suppressing the decrease in selectivity due to decomposition or polymerization of the reaction product.

[0156]

Reaction time

In the step of carrying out the dehydrohalogenation reaction in the present invention, with regard to the reaction time, if the contact time of the raw material compound with the catalyst (W/F ₀ ) [W: mass (g) of the catalyst, F ₀ : flow rate (cc/sec) raw material compound] longer, the conversion rate of the raw material compound can be increased; however, the amount of catalyst increases and large equipment is required, which is inefficient.

[0157]

Therefore, in the step of carrying out the dehydrohalogenation reaction in the present invention, with regard to the contact time, the contact time (W/F ₀ ) of the combination of the raw material (halogenated alkane compound) with the catalyst is preferably 0.1 to 200 gsec/cc , more preferably 0.2 to 150 gsec/cc, even more preferably 0.4 to 100 gsec/cc, and particularly preferably 0.5 to 50 gsec/cc, in terms of improving the conversion rate of the raw material compound (halogenated alkane compound) and reducing the cost of equipment.

[0158]

The contact time of the feedstock compound with the catalyst refers to the contact time between the feedstock compound and the catalyst.

[0159]

When the dehydrohalogenation reaction of the present invention is carried out in the presence of a gas phase catalyst, the target compound (halogenated alkene compound) can be obtained with higher selectivity, especially by suitably adjusting the reaction temperature and the reaction time (contact time) depending on the catalyst.

[0160]

In the dehydrohalogenation reaction of the present invention, when chromium oxide is used as a catalyst, the reaction temperature is preferably 300°C or higher, and more preferably 350°C or higher. In addition, the contact time is preferably 10 gs/cc or more, more preferably 20 gs/cc or more, and even more preferably 40 gs/cc or more.

[0161]

In the dehydrohalogenation reaction of the present invention, when alumina is used as a catalyst, the reaction temperature is preferably 300° C. or higher, and the contact time is preferably 5 gsec/cc or more.

[0162]

In the dehydrohalogenation reaction of the present invention, when activated carbon is used as a catalyst, the reaction temperature is preferably 50 to 600°C, and more preferably 100 to 400°C. In addition, the contact time is preferably 0.2 to 100 gs/cc, more preferably 0.3 to 50 gs/cc, and even more preferably 0.5 to 43 gs/ cc

[0163]

Reaction pressure

In the step of carrying out the dehydrohalogenation reaction in the present invention, the reaction pressure is preferably -0.05 to 2 MPa, more preferably -0.01 to 1 MPa, and even more preferably from normal pressure to 0.5 MPa from the viewpoint of more effectively promoting the reaction. dehydrohalogenation. In the present invention, the pressure is overpressure, unless otherwise indicated.

[0164]

In the dehydrohalogenation reaction step of the present invention, a reactor for reacting a raw material compound (halogenated alkane compound) and a catalyst (activated carbon, metal catalyst, etc.) by bringing them into contact with each other is not limited in shape and structure as long as it can withstand the temperatures and pressures described above. Examples of the reactor include a vertical reactor, a horizontal reactor, a multitube reactor, and the like. Examples of the reactor material include glass, stainless steel, iron, nickel, iron-nickel alloys, and the like.

[0165]

Examples of dehydrohalogenation reactions

The step of carrying out the dehydrohalogenation reaction in the present invention can be carried out in a batch process or a flow process in which the feed compound (halogenated alkane compound) is continuously fed into the reactor and the target compound (halogenated alkene compound) is continuously withdrawn from the reactor. The target compound (halogenated alkene compound) does not remain in the reactor and the dehydrohalogenation reaction can proceed further; thus, it is preferable to carry out the reaction in a flow process.

[0166]

The step of carrying out the dehydrohalogenation reaction in the present invention is preferably carried out in the gas phase, especially with a gas phase continuous flow process using a fixed bed reactor. When using a gas-phase continuous flow process, the device, work, etc. can be simplified, which is cost-effective.

[0167]

In the dehydrohalogenation reaction step of the present invention, the reaction atmosphere is preferably an inert gas atmosphere from the viewpoint of suppressing degradation of the catalyst (activated carbon, metal catalyst, etc.). In the present invention, the inert gas is preferably at least one gas selected from the group consisting of nitrogen, helium, argon and carbon dioxide. Of these inert gases, nitrogen is more preferable in terms of cost reduction. The concentration of the inert gas is preferably from 0 to 50 mol%. gas component introduced into the reactor.

[0168]

In the step of carrying out the dehydrohalogenation reaction in the present invention, after completion of the reaction, purification may optionally be carried out according to conventional methods to result in a halogenated alkene compound represented by formula (2B), which is an objective compound.

[0169]

(2-1-3) Target compound (Halogenated alkene compound)

The target compound of the present invention, obtained as described above, is a halogenated alkene compound represented by the formula (2B):

CX ⁸ A ¹ = CHA ² (2B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group, and X ⁸ represents a halogen atom.

[0170]

In formula (2B), A ¹ , A ² and X ⁸ are the same as A ¹ , A ² and X ⁸ in formula (1B), respectively. Therefore, specific examples of the halogenated alkene compound represented by formula (2B) which are produced include CF ₃ CCl=CHCF ₃ ((Z) or (E)-1326mxz), CF ₃ CCl=CHF, CFCl=CHF, CF ₃ CF= CHCF ₃ ((Z) or (E)-1327myz), CF ₃ CF=CHF, CF ₂ =CHF, CF ₃ CCl=CHC ₂ F ₅ , C ₂ F ₅ CCl=CHC ₂ F ₅ , C ₂ F ₅ CCl =CHF, CF ₃ CF=CHC ₂ F ₅ , C ₂ F ₅ CF=CHC ₂ F ₅ , C ₂ F ₅ CF=CHF, etc. These compounds contain both Z and E isomers.

[0171]

The halogenated alkene compound thus obtained can be effectively used for various applications, such as pickling gases for the formation of advanced microstructures in semiconductors, liquid crystals, etc., as well as cleaning gases, precipitating gases, coolants, heat transfer media and building materials. blocks for organic synthesis. The precipitating gas and building block for organic synthesis are described later.

[0172]

2-2: Method for producing a fluorinated alkyne compound from a halogenated alkene compound

The method for producing a fluorinated alkyne compound of the present invention is a method for producing a fluorinated alkyne compound represented by the formula (3B):

CA ¹ ≡ ^{CA 2} (3B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group,

and this method includes introducing a halogenated alkene compound represented by formula (2B):

CX ⁸ A ¹ = CHA ² (2B),

where A ¹ and A ² have the meanings defined above, and X ⁸ represents a halogen atom, in the dehydrohalogenation reaction in the presence of a catalyst.

[0173]

(2-2-1) Raw material compound (Halogenated alkene compound)

The halogenated alkene compound as a substrate that can be used in the production method of the present invention is, as described above, the halogenated alkene compound represented by the formula (2B):

CX ⁸ A ¹ = CHA ² (2B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group, and X ⁸ represents a halogen atom. This compound corresponds to the objective compound of "2-1: Process for the production of a halogenated alkene compound from a halogenated alkane compound".

[0174]

In the formula (2B), as the perfluoroalkyl group denoted as A ¹ and A ² and the halogen atom denoted as X ⁸ , those mentioned above can be used. The same applies to preferred types.

[0175]

Specific examples of the halogenated alkene compound as a substrate that satisfies the above conditions include CF ₃ CCl=CHCF ₃ ((Z) or (E)-1326mxz), CF ₃ CCl=CHF, CFCl=CHF, CF ₃ CF=CHCF ₃ ((Z) or (E)-1327myz), CF ₃ CF=CHF, CF ₂ =CHF, CF ₃ CCl=CHC ₂ F ₅ , C ₂ F ₅ CCl=CHC ₂ F ₅ , C ₂ F ₅ CCl=CHF , CF ₃ CF=CHC ₂ F ₅ , C ₂ F ₅ CF=CHC ₂ F ₅ , C ₂ F ₅ CF=CHF, etc. These compounds contain both Z and E isomers. These halogenated alkene compounds may be used singly or in combination of two or more. Such halogenated alkene compounds may be known or commercially available products.

[0176]

(2-2-2) Dehydrohalogenation reaction

In the step of introducing the halogenated alkene compound into the dehydrohalogenation reaction in the present invention, in terms of the ability to produce a fluorinated alkyne compound from a halogenated alkene compound with high conversion (yield) and high selectivity, for example, in the halogenated alkene compound represented by formula (2B) as substrate, A ¹ and A ² are preferably both trifluoromethyl groups (CF ₃ -), and X ⁸ is more preferably a fluorine atom or a chlorine atom.

[0177]

That is, this reaction is preferably a dehydrofluorination reaction or a dehydrochlorination reaction according to the following reaction equations:

CF ₃ CCl \u003d CHCF ₃ ((Z) or (E)-1326mxz) → CF ₃ C≡CCF ₃ (PF2B) + HCl

CF ₃ CF=CHCF ₃ ((Z) or (E)-1327myz) → CF ₃ C≡CCF ₃ (PF2B) + HF

[0178]

The step of introducing the halogenated alkene compound into the dehydrohalogenation reaction in the present invention may be carried out in liquid phase or gas phase. Particularly from a performance point of view, it is preferable to carry out this step in the gas phase.

[0179]

The step of introducing a halogenated alkene compound into the dehydrohalogenation reaction in the present invention is preferably carried out in the presence of a catalyst and/or a base from the viewpoint of obtaining a target compound with higher selectivity and higher conversion. More specifically, when a liquid phase reaction is used, this step is preferably carried out in the presence of a base and optionally a catalyst, and when a gas phase reaction is used, this step is preferably carried out in the presence of a catalyst. For detailed information on liquid phase reaction (solvent, base, catalyst, cyclic halogen carbide compound, closed reaction process and pressurized reaction process conditions, etc.), explanation of section "1-1: Method for producing halogenated butene compound from halogenated butane compound" may be used, except that the expression "reaction to obtain a halogenated butene compound from a halogenated butane compound by a dehydrofluorination reaction" is read as "reaction to obtain a fluorinated alkyne compound from a halogenated alkene compound by a dehydrohalogenation reaction". In addition, for detailed information on the gas phase reaction (catalyst, cyclic halocarbide compound, reaction temperature, reaction time, reaction pressure, etc.), the explanation of section "2-1: Method for producing a halogenated alkene compound from a halogenated alkane compound" can be used, except that the expression "reaction to obtain a halogenated alkene compound from a halogenated alkane compound by a dehydrohalogenation reaction" is read as "reaction to obtain a fluorinated alkyne compound from a halogenated alkene compound by a dehydrohalogenation reaction". The same applies to preferred types and contents.

[0180]

After the completion of the dehydrohalogenation reaction, purification may optionally be carried out according to conventional methods, resulting in a fluorinated butyne compound represented by formula (3B).

[0181]

(2-2-3) Target Compound (Fluorinated Butyne Compound)

The target compound of the present invention, obtained as described above, is a fluorinated butyne compound represented by the formula (3B):

CA ¹ ≡ ^{CA 2} (3B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group.

[0182]

In formula (3B), A ¹ and A ² are the same as A ¹ and A ² in formula (2B), respectively. Thus, specific examples of the fluorinated butyne compound represented by the formula (3B) which is obtained include CF ₃ C≡CCF ₃ (PF2B), CF ₃ C≡CF, CF≡CF, CF ₃ C≡CC ₂ F ₅ , C ₂ F ₅ C≡CC ₂ F ₅ , C ₂ F ₅ C≡CF, etc.

[0183]

The fluorinated butyne compound thus obtained can be effectively used for various applications, such as pickling gases for the formation of advanced microstructures in semiconductors, liquid crystals, etc., as well as cleaning gases, precipitating gases, coolants, heat transfer media and building materials. blocks for organic synthesis. The precipitating gas and building block for organic synthesis are described later.

[0184]

2-3: Process for producing a fluorinated alkyne compound from a halogenated alkane compound via a halogenated alkene compound

The method for producing a fluorinated alkyne compound of the present invention is a method for producing a fluorinated alkyne compound represented by the formula (3B):

CA ¹ ≡ ^{CA 2} (3B),

where A ¹ and A ² are the same or different and each represents a fluorine atom or a perfluoroalkyl group,

and this way includes:

(IB) introducing a halogenated alkane compound represented by formula (1B):

CHX ⁸ A ¹ CHX ⁹ A ² (1B),

where A ¹ and A ² are as defined above, and X ⁸ and X ⁹ are the same or different and each represents a halogen atom, in a dehydrohalogenation reaction in the presence of a gas phase catalyst to obtain a halogenated alkene compound represented by formula (2B):

CX ⁸ A ¹ = CHA ² (2B),

where A ¹ , A ² and X ⁸ have the meanings defined above;

(IIB) after step (IB) removing the hydrogen halide; And

(IIIB) after step (IIB), introducing the resulting halogenated alkene compound represented by formula (2B):

CX ⁸ A ¹ = CHA ² (2B),

where A ¹ , A ² and X ⁸ have the meanings defined above, in the reaction of dehydrohalogenation in the presence of a catalyst in the gas phase to obtain a fluorinated alkyne compound represented by formula (3B):

CA ¹ ≡ ^{CA 2} (3B),

where A ¹ and A ² have the meanings defined above.

[0185]

(2-3-1) Stage (IB)

In the method for producing a fluorinated butyne compound of the present invention, the explanation of "2-1: Method for producing a halogenated alkene compound from a halogenated alkane compound" can be applied to the step (IB) as it is.

[0186]

(2-3-2) Stage (IIB)

The method for producing a fluorinated alkyne compound of the present invention includes introducing a halogenated alkane compound represented by formula (1B) into a dehydrohalogenation reaction to obtain a halogenated alkene compound represented by formula (2B) (step (IB)), and then removing hydrogen halide from a mixture containing a halogenated alkene compound; and a hydrogen halide (step (IIB)).

[0187]

In the process for producing a fluorinated alkyne compound of the present invention, after step (IB), the hydrogen halide generated from the dehydrohalogenation reaction in step (IB) is separated and/or removed, followed by the production of a fluorinated alkyne compound in the next step (IIIB), resulting in whereby the fluorinated alkyne compound, which is the target compound, can be produced by the dehydrohalogenation reaction with high conversion (yield) and high selectivity.

[0188]

For a method for removing hydrogen halide from a mixture containing a halogenated alkene compound and a hydrogen halide obtained in step (IB), explanation of "(1-3-2) Step (IIA)" of "Method for producing a halogenated butyne compound from a halogenated butane compound through "halogenated butene compound" may be used as is, except that it is read as hydrogen halide separation instead of hydrogen fluoride separation.

[0189]

(2-3-3) Stage (IIIB)

In the process for producing a fluorinated alkyne compound of the present invention, the explanation of "2-2: Method for producing a fluorinated alkyne compound from a halogenated alkene compound" can be applied to step (IIIB) as it is.

[0190]

(2-3-4) Examples of dehydrohalogenation reaction

In the step of carrying out the dehydrohalogenation reaction in the present invention, the reaction can be carried out in a batch process or in an in-line process in which the feed compound (halogenated alkane compound) is continuously fed into the reactor, and the target compound (halogenated alkene compound) is continuously withdrawn from the reactor in the step ( IB). The hydrogen halide is then removed from the mixture containing the halogenated alkene compound and hydrogen halide (step (IIB)). Step (IIIB) can be carried out in a batch process or a flow process in which the feed compound (halogenated alkene compound) is continuously fed into the reactor and the target compound (fluorinated alkyne compound) is continuously withdrawn from the reactor. At each stage, the target compound (halogenated alkene compound or fluorinated alkyne compound) does not remain in the reactor, and the dehydrohalogenation reaction can proceed further; thus, it is preferable to carry out the reaction in a flow process.

[0191]

In the dehydrohalogenation reaction step of the present invention, the reaction is preferably carried out in the gas phase, especially by a gas phase continuous flow process using a fixed bed reactor. When using a gas-phase continuous flow process, the device, work, etc. can be simplified, which is cost-effective.

[0192]

In the dehydrohalogenation reaction step of the present invention, the reaction atmosphere is preferably an inert gas atmosphere from the viewpoint of suppressing degradation of the catalyst (activated carbon, metal catalyst, etc.). In the present invention, the inert gas is preferably at least one gas selected from the group consisting of nitrogen, helium, argon and carbon dioxide. Of these inert gases, nitrogen is more preferable in terms of cost reduction. The concentration of the inert gas is preferably from 0 to 50 mol%. gas component introduced into the reactor.

[0193]

In the step of carrying out the dehydrohalogenation reaction in the present invention, after the completion of the reaction as described above, purification may optionally be carried out according to conventional methods to result in the target compound (halogenated alkene compound or fluorinated alkyne compound).

[0194]

3. Composition

A halogenated butene compound, a halogenated butyne compound, a halogenated alkene compound, or a fluorinated alkyne compound can be prepared as described above; however, these compounds can be obtained in the form of compositions containing the appropriate target compounds.

[0195]

3-1: Compositions containing a halogenated butene compound or a halogenated alkene compound

According to the production method of the present invention, for example, when using the method described in "1-1: Method for producing a halogenated butene compound from a halogenated butane compound" above, for example, the halogenated butene compound represented by the formula (2A) can be obtained in the form of a composition containing both E- and Z-isomers. In addition, this composition may contain a halogenated butyne compound represented by formula (3A):

CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A),

where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are as defined above, and

halogenated butadiene compound represented by the formula (4):

CX ¹ X ² = CX ⁴ CF = CX ⁵ X ⁶ (4),

where X ¹ , X ² , X ⁴ , X ⁵ and X ⁶ have the meanings defined above.

[0196]

In formulas (2A), (3A) and (4), examples of the halogen atom designated as X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ include fluorine atom, chlorine atom, bromine atom and an iodine atom; preferably a fluorine atom and a chlorine atom; and more preferably a fluorine atom.

[0197]

When the total amount of the composition of the present invention is taken as 100 mol %, the content of the halogenated butene compound represented by formula (2A) is preferably 80.00 to 99.99 mol %, more preferably 90.00 to 99.98 %. they say and even more preferably from 92.00 to 99.97 mol%. In addition, the content of the halogenated butyne compound represented by formula (3A) is preferably 0.00 to 3.00 mol %. and more preferably from 0.01 to 2.00 mol%, but may be from 1.00 to 10.00 mol%. (especially from 2.00 to 8.00% mol.) depending on the synthesis conditions. Moreover, the content of the halogenated butadiene compound represented by formula (4) is preferably 0.00 to 0.50 mol%. and more preferably from 0.01 to 0.30 mol%. When the halogenated butene compound represented by formula (2A) contains both E and Z isomers, the above content refers to their total amount.

[0198]

According to the production method of the present invention, as the halogenated butene compound represented by the formula (2A), the E-isomer can be selectively synthesized. Thus, the content of (E)-halogenated butene compound is preferably from 85.00 to 99.98 mol%. (especially from 86.00 to 99.00% mol.), and the content of (Z)-halogenated butene compounds is preferably from 0.01 to 15.00% mol. (especially from 1.00 to 14.00% mol).

[0199]

According to the production method of the present invention, even when produced as a halogenated butene composition, the halogenated butene compound represented by the formula (2A) can be produced in high conversion, high yield and high selectivity as described above. Thus, components other than the halogenated butene compound represented by formula (2A) can be reduced in the halogenated butene composition, which can shorten the purification work to obtain the halogenated butene compound represented by formula (2A).

[0200]

On the contrary, by applying the method described in "2-1: Method for producing a halogenated alkene compound from a halogenated alkane compound", for example, a composition containing a halogenated alkene compound represented by formula (2B) and at least one an additional compound containing at least one hydrofluorocarbon (HFC) compound other than the halogenated alkene compound represented by formula (2B).

[0201]

The additional compound is preferably at least one selected from the group consisting of hexafluorobutene, hexafluorobutane and octafluorobutane.

[0202]

More specifically, in the process for producing a halogenated alkene compound from a halogenated alkane compound of the present invention, when 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (1326mxz) is obtained as an end product, (Z)-1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz(Z)).

[0203]

In the composition containing the halogenated alkene compound represented by formula (2B) of the present invention, when the total amount of the composition is taken as 100 mole %, the content of the halogenated alkene compound represented by formula (2B) is preferably 80 mole %. or more, and the content of additional compounds is preferably 20 mol%. or less. In the composition containing the halogenated alkene compound represented by formula (2B) of the present invention, when the total amount of the composition is taken as 100 mole %, the content of the halogenated alkene compound represented by formula (2B) is preferably 85 mole %. or more, more preferably 90 mol%. or more and even more preferably 95 mol%. or more. In the composition containing the halogenated alkene compound represented by the formula (2B) of the present invention, when the total amount of the composition is taken as 100 mole %, the content of the halogenated alkene compound represented by the formula (2B) is preferably 80 to 99.9%. mol., more preferably from 85 to 99.9% mol., even more preferably from 90 to 99.9% mol. and especially preferably from 95 to 99.9 mol%.

[0204]

3-2: Composition containing a halogenated butyne compound or a fluorinated alkyne compound

According to the production method of the present invention, for example, when the method described in "2-2: Method for producing a fluorinated alkyne compound from a halogenated alkene compound" is applied, for example, a composition containing a fluorinated alkyne compound represented by the formula (3B ), and at least one additional compound containing at least one hydrofluorocarbon (HFC) compound other than the fluorinated alkyne compound represented by formula (3B). When the method described in "1-2: Method for producing a halogenated butene compound from a halogenated butene compound" is used, a composition containing a halogenated butyne compound represented by formula (3A) and at least one additional compound containing a hydrofluorocarbon (HFC) compound other than the halogenated butyne compound represented by formula (3A).

[0205]

The additional compound is preferably at least one selected from the group consisting of trifluoromethane, difluoromethane, tetrafluoromethane and monofluoromethane.

[0206]

In the method for producing a halogenated butyne compound from a halogenated butene compound and the method for producing a fluorinated alkyne compound from a halogenated alkene compound of the present invention, when 1,1,1,4,4,4-hexafluoro-2-butyne (PF2B) is obtained as an end product , trifluoromethane (HFC-23, R23) can be obtained.

[0207]

In the composition containing a halogenated butyne compound or a fluorinated alkyne compound in the present invention, when the total amount of the composition is taken as 100 mole %, the content of the halogenated butyne compound or the fluorinated alkyne compound is preferably 80 mole %. or more, and the content of additional compounds is preferably 20 mol%. or less. In a composition containing a halogenated butyne compound or a fluorinated alkyne compound, when the total amount of the composition is taken as 100 mole %, the content of the halogenated butyne compound or the fluorinated alkyne compound is preferably 85 mole %. or more, more preferably 90 mol%. or more and even more preferably 95 mol%. or more. In the composition containing the halogenated butyne compound or the fluorinated alkyne compound of the present invention, when the total amount of the composition is taken as 100 mole %, the content of the halogenated butyne compound or the fluorinated alkyne compound is preferably 80 to 99.9 mole %, more preferably 85 to 99.9 mol%, even more preferably 90 to 99.9 mol%. and especially preferably from 95 to 99.9 mol%.

[0208]

3-3: Use of a composition containing a halogenated butene compound, a halogenated butyne compound, a halogenated alkene compound or a fluorinated alkyne compound

According to the production methods of the present invention, even when prepared as a composition containing a halogenated butene compound, a halogenated butyne compound, a halogenated alkene compound or a fluorinated alkyne compound, a halogenated butene compound, a halogenated butyne compound, a halogenated alkene compound or a fluorinated alkyne compound can be obtained especially with high selectivity. As a result, the content of components other than a halogenated butene compound, a halogenated butyne compound, a halogenated alkene compound, and a fluorinated alkyne compound can be reduced in the composition. According to the production methods of the present invention, purification work can be reduced to produce a halogenated butene compound, a halogenated butyne compound, a halogenated alkene compound, or a fluorinated alkyne compound.

[0209]

The composition containing a halogenated butene compound, a halogenated butyne compound, a halogenated alkene compound or a fluorinated alkyne compound of the present invention can be effectively used for various applications, such as etch gases to form advanced microstructures in semiconductors, liquid crystals, etc., as well as cleaning gases, precipitating gases, refrigerants, heat transfer media and building blocks for organic synthesis, as in the case of halogenated butene compound, halogenated butyne compound, halogenated alkene compound or fluorinated alkyne compound alone.

[0210]

The precipitating gas is the gas that the etch-resistant polymer layer deposits.

[0211]

A building block for organic synthesis refers to a substance that can be a precursor to a compound having a highly reactive skeleton. For example, when the composition of the present invention is reacted with a fluorine-containing organosilicon compound such as CF ₃ Si(CH ₃ ) ₃ , a fluoroalkyl group such as a CF ₃ group may be introduced, converting it into a substance which may be a purifier or a fluorine-containing pharmaceutical intermediate. product.

[0212]

While embodiments of the invention have been described above, various changes in form and detail may be made without departing from the spirit and scope of the claims.

Examples

[0213]

Characteristic features of the present invention are explained below by considering examples. The present invention is not limited to these examples.

[0214]

In the methods for producing a halogenated butene compound of Examples 1 to 7, the starting material compound is a halogenated butane compound represented by the formula (1A), where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are fluorine atoms , and a halogenated butene compound is obtained by a dehydrofluorination reaction according to the following reaction equation:

CF ₃ CFHCFHCF ₃ → CF ₃ CF=CHCF ₃ +HF.

[0215]

In the production methods of the halogenated alkene compound and the fluorinated butyne compound of Example 8, the starting material compound is the halogenated alkane compound represented by the formula (1B), where X ⁸ and X ⁹ are chlorine atoms, and A ¹ and A ² are trifluoromethyl groups, and a halogenated alkene compound and a halogenated butyne compound are obtained by a dehydrochlorination reaction according to the following reaction equations:

CF ₃ CHClCHClCF ₃ (336mdd) → CF ₃ CCl=CHCF ₃ ((Z) or (E)-1326mxz) + HCl

CF ₃ CCl \u003d CHCF ₃ ((Z) or (E)-1326mxz) → CF ₃ C≡CCF ₃ (PF2B) + HCl.

[0216]

In the methods for producing a halogenated alkene compound and a fluorinated butyne compound of Examples 9 to 20, the starting material compound is a halogenated alkane compound represented by the formula (1B), where X ⁸ and X ⁹ are fluorine atoms, and A ¹ and A ² are trifluoromethyl groups , and a halogenated alkene compound and a fluorinated butyne compound are obtained by a dehydrofluorination reaction according to the following reaction equations:

CF ₃ CHFCHFCF ₃ (338mee) → CF ₃ CF=CHCF ₃ ((Z) or (E)-1327myz) + HF

CF ₃ CF=CHCF ₃ ((Z) or (E)-1327myz) → CF ₃ C≡CCF ₃ (PF2B) + HF.

[0217]

Examples 1-3: Liquid phase reaction

An autoclave (200 cc) is used as the reaction system.

[0218]

Due to the use of an autoclave as the reaction system, this reaction system refers to (1) a closed reaction process in the presence of a base, or (2) an elevated pressure reaction process carried out in the presence of a base at a reaction temperature of 10°C or higher and a reaction pressure of 0 kPa or more. Pressurization in this way involves sealing.

[0219]

To the autoclave, 7.0 g of a 50% (w/w) aqueous solution of KOH or a 50% (w/w) solution of potassium tetra-butoxide (t-BuOK) in dibutyl ether (Bu ₂ O) was added as a reaction solution. Optionally, 0.28 g of methyltrioctylammonium chloride (trade name: Aliquat 336) is added as a catalyst. In addition, 8.0 g of the starting material compound (CF ₃ CFHCFHCF ₃ ) was added. After the lid is closed to create a closed system, nitrogen is supplied and the pressure is increased. The pressure at this time is 20 kPa. Stirring is then carried out at room temperature (25° C.) to promote the reaction. After the start of the dehydrofluorination reaction, samples are taken as needed. The reaction is stopped when there are no changes in the reaction system. The pressure at the end of the reaction is 80 kPa.

[0220]

After stopping the stirring, the reaction product is cooled to 0°C. Then, mass spectrometry was carried out with a gas chromatography/mass spectrometry combination (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"). Structural analysis by NMR spectra was performed using an NMR instrument (manufactured by JEOL Ltd., trade name "400YH"). The results of mass spectrometry and structural analysis confirm that CF ₃ CF=CHCF ₃ is obtained as the target compound. The results are presented in table 1.

[0221]

Examples 4-6: Gas phase reaction (Activated carbon)

A stainless steel tube (outer diameter 1/2 dm) as a reaction tube was filled with 10 g of an activated carbon catalyst (manufactured by Osaka Gas Chemicals Co., Ltd.; specific surface area 1200 m ² /g) as a catalyst. . After drying at 200° C. for 2 hours under nitrogen atmosphere, the CF ₃ CFHCFHCF ₃ compound (raw material compound) is allowed to flow through the reaction tube at normal pressure, so that the contact time (W/F) of CF ₃ CFHCFHCF ₃ (raw material compound) and activated carbon catalyst is 15 gsec/cc, 30 gsec/cc or 47 gsec/cc.

[0222]

The reaction proceeds using a gas-phase continuous flow process.

[0223]

The reaction tube is heated at 450°C to start the dehydrofluorination reaction.

[0224]

One hour after the start of the dehydrofluorination reaction, the distillate that has passed through the purification column is collected.

[0225]

Thereafter, mass spectrometry was carried out with a combination gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"). Structural analysis by NMR spectra was performed using an NMR instrument (manufactured by JEOL Ltd., trade name "400YH"). The results of mass spectrometry and structural analysis confirm that CF ₃ CF=CHCF ₃ is obtained as the target compound. The results are presented in table 1.

[0226]

Example 7 Gas Phase Reaction (Chromium Oxide Catalyst)

The reactions are allowed to proceed in the same manner as in Examples 4-6, except that a chromium oxide (Cr ₂ O ₃ ) catalyst is used as the catalyst, the reaction temperature is 350°C, and the contact time (W/F ) CF ₃ CFHCFHCF ₃ (compound of starting material) and chromium oxide catalyst is 47 gsec/cc. The results of mass spectrometry and structural analysis confirm that CF ₃ CF=CHCF ₃ is obtained as the target compound. The results are presented in table 1.

[0227]

Table 1

Example 1 2 3 4 5 6 7 Reaction Liquid-phase Liquid-phase Liquid-phase Gas-phase Gas-phase Gas-phase Gas-phase Solvent Water Bu ₂ O Water - - - - Base KOH t-BuOK KOH - - - - Catalyst Aliquat 336 - - Assets. coal Assets. coal Assets. coal _{Cr2O3 _} Temperature (°C) 25 60 25 450 450 450 350 W/F (gs/cc) - - - 47 thirty 15 47 Reaction time (hour) 0.5 2 5 1 1 1 1 Conversion rate (mol %) 95.2 89.2 93.4 99.1 99.0 98.0 80.1 Selectivity (mol %) _CF3 CF= _CHCF3 99.48 96.85 99.17 97.6 97.0 98.4 94.1 E-isomer 98.58 96.03 97.17 86.3 86.9 89.1 87.2 Z-isomer 0.90 0.82 2.00 11.3 10.1 9.3 6.9 _{CF3 C≡CCF3} 0.220 2.54 0.11 0.72 0.71 0.69 0.6 _CF2 =CFCF= _CF2 0.001 0.02 0.001 0.10 0.10 0.10 0.002 Other 0.30 0.81 0.73 1.52 2.09 0.71 5.30 Total 100 100 100 100 100 100 100

[0228]

Example 8 (Dehydrochlorination)

336mdd (CF ₃ CHClCHClCF ₃ ) → 1326mxz (CF ₃ CCl=CHCF ₃ ) → PF2B (CF ₃ C≡CCF ₃ )

(1) 336mdd (CF ₃ CHClCHClCF ₃ ) → 1326mxz (CF ₃ CCl=CHCF ₃ )

A stainless steel tube (outer diameter 1/2 dm) was used as the reaction tube, and 10 g of activated carbon catalyst (specific surface area 1200 m ² /g) was filled as a catalyst. After drying at 200° C. for 2 hours under nitrogen atmosphere, the CF ₃ CHClCHClCF ₃ compound (raw material compound) is allowed to flow through the reactor at normal pressure, so that the contact time (W/F ₀ ) of CF ₃ CHClCHClCF ₃ (raw material compound ) and an activated carbon catalyst is 5 gsec/cc or 25 gsec/cc.

[0229]

The reaction proceeds using a gas-phase continuous flow process.

[0230]

The reactor is heated at 300°C or 400°C to start the dehydrochlorination.

[0231]

(2) Hydrogen chloride removal

One hour after the start of the dehydrochlorination, the distillate that has passed through the purification column is collected.

[0232]

Thereafter, mass spectrometry was carried out with a combination gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"). Structural analysis by NMR spectra was performed using an NMR instrument (manufactured by JEOL Ltd., trade name "400YH").

[0233]

The results of mass spectrometry and structural analysis confirmed that a halogenated alkene compound (1326mxz: CF ₃ CCl=CHCF ₃ ) was obtained as the target compound.

[0234]

In addition, in the process for producing a halogenated alkene compound from a halogenated alkane compound, (Z)-1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz(Z)) besides 1326mxz ( CF ₃ CCl=CHCF ₃ ).

[0235]

table 2

336mdd (CF ₃ CHClCHClCF ₃ ) → 1326mxz (CF ₃ CCl=CHCF ₃ )

Reaction temperature
(°C) W/F contact time ₀
(g.sec/cc) Conversion rate from compound of starting material 336mdd
(mol %) Selectivity
(mol %) Target connection 1326mxz R23 PF2B 1327myz Z1336mzz 1316mxx Other Example 8-1 300 5 94.08 95.89 0.00 0.00 0.00 2.71 0.73 0.67 Example 8-2 300 25 93.36 96.02 0.00 0.00 0.00 3.18 0.42 0.38 Example 8-3 400 5 97.21 89.90 0.04 0.15 0.06 4.58 2.27 2.49 Example 8-4 400 25 91.85 90.26 0.04 0.09 0.31 5.59 1.92 1.78

336mdd: CF ₃ CHClCHClCF ₃

1326mxz: CF ₃ CCl=CHCF ₃

R23: CHF ₃

PF2B: _{CF3 C≡CCF3}

1327myz: CF ₃ CF=CHCF ₃

Z1336mzz: _CF3CH = _CHCF3

1316mxx: CF ₃ CCl=CClCF ₃

[0236]

(3) 1326mxz (CF ₃ CCl=CHCF ₃ ) → PF2B (CF ₃ C≡CCF ₃ )

A stainless steel tube (outer diameter 1/2 dm) was used as the reaction tube, and 10 g of activated carbon catalyst (specific surface area 1200 m ² /g) was filled as a catalyst.

[0237]

In this operation, the reaction is carried out by returning the reaction gas containing the halogenated alkene compound obtained in the above manner to the reactor (first reactor) or allowing it to flow to the next reactor (second reactor) filled with an activated carbon catalyst.

[0238]

At this time, the concentration of hydrogen chloride in the reaction gas containing the halogenated alkene compound is 50 mol%. The reaction gas from the first reactor is subjected to fractionation, alkali treatment, Secard treatment, alumina treatment, or the like, to bring the hydrogen chloride concentration to 20 mol %, 3 mol %. or 0.1% mol.

[0239]

After drying at 200° C. for 2 hours under nitrogen atmosphere, the CF ₃ CCl=CHCF ₃ compound (the starting material compound) is allowed to flow through the reactor at normal pressure, so that the contact time (W/F ₀ ) of CF ₃ CCl=CHCF ₃ (compound of starting material) and activated carbon catalyst is 0.5 gsec/cc, 20 gsec/cc or 43 gsec/cc.

[0240]

The reaction proceeds using a gas-phase continuous flow process.

[0241]

The reactor is heated at 400°C to start the dehydrochlorination.

[0242]

One hour after the start of the dehydrochlorination, the distillate that has passed through the purification column is collected.

[0243]

Thereafter, mass spectrometry was carried out with a combination gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"). Structural analysis by NMR spectra was performed using an NMR instrument (manufactured by JEOL Ltd., trade name "400YH").

[0244]

The results of mass spectrometry and structural analysis confirm that a fluorinated alkyne compound (PF2B (CF ₃ C≡CCF ₃ )) is obtained as the target compound.

[0245]

In addition, in the process for producing a fluorinated alkyne compound from a halogenated alkene compound, trifluoromethane (HFC-23, R23) is obtained as a target product in addition to PF2B.

[0246]

Table 3:

1326mxz (CF ₃ CCl=CHCF ₃ ) → PF2B (CF ₃ C≡CCF ₃ )

Reaction temperature
(°C) W/F contact time ₀
(g.sec/cc) Conversion rate from starting material compound 1326mx (mol %) Selectivity
(mol %) Target connection PF2B 1327myz R23 Other Hydrochloric acid concentration: 0.1% mol. Example 8-5 400 43 14.32 2.80 81.09 0.34 15.77 Example 8-6 400 20 14.21 10.43 70.64 0.34 18.59 Example 8-7 400 0.5 13.20 96.50 4.32 0.21 3.29 Hydrochloric acid concentration: 3% mol. Example 8-8 400 43 14.32 2.10 83.09 0.34 14.81 Example 8-9 400 20 14.21 9.43 79.54 0.34 11.03 Example 8-10 400 0.5 13.20 85.50 9.44 0.21 5.06 Hydrochloric acid concentration: 20 mol %. Example 8-11 400 43 5.33 0.09 31.32 0.01 69.58 Example 8-12 400 20 6.43 5.12 10.11 0.20 84.57 Example 8-13 400 0.5 6.21 5.17 4.04 0.03 90.76 Hydrochloric acid concentration: 50 mol%. Example 8-14 400 43 1.25 0.09 0.32 0.01 99.58 Example 8-15 400 20 0.89 0.12 0.11 0.20 99.57 Example 8-16 400 0.5 0.88 0.17 0.04 0.03 99.76

1326mxz: CF ₃ CCl=CHCF ₃

PF2B: _{CF3 C≡CCF3}

R23: CHF ₃

1327myz: CF ₃ CF=CHCF ₃

[0247]

Example 9 (Dehydrofluorination)

338mee (CF ₃ CHFCHFCF ₃ ) → 1327myz (CF ₃ CF=CHCF ₃ ) → PF2B (CF ₃ C≡CCF ₃ )

(1) 338mee (CF ₃ CHFCHFCF ₃ ) → 1327myz (CF ₃ CF=CHCF ₃ ).

A stainless steel tube (outer diameter 1/2 dm) was used as the reaction tube, and 10 g of activated carbon catalyst (specific surface area 1200 m ² /g) was filled as a catalyst.

[0248]

After drying at 200° C. for 2 hours under a nitrogen atmosphere, the CF ₃ CHFCHFCF ₃ (raw material compound) is allowed to flow through the reactor at normal pressure, so that the contact time (W/F ₀ ) of the CF ₃ CHFCHFCF ₃ (raw material compound ) and an activated carbon catalyst is 5 gsec/cc or 25 gsec/cc.

[0249]

The reaction proceeds using a gas-phase continuous flow process.

[0250]

The reactor is heated at 100°C, 200°C, 300°C or 400°C to start dehydrofluorination.

[0251]

(2) Hydrogen fluoride removal

One hour after the start of the dehydrofluorination, the distillate that has passed through the purification column is collected.

[0252]

Thereafter, mass spectrometry was carried out with a combination gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"). Structural analysis by NMR spectra was performed using an NMR instrument (manufactured by JEOL Ltd., trade name "400YH").

[0253]

The results of mass spectrometry and structural analysis confirm that a halogenated alkene compound (1327myz: CF ₃ CF=CHCF ₃ ) is obtained as the target compound.

[0254]

(3) 1327myz (CF ₃ CF=CHCF ₃ ) → PF2B (CF ₃ C≡CCF ₃ )

A stainless steel tube (outer diameter 1/2 dm) was used as the reaction tube, and 10 g of activated carbon catalyst (specific surface area 1200 m ² /g) was filled as a catalyst.

[0255]

In this operation, the reaction is carried out by returning the reaction gas containing the halogenated alkene compound obtained as described above to the reactor (first reactor) or allowing it to flow to the next reactor (second reactor) filled with an activated carbon catalyst.

[0256]

At this time, the concentration of hydrogen chloride in the reaction gas containing the halogenated alkene compound is 50 mol%. The reaction gas from the first reactor is subjected to fractionation, alkali treatment, Secard treatment, alumina treatment, or the like, to bring the hydrogen chloride concentration to 20 mol %, 3 mol %. or 0.1% mol.

[0257]

After drying at 200° C. for 2 hours under a nitrogen atmosphere, the CF ₃ CF=CHCF ₃ compound (the starting material compound) is allowed to flow through the reactor at normal pressure, so that the contact time (W/F ₀ ) of CF ₃ CCl=CHCF ₃ (compound of starting material) and activated carbon catalyst is 0.5 gsec/cc, 20 gsec/cc or 43 gsec/cc.

[0258]

The reaction proceeds using a gas-phase continuous flow process.

[0259]

The reactor is heated at 400°C to start dehydrofluorination.

[0260]

One hour after the start of the dehydrofluorination, the distillate that has passed through the purification column is collected.

[0261]

Thereafter, mass spectrometry was carried out with a combination gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"). Structural analysis by NMR spectra was performed using an NMR instrument (manufactured by JEOL Ltd., trade name "400YH").

[0262]

The results of mass spectrometry and structural analysis confirm that a fluorinated alkyne compound (PF2B (CF ₃ C≡CCF ₃ )) is obtained as the target compound.

[0263]

In addition, in the process for producing a fluorinated alkyne compound from a halogenated alkene compound, trifluoromethane (HFC-23, R23) is obtained as a target product in addition to PF2.

[0264]

Table 4

1327myz (CF ₃ CF=CHCF ₃ ) → PF2B (CF ₃ C≡CCF ₃ )

Reaction temperature
(°C) W/F contact time ₀
(g.sec/cc) Conversion rate from starting material compound 1327myz
(mol %) Selectivity
(mol %) Target Compound
PF2B R23 Other Hydrofluoric acid concentration: 0.1% mol. Example 9-1 400 40 2.4 77.4 11.2 11.3 Example 9-2 400 10 13.2 89.5 1.1 9.4 Example 9-3 400 2.8 27.9 98.8 0.4 0.7 Hydrofluoric acid concentration: 3% mol. Example 9-4 400 40 2.7 76.9 11.2 11.9 Example 9-5 400 10 12.9 89.9 1.2 8.9 Example 9-6 400 2.8 28.2 98.8 0.7 0.5 Hydrofluoric acid concentration: 20 mol %. Example 9-7 400 40 0.8 0.09 0.01 99.9 Example 9-8 400 10 1.2 1.12 0.19 98.7 Example 9-9 400 2.8 3.3 2.11 0.03 97.9

1327myz: CF ₃ CF=CHCF ₃

PF2B: _{CF3 C≡CCF3}

R23: CHF ₃

[0265]

Examples 10-16 (Dehydrofluorination)

338mee (CF ₃ CHFCHFCF ₃ ) → 1327myz (CF ₃ CF=CHCF ₃ )

A stainless steel tube (outer diameter 1/2 dm) was used as the reaction tube, and 10 g of activated carbon catalyst (specific surface area 1200 m ² /g) was filled as a catalyst. After drying at 200° C. for 2 hours under a nitrogen atmosphere, the CF ₃ CHFCHFCF ₃ (raw material compound) is allowed to flow through the reactor at normal pressure, so that the contact time (W/F ₀ ) of the CF ₃ CHFCHFCF ₃ (raw material compound ) and activated carbon catalyst is from 2 to 47 gsec/cc. Thereafter, in Examples 10-13, 4 moles of octafluorocyclobutane (c-C ₄ F ₈ ; C318) per mole of CF ₃ CHFCHFCF ₃ (compound of starting material) are allowed to flow through the reactor.

[0266]

The reaction proceeds using a gas-phase continuous flow process.

[0267]

The reactor is heated at 400°C to start the dehydrochlorination.

[0268]

One hour after the start of the dehydrochlorination, the distillate that has passed through the purification column is collected.

[0269]

Thereafter, mass spectrometry was carried out by a combination gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"). Structural analysis by NMR spectra was performed using an NMR instrument (manufactured by JEOL Ltd., trade name "400YH").

[0270]

The results of mass spectrometry and structural analysis confirm that a halogenated alkene compound (1327myz: CF ₃ CF=CHCF ₃ ) is obtained as the target compound.

[0271]

In addition, in the process for producing a halogenated alkene compound from a halogenated alkane compound, 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz), 1,1,1,4,4 ,4-hexafluoro-2-butyne (PF2B), etc. in addition to 1327myz (CF ₃ CF=CHCF ₃ ).

[0272]

Table 5

338mee (CF ₃ CHFCHFCF ₃ ) → 1327myz (CF ₃ CF=CHCF ₃ )

Reaction temperature
(°C) W/F contact time ₀
(g.sec / cm ³ ) Molar ratio
C318/336mee Conversion rate from starting material compound 336mee
(mol %) Selectivity
(mol %) Target compound 1327myz PF2B 1336mzz Other Example 10 400 15 4 93.31 82.60 1.38 10.88 5.14 Example 11 400 6 4 97.54 94.44 5.02 0.00 0.53 Example 12 400 3 4 93.85 93.01 5.66 0.00 1.33 Example 13 400 2 4 91.45 90.95 6.05 0.00 3.00 Example 14 400 47 Without C318 41.22 94.08 0.12 0.00 5.80 Example 15 400 20 Without C318 22.21 94.99 0.14 0.00 4.87 Example 16 400 10 Without C318 10.22 97.08 0.09 0.00 2.83

336mee: CF ₃ CHFCHFCF ₃

1327myz: CF ₃ CF=CHCF ₃

PF2B: _{CF3 C≡CCF3}

1336mzz: _CF3CH = _CHCF3

[0273]

Examples 17-20 (Dehydrofluorination)

1327myz (CF ₃ CF=CHCF ₃ ) → PF2B (CF ₃ C≡CCF ₃ )

A stainless steel tube (outer diameter 1/2 dm) was used as the reaction tube, and 10 g of activated carbon catalyst (specific surface area 1200 m ² /g) was filled as a catalyst. After drying at 200° C. for 2 hours under nitrogen atmosphere, the CF ₃ CF=CHCF ₃ compound (the starting material compound) is allowed to flow through the reactor at normal pressure, so that the contact time (W/F ₀ ) of the CF ₃ CF=CHCF ₃ (compound of starting material) and activated carbon catalyst is 2 gs/cc, 2.8 gs/cc or 10 gs/cc. Thereafter, in Examples 17-18, 4 moles of octafluorocyclobutane (c-C ₄ F ₈ ; C318) per mole of CF ₃ CF=CHCF ₃ (compound of starting material) are allowed to flow through the reactor.

[0274]

The reaction proceeds using a gas-phase continuous flow process.

[0275]

The reactor is heated at 400°C to start the dehydrochlorination.

[0276]

One hour after the start of the dehydrochlorination, the distillate that has passed through the purification column is collected.

[0277]

Thereafter, mass spectrometry was carried out with a combination gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"). Structural analysis by NMR spectra was performed using an NMR instrument (manufactured by JEOL Ltd., trade name "400YH").

[0278]

The results of mass spectrometry and structural analysis confirm that a fluorinated alkyne compound (PF2B: CF ₃ C≡CCF ₃ ) is obtained as the target compound.

[0279]

In addition, in the process for producing a halogenated alkene compound from a halogenated alkane compound, trifluoromethane (HFC-23, R23) in addition to PF2B (CF ₃ C≡CCF ₃ ) is obtained as a target product.

[0280]

Table 6

1327myz (CF ₃ CF=CHCF ₃ ) → PF2B (CF ₃ C≡CCF ₃ )

Reaction temperature (°C) W/F contact time ₀
(g.sec/cc) Molar ratio
C318/336mee Conversion rate from starting material compound 1327myz
(mol %) Selectivity
(mol %) Target connection PF2B R23 Other Example 17 400 10 4 42.9 98.16 1.30 0.54 Example 18 400 2 4 52.5 98.28 1.20 0.52 Example 19 400 10 Without C318 13.19 89.53 1.12 9.36 Example 20 400 2.8 Without C318 27.87 98.83 0.43 0.74

1327myz: CF ₃ CF=CHCF ₃

PF2B: _{CF3 C≡CCF3}

R23: CHF ₃

Claims (68)

1. Process for the production of a halogenated butene compound represented by the formula (2A) CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A), where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom, and this method includes introducing a halogenated butane compound represented by formula (1A) CX ¹ X ² X ³ CHX ⁴ CFHCX ⁵ X ⁶ X ⁷ (1A), where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, in the dehydrofluorination reaction in the gas phase or liquid phase, wherein the dehydrofluorination reaction is carried out in the presence of at least one catalyst selected from the group consisting of an activated carbon catalyst, a chromium oxide catalyst and an aluminosilicate catalyst, when the dehydrofluorination reaction is carried out in the gas phase. 2. Process for the production of a halogenated butyne compound represented by the formula (3A) CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A), where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom, and this method includes introducing a halogenated butene compound represented by formula (2A) CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A), where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, and X ⁴ represents a halogen atom, in the gas phase dehydrohalogenation reaction, wherein the dehydrohalogenation reaction is carried out in the presence of at least one catalyst selected from the group consisting of an activated carbon catalyst, a chromium oxide catalyst, and an aluminosilicate catalyst. 3. Process for the production of a halogenated butyne compound represented by the formula (3A) CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A), where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom, and this way includes: (IA) introducing a halogenated butane compound represented by formula (1A) CX ¹ X ² X ³ CHX ⁴ CFHCX ⁵ X ⁶ X ⁷ (1A), where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, and X ⁴ represents a halogen atom, in the gas phase or liquid phase dehydrofluorination reaction to obtain a halogenated butene compound represented by the formula ( 2A) CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A), where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, wherein the dehydrohalogenation reaction is carried out in the presence of at least one catalyst selected from the group consisting of an activated carbon catalyst, a chromium oxide catalyst, and an aluminosilicate catalyst when the dehydrofluorination reaction is carried out in the gas phase; (IIA) after step (IA) removal of hydrogen fluoride; And (IIIA) after step (IIA) introduction of the resulting halogenated butene compound represented by formula (2A) CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A), where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are as defined above, in a gas phase dehydrohalogenation reaction to obtain a halogenated butyne compound represented by formula (3A) CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A), where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, wherein the dehydrohalogenation reaction is carried out in the presence of at least one catalyst selected from the group consisting of an activated carbon catalyst, a chromium oxide catalyst, and an aluminosilicate catalyst. 4. Process for the production of a halogenated butene compound represented by the formula (2A) CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A), where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom, and this method includes introducing a halogenated butane compound represented by formula (1A) CX ¹ X ² X ³ CHX ⁴ CFHCX ⁵ X ⁶ X ⁷ (1A), where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, in the dehydrofluorination reaction in the presence of a cyclic halocarbide compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound replaced by halogen atoms. 5. Process for the production of a halogenated butyne compound represented by the formula (3A) CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A), where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom, and this method includes introducing a halogenated butene compound represented by formula (2A) CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A), where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, and X ⁴ represents a halogen atom, in the dehydrohalogenation reaction in the presence of a cyclic halogen carbide compound in which all hydrogen atoms bonded to atoms carbon, in the hydrocarbon compound are replaced by halogen atoms. 6. Process for the production of a halogenated butyne compound represented by the formula (3A) CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A), where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a halogen atom, and this way includes: (IA) introducing a halogenated butane compound represented by formula (1A) CX ¹ X ² X ³ CHX ⁴ CFHCX ⁵ X ⁶ X ⁷ (1A), where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ are as defined above, and X ⁴ represents a halogen atom, in the dehydrofluorination reaction to obtain a halogenated butene compound represented by formula (2A) CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A), where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, where the dehydrohalogenation reaction is carried out in the presence of a cyclic halogen carbide compound in which all hydrogen atoms associated with carbon atoms in the hydrocarbon compound are replaced by halogen atoms; (IIA) after step (IA) removal of hydrogen fluoride; And (IIIA) after step (IIA) introduction of the resulting halogenated butene compound represented by formula (2A) CX ¹ X ² X ³ CX ⁴ = CHCX ⁵ X ⁶ X ⁷ (2A), where X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and X ⁷ are as defined above, in a dehydrohalogenation reaction to obtain a halogenated butyne compound represented by formula (3A) CX ¹ X ² X ³ C≡CCX ⁵ X ⁶ X ⁷ (3A), where X ¹ , X ² , X ³ , X ⁵ , X ⁶ and X ⁷ have the meanings defined above, wherein the dehydrohalogenation reaction is carried out in the presence of a cyclic halocarbide compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound have been replaced by halogen atoms. 7. The production method according to any one of paragraphs. 1 and 3-6, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in liquid phase. 8. The production method according to claim 7, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in the presence of a base. 9. The production method according to claim 7, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in the presence of a base and a catalyst. 10. The production method according to claim 7, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in a closed reaction process. 11. The production method according to any one of paragraphs. 1 and 3-6, wherein the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in the gas phase. 12. The production method according to any one of paragraphs. 4-6, wherein the dehydrofluorination reaction step and/or dehydrohalogenation reaction step is carried out in the presence of at least one catalyst selected from the group consisting of an activated carbon catalyst, a chromium oxide catalyst, a zeolite catalyst, and an aluminosilicate catalyst. 13. The production method according to any one of paragraphs. 1-6, wherein the dehydrofluorination reaction step and/or dehydrohalogenation reaction step is carried out by a gas phase continuous flow process. 14. The production method according to any one of paragraphs. 1-3, in which the step of the dehydrofluorination reaction and/or the dehydrohalogenation reaction is carried out in the presence of a cyclic halocarbide compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound have been replaced by halogen atoms.

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