WO2020170980A1

WO2020170980A1 - Method for producing halogenated butene

Info

Publication number: WO2020170980A1
Application number: PCT/JP2020/005856
Authority: WO
Inventors: 友亮江藤; 中村　新吾
Original assignee: ダイキン工業株式会社
Priority date: 2019-02-21
Filing date: 2020-02-14
Publication date: 2020-08-27
Also published as: TW202043182A; KR20210129107A; TWI829871B; JP6827246B2; KR102683558B1; CN113474319A; JP2020132585A

Abstract

A method for producing a halogenated butene compound represented by CX¹X²X³CX⁴=CHCX⁷X⁸X⁹ [In the formula, X¹, X², X³, X⁴, X⁷, X⁸ and X⁹ are identical or different and represent halogen atoms.], the method being equipped with a step for reacting a hydrogen halide with a halogenated butyne compound represented by CX¹X²X³C≡CCX⁷X⁸X⁹ [In the formula, X¹, X², X³, X⁷, X⁸ and X⁹ are the same as indicated above.] in the presence of a catalyst. This production method makes it possible to selectively obtain a butene compound which has seven halogen atoms at a high conversion ratio.

Description

Method for producing halogenated butene compound

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

Butene compounds having 7 halogen atoms, typified by heptafluorobutene, are expected as dry etching gas for semiconductors, cleaning gas, building blocks for organic synthesis, etc.

As a method for producing this butene compound having 7 halogen atoms, for example, in Non-Patent Document 1, after CF ₃ C≡CCF ₃ and AgF are reacted to obtain CF ₃ CF=C(CF ₃ )Ag, , CF ₃ CF=CHCF ₃ was obtained by reacting with HCl in acetonitrile.

The present disclosure has an object to provide a method capable of obtaining a butene compound having a high conversion rate and having 7 halogen atoms with a high selectivity.

The present disclosure includes the following configurations.
Item 1. General formula (1):
CX ¹ X ² X ³ CX ⁴ = CHCX ⁷ X ⁸ X ⁹ (1)
[In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ are the same or different and each represents a halogen atom. ]
A method for producing a halogenated butene compound represented by
In the presence of a catalyst,
General formula (2):
CX ¹ X ² X ³ C ≡ CCX ⁷ X ⁸ X ⁹ (2)
[Wherein X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same as defined above. ]
A method for producing, comprising a step of reacting a halogenated butyne compound represented by with a hydrogen halide.
Item 2. The halogenated butene compound represented by the general formula (1) is CF ₃ CF=CHCF ₃ , and the halogenated butyne compound represented by the general formula (2) is CF ₃ C≡CCF ₃ . Item 2. The manufacturing method according to Item 1.
Item 3. Item 3. The production method according to Item 1 or 2, wherein the catalyst contains at least one selected from the group consisting of a fluorinated or non-fluorinated activated carbon catalyst and a fluorinated or non-fluorinated Lewis acid catalyst.
Item 4. Item 1 to, wherein the catalyst is a fluorinated or non-fluorinated Lewis acid catalyst, and the Lewis acid catalyst is at least one selected from the group consisting of a chromium oxide catalyst, an alumina catalyst, a silica-alumina catalyst, and a zeolite catalyst. The manufacturing method according to any one of 3 above.
Item 5. Item 5. The method according to any one of Items 1 to 4, wherein 30 to 250 mol of hydrogen halide is reacted with 1 mol of the halogenated butyne compound represented by the general formula (2).
Item 6. General formula (1):
CX ¹ X ² X ³ CX ⁴ = CHCX ⁷ X ⁸ X ⁹ (1)
[In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ are the same or different and each represents a halogen atom. ]
A halogenated butene compound represented by
General formula (3):
CX ¹ X ² X ³ CX ⁴ X ⁵ CHX ⁶ CX ⁷ X ⁸ X ⁹ (3)
[In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ are the same as defined above. One of X ⁵ and X ⁶ represents a hydrogen atom, and the other represents a halogen atom. ]
A composition containing a halogenated butane compound represented by
A composition in which the content of the halogenated butene compound represented by the general formula (1) is 91.00 to 99.99 mol% based on 100 mol% of the total amount of the composition.
Item 7. Item 7. The composition according to Item 6, which is used as a cleaning gas, an etching gas, or a building block for organic synthesis.

According to the present disclosure, a butene compound having 7 halogen atoms can be synthesized by a method having a high conversion rate and a high selectivity.

In the present specification, “inclusion” is a concept that includes all of “comprise”, “consistently essentially of”, and “consistent of”. Further, in the present specification, when the numerical range is shown by “A to B”, it means A or more and B or less.

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

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

Conventionally, according to the method of Non-Patent Document 1, CF ₃ C≡CCF ₃ is reacted with AgF to obtain CF ₃ CF=C(CF ₃ )Ag, and then CF ₃ C═C(CF ₃ )Ag is reacted with HCl in acetonitrile to obtain CF _3. _{Although 3} CF=CHCF ₃ was obtained, the two-step reaction was required and the total yield was only 57%.

From the above, according to the conventional method, the yield was only 57% and the number of steps was large. According to the production method of the present disclosure, a butene compound having 7 halogen atoms can be synthesized by a method having a higher conversion rate and a higher selectivity than ever before.

1. Method for producing halogenated butene compound The method for producing a halogenated butene compound of the present disclosure,
General formula (1):
CX ¹ X ² X ³ CX ⁴ = CHCX ⁷ X ⁸ X ⁹ (1)
[In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ are the same or different and each represents a halogen atom. ]
A method for producing a halogenated butene compound represented by
In the presence of a catalyst,
General formula (2):
CX ¹ X ² X ³ C ≡ CCX ⁷ X ⁸ X ⁹ (2)
[Wherein X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same as defined above. ]
And a step of reacting a halogenated butyne compound represented by

In the production method of the present disclosure, when the reaction between the halogenated butyne compound represented by the general formula (2) and hydrogen halide is carried out without a catalyst, the halogenated butyne compound represented by the general formula (2) 1 General formula (3) in which 2 mol of hydrogen halide is added to mol:
CX ¹ X ² X ³ CX ⁴ X ⁵ CHX ⁶ CX ⁷ X ⁸ X ⁹ (3)
[In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ are the same as defined above. One of X ⁵ and X ⁶ represents a hydrogen atom, and the other represents a halogen atom. ]
A considerable amount of the halogenated butane compound represented by is produced as a by-product (eg, more than 9.00 mol %).

On the other hand, by reacting the halogenated butyne compound represented by the general formula (2) with hydrogen halide in the presence of a catalyst, 1 mol of the halogenated butyne compound represented by the general formula (2) can be obtained. The addition of 2 moles of hydrogen halide is suppressed, and 1 mole of hydrogen halide is added to 1 mole of the halogenated butyne compound represented by the general formula (2). The halogenated butene compound represented can be obtained selectively. This is because the trihalogenated methyl groups (CX ¹ X ² X ³ and CX ⁷ X ⁸ X ⁹ ) are the effects of strong electron withdrawing groups. Due to the strong electron-withdrawing effect, the trihalogenated methyl group reduces the electron density of the electrons of the adjacent double bond or triple bond, so that the addition reaction to the unsaturated bond is less likely to occur. Since a halogenated butyne compound has a triple bond, it easily undergoes an addition reaction of hydrogen halide due to its high reactivity.However, a halogenated butene compound reacts with hydrogen halide due to the effect of a trihalogenated methyl group. Without being a halogenated butane compound, a halogenated butene compound can be selectively obtained.

The halogenated butyne compound as a substrate that can be used in the production method of the present disclosure has the general formula (2):
CX ¹ X ² X ³ C ≡ CCX ⁷ X ⁸ X ⁹ (2)
[In the formula, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same or different and each represents a halogen atom. ]
It is a halogenated butyne compound represented by.

In the general formula (2), examples of the halogen atom represented by X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the halogenated butyne compound that is the substrate, a halogenated butene compound is particularly preferable in terms of high conversion, yield and selectivity, and X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ is preferably a fluorine atom.

The above X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ may be the same or different.

Specific examples of the halogenated butyne compound as a substrate satisfying the above conditions include CF ₃ C≡CCF ₃ , CCl ₃ C≡CCCl ₃ , and CBr ₃ C≡CCBr ₃ . These halogenated butyne compounds can be used alone or in combination of two or more. As such a halogenated butyne compound, a known or commercially available product can be adopted. It is also possible to synthesize them according to a conventional method such as JP-A 2012-001448.

Examples of hydrogen halides that react with halogenated butyne compounds include hydrogen fluoride, hydrogen chloride, and hydrogen bromide. Hydrogen fluoride is preferable from the viewpoints of the conversion rate, yield and selectivity of the reaction. These hydrogen halides can be used alone or in combination of two or more.

It is usually preferable to supply the hydrogen halide together with the halogenated butyne compound (substrate) to the reactor in the gas phase. The amount of hydrogen halide to be reacted with the halogenated butyne compound (substrate) is preferably 30 to 250 mol, more preferably 35 to 240 mol, and more preferably 40 to 230 mol, relative to 1 mol of the halogenated butyne compound (substrate). Is more preferable. By setting this range, it is possible to further reduce the generation of impurities by further suppressing the excessive addition reaction due to hydrogen halide while advancing the addition reaction due to hydrogen halide better. The halogenated butene compound (1) has a high selectivity and can be recovered in a high yield.

The step of reacting a halogenated butyne compound and hydrogen halide in the present disclosure is an addition reaction with hydrogen halide and is performed in the presence of a catalyst. The step (addition reaction) of reacting the halogenated butyne compound with hydrogen halide in the production method of the present disclosure is preferably performed in a gas phase, particularly in a gas phase continuous flow system using a fixed bed reactor. When the gas phase continuous flow system is used, the apparatus, operation and the like can be simplified, and it is economically advantageous.

In the step of reacting a halogenated butyne compound and hydrogen halide in the present disclosure, for example, as a substrate, in the halogenated butyne compound represented by the general formula (2), X ¹ , X ² , X ³ , X ⁷ , More preferably, X ⁸ and X ⁹ are fluorine atoms.

That is, the following reaction formula:
CF ₃ C ≡ CCF ₃ + HF → CF ₃ CF=CHCF ₃
Accordingly, the addition reaction with hydrogen fluoride is preferable.

As the catalyst used in the production method of the present disclosure, a fluorinated or non-fluorinated activated carbon catalyst, a fluorinated or non-fluorinated Lewis acid catalyst and the like are preferable.

The activated carbon catalyst is not particularly limited, and examples thereof include powdered activated carbon such as crushed coal, shaped coal, granular coal, and spherical coal. As the powdered activated carbon, it is preferable to use powdered activated carbon having a particle size of 4 mesh (4.75 mm) to 100 mesh (0.150 mm) in the JIS test (JIS Z8801). Known or commercially available products can be adopted as these activated carbons.

Since activated carbon shows stronger activity when fluorinated, it is possible to use fluorinated activated carbon obtained by previously fluorinating activated carbon before use in the reaction. That is, as the activated carbon catalyst, both non-fluorinated activated carbon and fluorinated activated carbon can be used.

Examples of the fluorinating agent for fluorinating activated carbon include inorganic fluorinating agents such as HF, hydrofluorocarbons (HFC) such as hexafluoropropene, chlorofluorocarbons (CFC) such as chlorofluoromethane, and hydrochlorofluorocarbons. Organic fluorinating agents such as (HCFC) can also be used.

As a method of fluorinating activated carbon, for example, a method of circulating the above-mentioned fluorinating agent under atmospheric pressure under a temperature condition of room temperature (25° C.) to 400° C. can be mentioned.

The Lewis acid catalyst is not particularly limited, and examples thereof include a chromium oxide catalyst, an alumina catalyst, a silica-alumina catalyst, and a zeolite catalyst. As these Lewis acid catalysts, both non-fluorinated Lewis acid catalysts and fluorinated Lewis acid catalysts can be adopted.

The chromium oxide catalyst is not particularly limited, but when chromium oxide is expressed by CrOm, 1.5<m<3 is preferable, 2<m<2.75 is more preferable, and 2<m<2.3 is further preferable. When chromium oxide is represented by CrO _m ·nH ₂ O, it may be hydrated so that the value of n is 3 or less, particularly 1 to 1.5.

The fluorinated chromium oxide catalyst can be prepared by fluorinating the above chromium oxide catalyst. This fluorination can be performed using, for example, HF, fluorocarbon or the like. Such a fluorinated chromium oxide catalyst can be synthesized, for example, according to the method described in JP-A No. 05-146680.

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

First, a precipitate of chromium hydroxide can be obtained by mixing an aqueous solution of chromium salt (chromium nitrate, chromium chloride, chromium alum, chromium sulfate, etc.) with aqueous ammonia. The physical properties of chromium hydroxide can be controlled by the reaction rate of the precipitation reaction at this time. The reaction rate is preferably high. The reaction rate depends on the temperature of the reaction solution, the method of mixing ammonia water (mixing rate), the stirring state, and the like.

The precipitate can be filtered, washed and dried. Drying can be performed, for example, in air at 70 to 200° C. for 1 to 100 hours. The catalyst at this stage is sometimes called a state of chromium hydroxide. The catalyst can then be disintegrated. From the viewpoint of pellet strength, catalyst activity, etc., the powder density of crushed powder (for example, particle size 1000 μm or less, especially 95% for particle size 46-1000 μm) is 0.6-1.1 g/ml, It is preferable to adjust the precipitation reaction rate so that it is preferably 0.6 to 1.0 g/ml. The specific surface area of the powder (specific surface area by BET method) is preferably 100 m ² /g or more, and more preferably 120 m ² /g or more under degassing conditions of 200° C. and 80 minutes. The upper limit of the specific surface area is, for example, about 220 m ² /g.

-If necessary, graphite can be mixed in an amount of 3% by weight or less with this chromium hydroxide powder, and pellets can be formed with a tableting machine. The size and strength of the pellet can be adjusted appropriately.

Amorphous chromium oxide can be obtained by firing the molded catalyst in an inert atmosphere, for example, in a nitrogen stream. The firing temperature is preferably 360° C. or higher, and from the viewpoint of suppressing crystallization, it is preferably 380 to 460° C. The firing time may be, for example, 1 to 5 hours.

The specific surface area of the calcined catalyst is, for example, preferably 170 m ² /g or more, more preferably 180 m ² /g or more, still more preferably 200 m ² /g or more, from the viewpoint of the activity of the catalyst. The upper limit of the specific surface area is generally preferably about 240 m ² / g, about 220 m ² / g is more preferable.

Next, fluorinated chromium oxide can be obtained by fluorinating the chromium oxide. The fluorination temperature may be set in a temperature range in which generated water does not condense, and the upper limit may be a temperature at which the catalyst is not crystallized by the heat of reaction. The fluorination temperature may be, for example, 100 to 460°C. There is no limitation on the pressure during fluorination, but it is preferable to carry out the pressure at the time of being subjected to the catalytic reaction.

Examples of the alumina catalyst include α-alumina and activated alumina. Examples of activated alumina include ρ-alumina, χ-alumina, κ-alumina, η-alumina, pseudo γ-alumina, γ-alumina, σ-alumina, and θ-alumina.

A silica-alumina catalyst can also be used as the composite oxide. The silica-alumina catalyst is a composite oxide catalyst containing silica (SiO ₂ ) and alumina (Al ₂ O ₃ ), and the total amount of silica and alumina is 100% by mass, for example, the content of silica is 20 to 90% by mass. In particular, 50 to 80% by weight of catalyst can be used.

Alumina catalysts and silica-alumina catalysts exhibit stronger activity when fluorinated, so it is possible to fluorinate the alumina catalyst in advance before use in the reaction and use it as a fluorinated alumina catalyst. Can also be fluorinated and used as a fluorinated silica-alumina catalyst.

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

As a method for fluorinating the alumina catalyst and the silica-alumina catalyst, for example, a method of circulating the above-mentioned fluorinating agent under atmospheric pressure under a temperature condition of room temperature (25°C) to 400°C to fluorinate is mentioned. You can

As the zeolite catalyst, well-known types of zeolite can be widely adopted. For example, a crystalline hydrous aluminosilicate of an alkali metal or an alkaline earth metal is preferable. The crystal form of zeolite is not particularly limited, and examples thereof include A type, X type, LSX type and the like. The alkali metal or alkaline earth metal in the zeolite is not particularly limited, and examples thereof include potassium, sodium, calcium and lithium.

∙ Since the zeolite catalyst becomes stronger by fluorinating, it can be used as a fluorinated zeolite catalyst by fluorinating the zeolite catalyst before use in the reaction.

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

As a method of fluorinating the zeolite catalyst, for example, a method of circulating the above fluorinating agent under atmospheric pressure under a temperature condition of room temperature (25° C.) to 400° C. and fluorinating it can be mentioned.

The above catalysts can be used alone or in combination of two or more. Among these, from the viewpoint of conversion rate, selectivity and yield, fluorinated or non-fluorinated activated carbon catalyst, fluorinated or non-fluorinated chromium oxide catalyst, fluorinated or non-fluorinated alumina catalyst and the like are preferable, and fluorinated Alternatively, a non-fluorinated activated carbon catalyst, a fluorinated or non-fluorinated chromium oxide catalyst and the like are more preferable.

When the above-mentioned fluorinated or non-fluorinated Lewis acid catalyst is used as the catalyst, it can be supported on a carrier. Examples of such a carrier include carbon, alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), silica (SiO ₂ ), titania (TiO ₂ ), and the like. As carbon, activated carbon, amorphous carbon, graphite, diamond or the like can be used.

In the production method of the present disclosure, in reacting a halogenated butyne compound with hydrogen halide in the presence of a catalyst, for example, it is preferable to contact the catalyst in a solid state (solid phase) with the halogenated butyne compound. In this case, the catalyst may be in the form of powder, but pellets are preferred when they are used in a gas phase continuous flow reaction.

Measured specific surface area by the BET method of the catalyst (hereinafter, sometimes referred to as "BET specific surface area".) Is preferably normally 10 ~ 3,000m ² / g, more preferably ^{10 ~ 2500m 2 / g, 20} ~ 2000m ² /g is more preferable, and 30 to 1500 m ² /g is particularly preferable. When the BET specific surface area of the catalyst is in such a range, the density of the catalyst particles does not become too small, so that the halogenated butene compound can be obtained with higher selectivity. Further, it is possible to further improve the conversion rate of the halogenated butyne compound.

In the step of reacting a halogenated butyne compound and hydrogen halide in the present disclosure, the lower limit of the reaction temperature is a target compound, which allows the addition reaction with hydrogen halide to proceed more efficiently to further improve the conversion rate. From the viewpoint that a halogenated butene compound can be obtained with higher selectivity, it is usually preferably 180° C. or higher, more preferably 200° C. or higher. When a Lewis acid catalyst is used as the catalyst, the lower limit of the reaction temperature is preferably 280°C or higher and more preferably 320°C or higher for the same reason.

The upper limit of the reaction temperature for reacting the halogenated butyne compound and hydrogen halide in the present disclosure is such that the addition reaction with hydrogen halide proceeds more efficiently and the conversion rate is further improved, and the halogenated butene compound as the target compound is improved. From the viewpoint of being able to obtain the compound with higher selectivity, and from the viewpoint of further suppressing the decrease in selectivity due to decomposition or polymerization of the reaction product, usually 500° C. or lower is preferable, 450° C. or lower is more preferable, and 400 C. or lower is more preferable.

The reaction time for reacting the halogenated butyne compound and hydrogen halide in the present disclosure is, for example, when a gas phase flow system is adopted, the contact time (W/F) of the raw material compound with the catalyst [W: weight of the metal catalyst (G), F: flow rate of raw material compound (cc/sec)] is 1.5 to 30 g from the viewpoint that the conversion rate of the reaction is particularly high and the halogenated butene compound can be obtained in a higher yield and a higher selectivity. -Sec./cc is preferable, 1.8-20 g-sec./cc is more preferable, and 2.0-10 g-sec./cc is further preferable. The above W/F specifies the reaction time particularly when the gas phase flow reaction is adopted, but the contact time can be appropriately set also when the batch reaction is adopted. In addition, the said contact time means the time when a substrate and a catalyst contact.

The reaction pressure for reacting the halogenated butyne compound and hydrogen halide in the present disclosure is preferably −0.05 MPa to 2 MPa, more preferably −0.01 MPa to 1 MPa from the viewpoint of more efficiently advancing the addition reaction with hydrogen halide. The atmospheric pressure to 0.5 MPa is more preferable. In the present disclosure, the pressure is a gauge pressure unless otherwise specified.

In the reaction of the halogenated butyne compound and hydrogen halide in the present disclosure, as a reactor in which the halogenated butyne compound and the catalyst are charged and reacted, as long as it can withstand the above temperature and pressure, the shape and structure are It is not particularly limited. Examples of the reactor include a vertical reactor, a horizontal reactor, a multitubular reactor and the like. Examples of the material of the reactor include glass, stainless steel, iron, nickel, iron-nickel alloy and the like.

The reaction between a halogenated butyne compound and hydrogen halide in the present disclosure (addition reaction with hydrogen halide) is a flow system or a batch system in which a substrate is continuously charged into a reactor and a target compound is continuously withdrawn from the reactor. It can be implemented by either method. If the target compound stays in the reactor, the elimination reaction may proceed further, so that it is preferable to carry out the flow-through method. The step of reacting the halogenated butyne compound and hydrogen halide in the present disclosure is preferably carried out in a gas phase, particularly preferably in a gas phase continuous flow system using a fixed bed reactor. When the gas phase continuous flow system is used, the apparatus, operation and the like can be simplified, and it is economically advantageous.

The atmosphere for the reaction between the halogenated butyne compound and hydrogen halide in the present disclosure is preferably an inert gas atmosphere, a hydrogen fluoride gas atmosphere or the like from the viewpoint of suppressing the deterioration of the catalyst. Examples of the inert gas include nitrogen, helium, and argon. Among these inert gases, nitrogen is preferable from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gas component introduced into the reactor.

The object compound of the present disclosure thus obtained has the general formula (1):
CX ¹ X ² X ³ CX ⁴ = CHCX ⁷ X ⁸ X ⁹ (1)
[In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ are the same or different and each represents a halogen atom. ]
It is a halogenated butene compound represented by.

X ^1, X ^2, X ³ in the general formula ^{(1), X 7, X} 8 and X ⁹ is, X ¹ in the general formula ^{(2), X 2, X} 3, X 7, X 8 and X ⁹ It corresponds to. Further, in the general formula (1), examples of the halogen atom represented by X ⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Therefore, the halogenated butene compound represented by the general formula (1) to be produced is, for example, specifically CF ₃ CF=CHCF ₃ , CCl ₃ CCl=CHCCl ₃ , CBr ₃ CBr=CHCBr _3, etc. Is mentioned.

After completion of the reaction between the halogenated butyne compound and hydrogen halide (addition reaction with hydrogen halide), if necessary, purification treatment can be carried out according to a conventional method to obtain the target compound, halogenated butene compound. According to the production method of the present disclosure, as described above, addition of 2 moles of hydrogen halide to 1 mole of halogenated butyne compound is suppressed, and 1 mole of 1 mole of halogenated butyne compound is suppressed. A halogenated butene compound to which hydrogen halide is added can be selectively obtained.

The halogenated butene compound obtained in this way can be effectively used for various purposes such as etching gas for forming the latest fine structure such as semiconductors and liquid crystals.

2. Halogenated butene composition As described above, a halogenated butene compound can be obtained, but a halogenated butene compound in which 1 mol of hydrogen halide is added to 1 mol of a halogenated butyne compound and a halogenated butyne compound It may be obtained in the form of a halogenated butene composition containing a halogenated butane compound to which 2 mol of hydrogen halide is added per 1 mol.

In the halogenated butene composition of the present disclosure, the halogenated butene compound is the halogenated butene compound represented by the general formula (1), and the halogenated butane compound is the halogenated butene compound represented by the general formula (3). It is a butane compound.

In the general formulas (1) and (3), the halogen atom represented by X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ is a fluorine atom or a chlorine atom. , A bromine atom and an iodine atom, and a fluorine atom is preferable.

Assuming that the total amount of the halogenated butene composition of the present disclosure is 100 mol %, the content of the halogenated butene compound represented by the general formula (1) is preferably 91.00 to 99.99 mol %, more preferably 92.00 to 99.98 mol %. .. The content of the halogenated butane compound represented by the general formula (3) is preferably 0.01 to 9.00 mol%, more preferably 0.02 to 8.00 mol%.

In addition, according to the production method of the present disclosure, even when obtained as a halogenated butene composition, the halogenated butene compound represented by the general formula (1) as described above, the reaction conversion rate Since it is high and can be obtained with high yield and high selectivity, it is possible to reduce the components other than the halogenated butene compound represented by the general formula (1) in the halogenated butene composition. The labor of purification for obtaining the halogenated butene compound represented by the general formula (1) can be reduced.

The halogenated butene composition of the present disclosure as described above can be effectively used for various applications such as an etching gas for forming the latest fine structure such as a semiconductor and a liquid crystal, and a building block for organic synthesis. The building block for organic synthesis means a substance that can be a precursor of a compound having a highly reactive skeleton. For example, when the halogenated butene composition of the present disclosure is reacted with a fluorine-containing organosilicon compound such as CF ₃ Si(CH ₃ ) _3, a fluoroalkyl group such as CF ₃ group is introduced to introduce a detergent or a fluorine-containing drug. It is possible to convert into a substance that can be an intermediate.

Although the embodiments of the present disclosure have been described above, various changes in form and details can be made without departing from the spirit and scope of the claims.

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

In the method for producing a halogenated butene compound of Examples 1 to 6 and Comparative Examples 1 and 2, the starting compound is a halogenated butyne compound represented by the general formula (2), which is represented by X ¹ , X ² , X ³ , X ³ . ⁷ , X ⁸ and X ⁹ are fluorine atoms, hydrogen halide is hydrogen fluoride, and the following reaction formula:
CF ₃ C ≡ CCF ₃ + HF → CF ₃ CF=CHCF ₃
According to the above, a halogenated butene compound was obtained by a hydrogen fluoride addition reaction.

Examples 1 to 4: Activated carbon catalyst (manufactured by Osaka Gas Chemical Co., Ltd.; specific surface area: 1200 m ² ) was used as a catalyst in a SUS pipe (outer diameter: 1/2 inch) which is a reaction tube for hydrogen fluoride addition reaction using activated carbon catalyst. /g) was added. After drying at 200°C for 2 hours in a nitrogen atmosphere, the pressure was normal pressure, and the contact time (W/F) between CF ₃ C≡CCF ₃ (substrate) and hydrogen fluoride and the activated carbon catalyst was 2 gsec/cc. As a result, CF ₃ C≡CCF ₃ (substrate) and hydrogen fluoride gas were passed through the reaction tube.

The reaction proceeded in a gas phase continuous flow system.

-The reaction tube was heated at 200°C, 250°C, 300°C or 400°C to start the hydrogen fluoride addition reaction.

CF _₃ C≡CCF ₃ (substrate) hydrogen fluoride gas is contacted with a molar ratio of the (HF / CF _₃ C≡CCF ₃ ratio) was set to 150, the contact time (W / F) so as to become 2 g · sec / cc The flow rates of the substrate and hydrogen fluoride gas were adjusted to 1 hour, and one hour after the start of the reaction, the distillate passed through the abatement tower was collected.

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

From the results of mass spectrometry and structural analysis, it was confirmed that CF ₃ CF=CHCF ₃ was produced as the target compound. In Example 1, the conversion from CF ₃ C≡CCF ₃ (substrate) was 99.75 mol %, the selectivity of CF ₃ CF=CHCF ₃ (target compound) was 99.85 mol %, CF ₃ CF ₂ CH ₂ CF ₃ The selectivity was 0.11 mol% and the selectivity of CF ₃ CFHCFHCF ₃ was 0.01 mol %. In Example 2, the conversion from CF ₃ C≡CCF ₃ (substrate) was 100.00 mol %, the selectivity of CF ₃ CF=CHCF ₃ (target compound) was 99.36 mol %, and the CF ₃ CF ₂ CH ₂ CF ₃ The selectivity was 0.34 mol% and the selectivity of CF ₃ CFHCFHCF ₃ was 0.26 mol %. In Example 3, the conversion from CF ₃ C≡CCF ₃ (substrate) is 100.00 mol %, the selectivity of CF ₃ CF=CHCF ₃ (target compound) is 98.45 mol %, and the selectivity of CF ₃ CF ₂ CH ₂ CF ₃ is The selectivity was 0.98 mol% and the selectivity of CF ₃ CFHCFHCF ₃ was 0.10 mol %. In Example 4, the conversion from CF ₃ C≡CCF ₃ (substrate) was 100.00 mol %, the selectivity of CF ₃ CF=CHCF ₃ (target compound) was 99.15 mol %, and the CF ₃ CF ₂ CH ₂ CF ₃ The selectivity was 0.80 mol% and the selectivity of CF ₃ CFHCFHCF ₃ was 0.02 mol %.

Examples 5 to 6: Hydrogen fluoride addition reaction using chromium oxide catalyst Chromium oxide catalyst (Cr ₂ O ₃ ) was used as a catalyst, reaction temperature was 350° C., CF ₃ C≡CCF ₃ (substrate) and hydrogen fluoride Adjust the total flow rate of CF ₃ C ≡ CCF ₃ (substrate) and hydrogen fluoride gas so that the contact time (W/F) of the gas with the chromium oxide catalyst is 4 gsec/cc or 5 gsec/cc The reaction was performed in the same manner as in Examples 1 to 4 except that the molar ratio of the hydrogen fluoride gas (HF/CF ₃ C≡CCF ₃ ratio) to be brought into contact with CF ₃ C≡CCF ₃ (substrate) was 50 or 200. Advanced.

From the results of mass spectrometry and structural analysis, it was confirmed that CF ₃ CF=CHCF ₃ was produced as the target compound. In Example 5, the conversion from CF ₃ C≡CCF ₃ (substrate) was 97.59 mol%, the selectivity of CF ₃ CF=CHCF ₃ (target compound) was 99.98 mol%, and the CF ₃ CF ₂ CH ₂ CF ₃ The selectivity was 0.01 mol %, and the selectivity of CF ₃ CFHCFHCF ₃ was 0.00 mol %. In Example 6, the conversion from CF ₃ C≡CCF ₃ (substrate) was 80.90 mol %, the selectivity of CF ₃ CF=CHCF ₃ (target compound) was 99.96 mol %, CF ₃ CF ₂ CH ₂ CF ₃ The selectivity was 0.03 mol %, and the selectivity of CF ₃ CFHCFHCF ₃ was 0.00 mol %.

Comparative Examples 1-2: Hydrogen Fluoride Addition Reaction without Catalyst The reaction temperature is 200° C. or 350° C., the contact time between CF ₃ C≡CCF ₃ (substrate) and the catalyst of hydrogen fluoride gas. (W/F) was set to 20 gsec/cc and the molar ratio of hydrogen fluoride gas (HF/CF ₃ C≡CCF ₃ ratio) to be brought into contact with CF ₃ C≡CCF ₃ (substrate) was set to 200. The reaction was allowed to proceed in the same manner as in Examples 1 to 4. In Comparative Examples 1 and 2, the W/F of 20 g·sec/cc means that the flow rate is the same as the case of W/F of 20 g·sec/cc in Examples 1 to 6 using a catalyst. It means that CF ₃ C ≡ CCF ₃ (substrate) was flown.

From the results of mass spectrometry and structural analysis, it was confirmed that CF ₃ CF=CHCF ₃ was produced as the target compound. In Comparative Example 1, although the flow rate of CF ₃ C≡CCF ₃ (substrate) was remarkably increased as compared with Examples 1 to 6, the conversion rate from CF ₃ C≡CCF ₃ (substrate) was 1.92 mol%, CF ₃ CF=CHCF ₃ (target compound) selectivity is 90.83 mol %, CF ₃ CF ₂ CH ₂ CF ₃ selectivity is 8.27 mol %, CF ₃ CFHCFHCF ₃ selectivity is 0.82 mol %. there were. In Comparative Example 2, although the flow rate of CF ₃ C≡CCF ₃ (substrate) was remarkably increased as compared with Examples 1 to 6, the conversion rate from CF ₃ C≡CCF ₃ (substrate) was 2.17 mol%, CF ₃ CF=CHCF ₃ (target compound) selectivity is 85.52 mol %, CF ₃ CF ₂ CH ₂ CF ₃ selectivity is 7.83 mol %, CF ₃ CFHCFHCF ₃ selectivity is 0.62 mol %. there were. Therefore, the conversion from CF ₃ C ≡ CCF ₃ (substrate) is extremely low, and CF ₃ CF ₂ CH ₂ CF ₃ which is an impurity is produced in a considerable amount, so the target compound CF ₃ CF=CHCF ₃ The selectivity of ₃ was also low.

The results are shown in Table 1.

Claims

General formula (1):
CX 1 X 2 X 3 CX 4 = CHCX 7 X 8 X 9 (1)
[In the formula, X 1 , X 2 , X 3 , X 4 , X 7 , X 8 and X 9 are the same or different and each represents a halogen atom. ]
A method for producing a halogenated butene compound represented by
In the presence of a catalyst,
General formula (2):
CX 1 X 2 X 3 C ≡ CCX 7 X 8 X 9 (2)
[Wherein X 1 , X 2 , X 3 , X 7 , X 8 and X 9 are the same as defined above. ]
A method for producing, comprising a step of reacting a halogenated butyne compound represented by with a hydrogen halide.
The halogenated butene compound represented by the general formula (1) is CF 3 CF=CHCF 3 , and the halogenated butyne compound represented by the general formula (2) is CF 3 C≡CCF 3 . The manufacturing method according to claim 1.
3. The production method according to claim 1, wherein the catalyst contains at least one selected from the group consisting of a fluorinated or non-fluorinated activated carbon catalyst and a fluorinated or non-fluorinated Lewis acid catalyst.
The catalyst is a fluorinated or non-fluorinated Lewis acid catalyst, and the Lewis acid catalyst is at least one selected from the group consisting of a chromium oxide catalyst, an alumina catalyst, a silica-alumina catalyst, and a zeolite catalyst. 4. The manufacturing method according to any one of 3 to 3.
The production method according to any one of claims 1 to 4, wherein 30 to 250 mol of hydrogen halide is reacted with 1 mol of the halogenated butyne compound represented by the general formula (2).
General formula (1):
CX 1 X 2 X 3 CX 4 = CHCX 7 X 8 X 9 (1)
[In the formula, X 1 , X 2 , X 3 , X 4 , X 7 , X 8 and X 9 are the same or different and each represents a halogen atom. ]
A halogenated butene compound represented by
General formula (3):
CX 1 X 2 X 3 CX 4 X 5 CHX 6 CX 7 X 8 X 9 (3)
[In the formula, X 1 , X 2 , X 3 , X 4 , X 7 , X 8 and X 9 are the same as defined above. One of X 5 and X 6 represents a hydrogen atom, and the other represents a halogen atom. ]
A composition containing a halogenated butane compound represented by
A composition in which the content of the halogenated butene compound represented by the general formula (1) is 91.00 to 99.99 mol% based on 100 mol% of the total amount of the composition.
The composition according to claim 6, which is used as a cleaning gas, an etching gas or a building block for organic synthesis.