JP2020132585A - Method for producing halogenated butene compound - Google Patents

Abstract

To obtain a butene compound having a high conversion rate and 7 halogen atoms at high selectivity.SOLUTION: A method for producing a halogenated butene compound represented by CXXXCX=CHCXXX[where X, X, X, X, X, Xand Xare the same or different to represent a halogen atom], including the step of reacting, in the presence of a catalyst, a halogenated butine compound represented by CXXXC≡CCXXX[where X, X, X, X, Xand Xare the same as above] with a hydrogen halide.SELECTED DRAWING: None

Description

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

A butene compound having seven halogen atoms represented by heptafluorobutene is a compound expected as a cleaning gas, a building block for organic synthesis, etc., in addition to a dry etching gas for semiconductors.

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

Journal of the American Chemical Society, 91, 1969, p. 6532-6534

An object of the present disclosure is 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 equation, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ indicate the same or different halogen atoms. ]
It is a method for producing a halogenated butene compound represented by.
In the presence of catalyst
General formula (2):
CX ¹ X ² X ³ C ≡ CCX ⁷ X ⁸ X ⁹ (2)
[In the equation, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same as above. ]
A production method comprising a step of reacting a halogenated butin compound represented by (1) with 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 1. The manufacturing method according to Item 1.
Item 3. Item 2. The production method according to Item 1 or 2, wherein the catalyst comprises 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 which 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 production method according to any one of 3.
Item 5. Item 6. The production 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 butin halide 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 equation, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ indicate the same or different halogen atoms. ]
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 equation, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ are the same as above, X ⁵ and X ⁶ indicate a hydrogen atom on one side and a halogen atom on the other side. .. ]
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%, where the total amount of the composition is 100 mol%.
Item 7. Item 6. 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 obtained with a high conversion rate and a high selectivity.

As used herein, "contains" is a concept that includes any of "comprise," "consist essentially of," and "consist of." Further, in the present specification, when the numerical range is indicated by "A to B", it means A or more and B or less.

In the present disclosure, the "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 the compound other than the raw material compound in the effluent gas from the reactor outlet. To do.

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

Conventionally, according to the method of Non-Patent Document 1, CF ₃ C ≡ CCF ₃ and Ag F are reacted to obtain CF ₃ CF = C (CF ₃ ) Ag, and then the reaction is carried out with HCl in acetonitrile to obtain CF. _{Although 3} CF = CHCF ₃ was obtained, a 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 reaction had a large number of steps. According to the production method of the present disclosure, a butene compound having 7 halogen atoms can be synthesized by a method obtained with a high conversion rate and a high selectivity as compared with the conventional method.

1. 1. Method for Producing Halogenated Butene Compound The method for producing the halogenated butene compound of the present disclosure is as follows.
General formula (1):
CX ¹ X ² X ³ CX ⁴ = CHCX ⁷ X ⁸ X ⁹ (1)
[In the equation, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ indicate the same or different halogen atoms. ]
It is a method for producing a halogenated butene compound represented by.
In the presence of catalyst
General formula (2):
CX ¹ X ² X ³ C ≡ CCX ⁷ X ⁸ X ⁹ (2)
[In the equation, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same as above. ]
The present invention comprises a step of reacting the halogenated butin compound represented by (1) with hydrogen halide.

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

On the other hand, by carrying out the reaction between the hydrogen halide compound represented by the general formula (2) and hydrogen halide in the presence of a catalyst, 1 mol of the halogenated butine compound represented by the general formula (2) is carried out. The addition of 2 mol of hydrogen halide was suppressed, and 1 mol of hydrogen halide was added to 1 mol of the butin halide compound represented by the general formula (2) according to the general formula (1). The represented halogenated butene compound can be selectively obtained. This is due to the effect of the strong electron-withdrawing groups of the methyl trihalogenates (CX ¹ X ² X ³ and C X ⁷ X ⁸ X ⁹ ). Due to its strong electron-withdrawing effect, the trihalogenated methyl group lowers the electron density of adjacent double-bonded or triple-bonded electrons, so that an addition reaction to the unsaturated bond is less likely to occur. Since the butine halide compound has a triple bond, the addition reaction of hydrogen halide easily occurs due to its high reactivity, but the butene halide compound reacts with hydrogen halide due to the effect of the methyl trihalogenate group. It does not become a halogenated butane compound, and a halogenated butene compound can be selectively obtained.

As described above, the butin halide 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 indicate the same or different halogen atoms. ]
It is a halogenated butin 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 butine compound as a substrate, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ¹ , X ² , X ³ , X ^8, and X ⁸ For all X ⁹ , a fluorine atom is preferable.

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

The halogenated butyne compound as satisfying a substrate as described above, _{specifically, CF 3 C≡CCF 3, CCl 3} C≡CCCl 3, CBr 3 C≡CCBr 3 , and the like. These halogenated butin compounds can be used alone or in combination of two or more. As such a halogenated butin compound, a known or commercially available product can be adopted. It is also possible to synthesize according to a conventional method such as Japanese Patent Application Laid-Open No. 2012-001448.

Examples of hydrogen halide that reacts with the halogenated butin compound include hydrogen fluoride, hydrogen chloride, and hydrogen bromide. From the viewpoint of reaction conversion rate, yield and selectivity, hydrogen fluoride is preferable. These hydrogen halides can be used alone or in combination of two or more.

It is usually preferable that the hydrogen halide is supplied to the reactor in a vapor phase state together with the halogenated butin compound (substrate). The supply amount of hydrogen halide to react with the halogenated butin compound (substrate) is preferably 30 to 250 mol, more preferably 35 to 240 mol, and 40 to 230 mol with respect to 1 mol of the halogenated butin compound (substrate). Is even more preferable. Within this range, the addition reaction by hydrogen halide can proceed more satisfactorily, and the excessive addition reaction by hydrogen halide can be further suppressed, so that the formation of impurities can be further reduced, and the product can be produced. The selectivity of the halogenated butene compound is high, and it can be recovered in high yield.

The step of reacting the halogenated butyne compound with hydrogen halide in the present disclosure is an addition reaction with hydrogen halide and is carried out in the presence of a catalyst. In the step (addition reaction) of reacting the halogenated butyne compound with hydrogen halide in the production method of the present disclosure, it is preferable to carry out the gas phase, particularly the gas phase continuous flow system using a fixed bed reactor. When the gas phase continuous flow system is used, the equipment, operation, etc. can be simplified and it is economically advantageous.

In the step of reacting the halogenated butine compound with hydrogen halide in the present disclosure, for example, in the halogenated butin compound represented by the general formula (2) as a substrate, 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
Therefore, it is preferable that the addition reaction is carried out by hydrogen fluoride.

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 carbon, briquette, granular charcoal, and spherical charcoal. 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 a JIS test (JIS Z8801). As these activated carbons, known or commercially available products can be adopted.

Since the activated carbon exhibits stronger activity by fluorination, it is also possible to use a fluorinated activated carbon in which the activated carbon is fluorinated in advance before being used in the reaction. That is, as the activated carbon catalyst, either non-fluorinated activated carbon or fluorinated activated carbon can be used.

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

Examples of the method for fluorinating activated carbon include a method in which the above-mentioned fluorinating agent is circulated under atmospheric pressure under a temperature condition of about room temperature (25 ° C.) to 400 ° C. to fluorinate.

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, either a non-fluorinated Lewis acid catalyst or a fluorinated Lewis acid catalyst can be adopted.

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

The fluorinated chromium oxide catalyst can be prepared by fluorination of the chromium oxide catalyst described above. 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-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 a 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 fast. The reaction rate depends on the reaction solution temperature, the ammonia water mixing method (mixing rate), the stirring state, and the like.

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

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

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

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

Then, by fluorinating chromium oxide, fluorinated chromium oxide can be obtained. The temperature of fluorination may be in a temperature range in which the generated water does not condense, and the upper limit may be a temperature in which the catalyst does not crystallize due to the heat of reaction. The temperature of fluorination can be, for example, 100 to 460 ° C. The pressure at the time of fluorination is not limited, but it is preferable to carry out at 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 the active 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, 50-80% by mass of catalyst can be used.

Since the alumina catalyst and the silica-alumina catalyst show stronger activity by fluorination, the alumina catalyst can be fluorinated in advance and used as the fluorinated alumina catalyst before being used in the reaction. Can also be fluorinated and used as a fluorinated silica-alumina catalyst.

The fluorinating agent for fluorination of alumina catalyst and silica-alumina catalysts, for example, can be used F _2, inorganic fluorinating agents such as HF, fluorocarbon-based organic fluorinating agent such as hexafluoropropene, and the like.

Examples of the method for fluorinating the alumina catalyst and the silica-alumina catalyst include a method in which the above-mentioned fluorinating agent is circulated under atmospheric pressure under a temperature condition of about room temperature (25 ° C.) to 400 ° C. for fluorination. Can be done.

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

Since the zeolite catalyst exhibits stronger activity by fluorination, the zeolite catalyst can be fluorinated in advance and used as a fluorinated zeolite catalyst before being used in the reaction.

The fluorinating agent for fluorination of zeolite catalysts, for example, can be used F _2, inorganic fluorinating agents such as HF, fluorocarbon-based organic fluorinating agent such as hexafluoropropene, and the like.

Examples of the method for fluorinating the zeolite catalyst include a method in which the above-mentioned fluorinating agent is circulated under atmospheric pressure under a temperature condition of about room temperature (25 ° C.) to 400 ° C. to fluorinate.

The above-mentioned 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, or the like is more preferable.

Further, 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 the carbon, activated carbon, amorphous carbon, graphite, diamond and the like can be used.

In the production method of the present disclosure, when reacting a halogenated butin compound with hydrogen halide in the presence of a catalyst, for example, it is preferable to bring the catalyst into contact with the halogenated butin compound in a solid state (solid phase). In this case, the shape of the catalyst may be powder, but the pellet shape is preferable when it is used for the gas phase continuous flow type 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 preferred, and 30-1500 m ² / g is particularly preferred. When the BET specific surface area of the catalyst is in such a range, the density of the catalyst particles is not too small, so that the halogenated butene compound can be obtained with a higher selectivity. It is also possible to further improve the conversion rate of the halogenated butin compound.

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

The upper limit of the reaction temperature at which the halogenated butine compound and hydrogen halide are reacted in the present disclosure is such that the addition reaction with hydrogen halide proceeds more efficiently to further improve the conversion rate, and the halogenated butene which is the target compound. From the viewpoint of obtaining a compound with a higher selectivity and further suppressing a 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. The temperature is more preferably ° C. or lower.

The reaction time for reacting the halogenated butine compound with hydrogen halide in the present disclosure is, for example, the contact time of the raw material compound with the catalyst (W / F) [W: weight of the metal catalyst when the vapor phase flow method is adopted. (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 higher selectivity. -Sec./cc is preferable, 1.8 to 20 g-sec./cc is more preferable, and 2.0 to 10 g-sec./cc is further preferable. The above W / F specifies the reaction time especially when the gas phase flow type reaction is adopted, but the contact time can be appropriately set even when the batch type reaction is adopted. The contact time means the time during which the substrate and the catalyst are in contact with each other.

The reaction pressure for reacting the hydrogen halide compound with hydrogen halide in the present disclosure is preferably -0.05MPa to 2MPa, more preferably -0.01MPa to 1MPa, from the viewpoint of more efficiently advancing the addition reaction with hydrogen halide. It is preferably normal pressure to 0.5 MPa, more preferably. In this disclosure, the pressure is a gauge pressure unless otherwise specified.

In the reaction between the butin halide compound and hydrogen halide in the present disclosure, the shape and structure of the reactor in which the butin halide compound and the catalyst are charged and reacted are as long as they can withstand the above temperature and pressure. There is no particular limitation. Examples of the reactor include a vertical reactor, a horizontal reactor, a multi-tube 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 hydrogen halide compound and hydrogen halide in the present disclosure is a distribution type or batch type in which a substrate is continuously charged into a reactor and a target compound is continuously extracted from the reactor. It can be carried out by any of the above methods. When the target compound stays in the reactor, the elimination reaction can proceed further, so it is preferable to carry out the reaction by a distribution method. The step of reacting the halogenated butin compound with hydrogen halide in the present disclosure is preferably carried out in the gas phase, and particularly preferably in the gas phase continuous flow system using a fixed bed reactor. When the gas phase continuous flow system is used, the equipment, operation, etc. can be simplified and it is economically advantageous.

Regarding the atmosphere when the reaction between the butin halide compound and hydrogen halide in the present disclosure is carried out, it is preferable to use an inert gas atmosphere, a hydrogen fluoride gas atmosphere, or the like from the viewpoint of suppressing deterioration of the catalyst. Examples of the inert gas include nitrogen, helium, argon and the like. 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 target compound of the present disclosure thus obtained is the general formula (1) :.
CX ¹ X ² X ³ CX ⁴ = CHCX ⁷ X ⁸ X ⁹ (1)
[In the equation, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ indicate the same or different halogen atoms. ]
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. Can be mentioned.

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

The halogenated butene compound thus obtained can be effectively used in various applications such as an etching gas for forming a state-of-the-art fine structure of a semiconductor, a liquid crystal, or the like.

2. 2. Halogenated Butene Composition The halogenated butene compound can be obtained as described above, but the halogenated butene compound in which 1 mol of hydrogen halide is added to 1 mol of the halogenated butine compound and the halogenated butene compound It may also be obtained in the form of a halogenated butene composition containing 2 mol of hydrogen halide added to 1 mol of the butane halide compound.

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

In the general formulas (1) and (3), the halogen atoms represented by X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are fluorine atom and chlorine atom. , Bromine atom and iodine atom, and 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%.

According to the production method of the present disclosure, even when it is obtained as a halogenated butene composition, the halogenated butene compound represented by the general formula (1) as described above can be used for the conversion rate of the reaction. Since it 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 purification effort for obtaining the halogenated butene compound represented by the general formula (1) can be reduced.

Such a halogenated butene composition of the present disclosure can be effectively used in various applications such as building blocks for organic synthesis, as well as etching gas for forming the most advanced fine structure of semiconductors, liquid crystals and the like. 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 organic silicon compound such as CF ₃ Si (CH ₃ ) _3, a fluoroalkyl group such as CF ₃ group is introduced to introduce a cleaning agent or a fluorine-containing pharmaceutical. It can be converted into a substance that can be an intermediate.

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

Examples are shown below to clarify the features of the present 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 X ¹ , X ² , X ³ , X in the halogenated butine compound represented by the general formula (2). 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
Therefore, 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 ) as a catalyst in SUS piping (outer diameter: 1/2 inch) which is a hydrogenation hydrogen fluoride reaction reaction tube using an activated carbon catalyst. / g) was added by 10 g. 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 g · sec / cc. CF ₃ C ≡ C CF ₃ (substrate) and hydrogen fluoride gas were circulated in the reaction tube so as to be.

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 initiate 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, and the distillate that passed through the abatement tower was collected 1 hour after the start of the reaction.

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 Ltd., trade name). Structural analysis was performed by NMR spectrum using "400YH").

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 rate from CF ₃ C ≡ CCF ₃ (substrate) was 99.75 mol%, the selectivity of CF ₃ CF = CHCF ₃ (target compound) was 99.84 mol%, and 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 rate from CF ₃ C ≡ CC F ₃ (substrate) was 100.00 mol%, the selectivity of CF ₃ CF = CH CF ₃ (target compound) was 99.36 mol%, and CF ₃ CF ₂ CH ₂ CF ₃ The selectivity was 0.34 mol% and the selectivity for CF ₃ CFH CFHCF ₃ was 0.26 mol%. In Example _3, CF 3 C≡CCF 3 conversion of (substrate) is 100.00 _{mol%, CF 3 CF = CHCF 3} ( object compound) of selectivity of 98.45 mol%, of CF ₃ CF ₂ CH ₂ CF ₃ The selectivity was 0.98 mol% and the selectivity of CF ₃ CFHCFHCF ₃ was 0.10 mol%. In Example 4, CF ₃ C≡CCF ₃ conversion of (substrate) is 100.00 _{mol%, CF 3 CF = CHCF 3} ( object compound) of selectivity of 99.15 mol%, of CF ₃ CF ₂ CH ₂ CF ₃ The selectivity was 0.80 mol% and the selectivity for CF ₃ CFH CFHCF ₃ was 0.02 mol%.

Examples 5 to 6: Hydrogen fluoride addition using a chromium oxide catalyst A hydrogen fluoride catalyst (Cr ₂ O ₃ ) is used as a reaction catalyst, the reaction temperature is 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 g · sec / cc or 5 g · sec / cc. the same reaction as and CF ₃ C≡CCF ₃ except that the molar ratio of hydrogen fluoride gas is contacted with (a substrate) (HF / CF ₃ C≡CCF ₃ ratio) was 50 or 200 examples 1-4 I made it progress.

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, CF ₃ C≡CCF ₃ conversion of 97.59 mol% from _{(substrate), CF 3 CF = CHCF 3} ( object compound) of selectivity of 99.98 mol%, of 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 rate 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%, and 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: Without using a catalyst-free hydrogen fluoride addition reaction catalyst, the reaction temperature was 200 ° C or 350 ° C, and the contact time between CF ₃ C ≡ CCF ₃ (substrate) and the hydrogen fluoride gas catalyst. Except that (W / F) was set to 20 g · sec / 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 proceeded in the same manner as in Examples 1 to 4. In addition, in Comparative Examples 1 and 2, the fact that the W / F was set to 20 g · sec / cc means that the flow rate was the same as when the W / F was set to 20 g · sec / cc in Examples 1 to 6 using the catalyst. CF ₃ C ≡ It means that CCF ₃ (substrate) was flowed.

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 significantly increased as compared with Examples 1 to 6, the conversion rate from CF ₃ C ≡ CCF ₃ (substrate) was high. 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, the conversion rate from CF ₃ C ≡ CCF ₃ (substrate) was significantly higher than that of Examples 1 to 6 even though the flow rate of CF ₃ C ≡ CCF ₃ (substrate) was significantly increased. 2.17 mol%, CF ₃ CF = CHCF ₃ (target compound) selectivity is 85.51 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 rate from CF ₃ C ≡ CCF ₃ (substrate) is extremely low, and the impurity CF ₃ CF ₂ CH ₂ CF ₃ is produced to a considerable extent, and the target compound CF ₃ CF = CHCF. The selectivity of ₃ was also low.

The results are shown in Table 1.

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 rate 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%, and 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 rate from CF ₃ C ≡ CC F ₃ (substrate) was 100.00 mol%, the selectivity of CF ₃ CF = CH CF ₃ (target compound) was 99.36 mol%, and CF ₃ CF ₂ CH ₂ CF ₃ The selectivity was 0.34 mol% and the selectivity for CF ₃ CFH CFHCF ₃ was 0.26 mol%. In Example _3, CF 3 C≡CCF 3 conversion of (substrate) is 100.00 _{mol%, CF 3 CF = CHCF 3} ( object compound) of selectivity of 98.45 mol%, of CF ₃ CF ₂ CH ₂ CF ₃ The selectivity was 0.98 mol% and the selectivity of CF ₃ CFHCFHCF ₃ was 0.10 mol%. In Example 4, CF ₃ C≡CCF ₃ conversion of (substrate) is 100.00 _{mol%, CF 3 CF = CHCF 3} ( object compound) of selectivity of 99.15 mol%, of CF ₃ CF ₂ CH ₂ CF ₃ The selectivity was 0.80 mol% and the selectivity for CF ₃ CFH CFHCF ₃ was 0.02 mol%.

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 significantly increased as compared with Examples 1 to 6, the conversion rate from CF ₃ C ≡ CCF ₃ (substrate) was high. 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, the conversion rate from CF ₃ C ≡ CCF ₃ (substrate) was significantly higher than that of Examples 1 to 6 even though the flow rate of CF ₃ C ≡ CCF ₃ (substrate) was significantly increased. 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 rate from CF ₃ C ≡ CCF ₃ (substrate) is extremely low, and the impurity CF ₃ CF ₂ CH ₂ CF ₃ is produced to a considerable extent, and the target compound CF ₃ CF = CHCF. The selectivity of ₃ was also low.

Claims (7)

General formula (1):
CX ¹ X ² X ³ CX ⁴ = CHCX ⁷ X ⁸ X ⁹ (1)
[In the equation, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ indicate the same or different halogen atoms. ]
It is a method for producing a halogenated butene compound represented by.
In the presence of catalyst
General formula (2):
CX ¹ X ² X ³ C ≡ CCX ⁷ X ⁸ X ⁹ (2)
[In the equation, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same as above. ]
A production method comprising a step of reacting a halogenated butin compound represented by (1) with 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. The production method according to claim 1 or 2, wherein the catalyst comprises 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. The production 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 butin halide 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 equation, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ indicate the same or different halogen atoms. ]
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 equation, X ¹ , X ² , X ³ , X ⁴ , X ⁷ , X ⁸ and X ⁹ are the same as above, X ⁵ and X ⁶ indicate a hydrogen atom on one side and a halogen atom on the other side. .. ]
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%, where the total amount of the composition is 100 mol%. The composition according to claim 6, which is used as a cleaning gas, an etching gas, or a building block for organic synthesis.