KR102683558B1 - Method for producing halogenated butene compounds - Google Patents

Abstract

^{CX 1 ​ ​ ​ ​ ​} A method for producing ^a halogenated butene compound represented by [wherein X ¹ , X ² , X ³ , X ⁴ , X ^{7 , A halogenated butyne compound represented by CX 1 ​ ​ ​ ​} , a process for reacting hydrogen halide is provided. The production method is a production method that can obtain a butene compound having 7 halogen atoms with a high conversion rate and high selectivity.

Description

Method for producing halogenated butene compounds

This disclosure relates to a method for producing halogenated butene compounds.

Butene compounds having seven halogen atoms, such as heptafluorobutene, are expected to be used as dry etching gas for semiconductors, cleaning gas, and building blocks for organic synthesis.

As a method for producing a butene compound having seven halogen atoms, for example, in Non-Patent Document 1, CF ₃ C≡CCF ₃ is reacted with AgF to obtain CF ₃ CF=C(CF ₃ )Ag, and then acetonitrile is added. By reacting with HCl, CF ₃ CF = CHCF ₃ is obtained.

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

The purpose of the present disclosure is to provide a method for obtaining a butene compound having a high conversion rate and 7 halogen atoms with a high selectivity.

This disclosure includes the following configurations.

Clause 1. General formula (1):

^{CX 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 represent halogen atoms.]

A method for producing a halogenated butene compound represented by,

In the presence of a catalyst,

General formula (2):

^{CX 1 ​ ​ ​ ​}

[Wherein, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same as above.]

A process of reacting a halogenated butyne compound represented by and hydrogen halide.

A manufacturing method comprising:

Item 2. In item 1, the halogenated butene compound represented by the general formula (1) is CF ₃ CF=CHCF ₃ , and the halogenated butene compound represented by the general formula (2) is CF ₃ C≡CCF ₃ . Manufacturing method described.

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. Items 1 to 3, 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 the preceding paragraphs.

Item 5. 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 halogenated butyne compound represented by the general formula (2).

Item 6. General formula (1):

^{CX 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 represent halogen atoms.]

A halogenated butene compound represented by

General formula (3):

^{CX 1 ​ ​ ​ ​ ​ ​ ​}

[In the formula, X ¹ , X ² , X ^{3 , X 4 ,} X ⁷ , X ⁸ and ]

A composition containing a halogenated butane compound represented by,

A composition in which the total amount of the composition is 100 mol% and the content of the halogenated butene compound represented by the general formula (1) is 91.00 to 99.99 mol%.

Item 7. The composition according to Item 6, 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 that obtains a high conversion rate and high selectivity.

In this specification, “contain” is a concept that includes all of “comprise,” “consist essentially of,” and “consist of.” In addition, in this specification, when the numerical range is expressed as "A to B", it means more than A and less than B.

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 compound in the effluent gas from the reactor outlet. .

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

Conventionally, according to the method of Non-Patent Document 1, CF ₃ C≡CCF ₃ and AgF were reacted to obtain CF ₃ CF=C(CF ₃ )Ag, and then reacted with HCl in acetonitrile to obtain CF ₃ CF=CHCF ₃ However, 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 required a large number of steps. According to the production method of the present disclosure, a butene compound having 7 halogen atoms can be synthesized in a method that obtains a high conversion rate and high selectivity even when compared to the prior art.

One. Halogenated butene Method of preparing the compound

The method for producing the halogenated butene compound of the present disclosure is:

General formula (1):

^{CX 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 represent halogen atoms.]

A method for producing a halogenated butene compound represented by,

In the presence of a catalyst,

General formula (2):

^{CX 1 ​ ​ ​ ​}

[Wherein, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same as above.]

A step of reacting a halogenated butyne compound represented by and hydrogen halide is provided.

In the production method of the present disclosure, the reaction between the halogenated butyne compound represented by general formula (2) and hydrogen halide is carried out without a catalyst, and 2 moles are used per mole of the halogenated butyne compound represented by general formula (2). General formula (3) with added hydrogen halide:

^{CX 1 ​ ​ ​ ​ ​ ​ ​}

[In the formula, X ¹ , X ² , X ^{3 , X 4 ,} X ⁷ , X ⁸ and ]

The halogenated butane compound represented by is produced to a significant extent (for example, more than 9.00 mol%) as a by-product.

On the other hand, by conducting the reaction between the halogenated butyne compound represented by the above-mentioned general formula (2) and hydrogen halide in the presence of a catalyst, 2 moles of hydrogen halide are obtained for 1 mole of the halogenated butyne compound represented by general formula (2). The addition is suppressed, and a halogenated butene compound represented by the general formula (1) can be selectively obtained by adding 1 mole of hydrogen halide to 1 mole of the halogenated butene compound represented by the general formula (2). ^This is ^due to the effect of the ^{trihalogenated} methyl ^{groups (} CX ¹ Due to its strong electron-withdrawing effect, the trihalogenated methyl group lowers the electron density of the electrons of the adjacent double bond or triple bond, making it difficult for addition reactions to occur with the unsaturated bond. Since the halogenated butene compound has a triple bond, addition reaction with hydrogen halide easily occurs due to its high reactivity. However, due to the effect of the trihalogenated methyl group, the halogenated butene compound does not react with hydrogen halide and does not become a halogenated butane compound. , halogenated butene compounds 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) as described above:

^{CX 1 ​ ​ ​ ​}

[In the formula, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same or different and represent halogen atoms.]

It is a halogenated butyne compound represented by .

In General Formula ( ² ), ^examples of the halogen atoms represented by X ¹ , X ² , X ³ , X ⁷ ,

As a halogenated butene compound as a substrate, from the viewpoint of producing a halogenated butene compound with particularly high conversion rate, yield and selectivity ^, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and desirable.

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

Specific examples of halogenated butyne compounds as substrates that satisfy the above conditions include CF ₃ C≡CCF ₃ , CCl ₃ C≡CCCl ₃ , and CBr ₃ C≡CCBr ₃ . These halogenated butyne compounds may be used individually or in combination of two or more types. These halogenated butyne compounds can be known or commercially available. In addition, it is also possible to synthesize according to commercial methods such as Japanese Patent Publication No. 2012-001448.

Examples of hydrogen halides to be reacted with the halogenated butyne compound include hydrogen fluoride, hydrogen chloride, and hydrogen bromide. Additionally, hydrogen fluoride is preferable from the viewpoint of conversion rate, yield, and selectivity of the reaction. These hydrogen halides may be used individually or in combination of two or more types.

Hydrogen halide is usually preferably supplied to the reactor in a gaseous state together with the halogenated butyne compound (substrate). The supply 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 still more preferably 40 to 230 mol, per 1 mol of halogenated butyne compound (substrate). By setting this range, the addition reaction with the hydrogen halide proceeds more favorably, while the excessive addition reaction with the hydrogen halide is further suppressed, so that the production of impurities can be further reduced, and the selectivity of the halogenated butene compound in the product is high, It can be recovered at high yield.

The step of reacting the halogenated butyne compound and hydrogen halide in the present disclosure is an addition reaction using hydrogen halide, and is performed in the presence of a catalyst. The step (addition reaction) of reacting the halogenated butyne compound with the hydrogen halide in the production method of the present disclosure is preferably carried out in a gas phase, particularly in a gas phase continuous flow method using a fixed bottom reactor. In the case of using the gas phase continuous distribution method, not only can equipment and operation be simplified, but it is also economically advantageous.

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

That is, the following reaction formula:

CF ₃ C≡CCF ₃ ＋HF→ CF ₃ CF=CHCF ₃

Accordingly, it is preferable that it is an addition reaction with hydrogen fluoride.

As a 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, etc. are preferable.

There is no particular limitation on the activated carbon catalyst, and examples include powdered activated carbon such as crushed carbon, coal carbon, granulated carbon, and spherical carbon. It is preferable to use powdered activated carbon that shows a particle size of 4 mesh (4.75 mm) to 100 mesh (0.150 mm) according to the JIS test (JIS Z8801). These activated carbons can be known or commercially available.

Since activated carbon exhibits stronger activity when fluorinated, fluorinated activated carbon may be used in which the activated carbon has been fluorinated in advance before use in the reaction. That is, as the activated carbon catalyst, both non-fluorinated activated carbon and fluorinated activated carbon can be used.

Fluorinating agents for fluorinating activated carbon include, for example, inorganic fluorinating agents such as HF, hydrofluorocarbons (HFCs) such as hexafluoropropene, chlorofluorocarbons (CFCs) such as chlorofluoromethane, Organic fluorinating agents such as hydrochlorofluorocarbon (HCFC) can also be used.

As a method of fluorinating activated carbon, for example, a method of fluorinating activated carbon by circulating the above-mentioned fluorinating agent under atmospheric pressure under temperature conditions of about room temperature (25°C) to 400°C is included.

The Lewis acid catalyst is not particularly limited and includes chromium oxide catalysts, alumina catalysts, silica alumina catalysts, and zeolite catalysts. As these Lewis acid catalysts, both non-fluorinated Lewis acid catalysts and fluorinated Lewis acid catalysts can be employed.

The chromium oxide catalyst is not particularly limited, but when chromium oxide is expressed as CrOm, 1.5<m<3 is preferable, 2<m<2.75 is more preferable, and 2<m<2.3 is more preferable. Additionally, 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, especially 1 to 1.5.

The fluorinated chromium oxide catalyst can be prepared by fluorinating the above-described chromium oxide catalyst. This fluorination can be performed using, for example, HF, fluorocarbon, etc. Such a fluorinated chromium oxide catalyst can be synthesized, for example, according to the method described in Japanese Patent Application Laid-Open No. Hei 05-146680.

Hereinafter, an example of a method for synthesizing a chromium oxide catalyst and a fluorinated chromium oxide catalyst is disclosed.

First, precipitation of chromium hydroxide can be obtained by mixing an aqueous solution of chromium salts (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 of the precipitation reaction. The reaction speed is preferably fast. The reaction speed is influenced by the reaction solution temperature, ammonia solution mixing method (mixing speed), stirring state, etc.

This precipitate can be filtered, washed, and then dried. Drying can be performed, for example, in the air at 70 to 200°C for 1 to 100 hours. The catalyst at this stage is sometimes referred to as chromium hydroxide. This catalyst can then be disintegrated. From the viewpoint of pellet strength, catalyst activity, etc., the powder density of the pulverized powder (for example, the particle size is 1000 μm or less, especially 95% of the particles of 46 to 1000 μm) is 0.6 to 1.1 g/ml, preferably It is desirable to adjust the precipitation reaction rate to 0.6 to 1.0 g/ml. The specific surface area (specific surface area according to the BET method) of the powder 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, for example. Additionally, the upper limit of the specific surface area is, for example, about 220 m ² /g.

In summary, 3% by weight or less of graphite can be mixed with this chromium hydroxide powder and pellets can be formed using a tablet press. The size and strength of the pellet can be adjusted appropriately.

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

From the viewpoint of catalyst activity, the specific surface area of the fired catalyst is preferably, for example, 170 m ² /g or more, more preferably 180 m ² /g or more, and still more preferably 200 m ² /g or more. Additionally, the upper limit of the specific surface area is usually preferably about 240 m ² /g, and more preferably about 220 m ² /g.

Next, fluorinated chromium oxide can be obtained by fluorinating the chromium oxide. The temperature of fluorination may be within a temperature range at which the produced 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 temperature of fluorination can be, for example, 100 to 460°C. There is no limitation on the pressure during fluorination, but it is preferable to carry out the fluorination at the pressure provided for the catalytic reaction.

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

Additionally, a silica alumina catalyst can also be used as a complex 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 silica content is 20 to 90% by mass. %, especially 50 to 80 mass % of the catalyst can be used.

Since the alumina catalyst and the silica alumina catalyst exhibit stronger activity by fluorination, the alumina catalyst may be fluorinated in advance before use in the reaction and used as a fluorinated alumina catalyst, or the silica alumina catalyst may be fluorinated to be used as a fluorinated silica alumina catalyst. You can also use it.

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

As a method of fluorinating an alumina catalyst and a silica alumina catalyst, for example, a method of fluorinating the above-mentioned fluorinating agent by circulating it under atmospheric pressure under temperature conditions of about room temperature (25°C) to 400°C is included.

As a zeolite catalyst, known types of zeolites 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 include A-type, X-type, and LSX-type. The alkali metal or alkaline earth metal in the zeolite is not particularly limited and includes potassium, sodium, calcium, and lithium.

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

As a 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, etc. can be used.

As a method of fluorinating a zeolite catalyst, for example, a method of fluorinating the zeolite catalyst by circulating the above-mentioned fluorinating agent under atmospheric pressure under temperature conditions of about room temperature (25° C.) to 400° C.

The above-described catalysts may be used individually or in combination of two or more types. Among these, from the viewpoint of conversion rate, selectivity and yield, fluorinated or non-fluorinated activated carbon catalysts, fluorinated or non-fluorinated chromium oxide catalysts, fluorinated or non-fluorinated alumina catalysts, etc. are preferable, and fluorinated or non-fluorinated activated carbon catalysts and fluorinated or non-fluorinated oxidation catalysts are preferable. Chromium catalysts and the like are more preferable.

Additionally, when using the above-mentioned fluorinated or non-fluorinated Lewis acid catalyst as a catalyst, it is also possible to support it on a carrier. Examples of these carriers include carbon, alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), silica (SiO ₂ ), and titania (TiO ₂ ). As carbon, activated carbon, amorphous carbon, graphite, diamond, etc. can be used.

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

The specific surface area of the catalyst measured by the BET method (hereinafter also referred to as “BET specific surface area”) is usually preferably 10 to 3,000 m ² /g, more preferably 10 to 2,500 m ² /g, and 20 ~2000 m ² /g is more preferred, and 30-1500 m ² /g is particularly preferred. When the BET specific surface area of the catalyst is within this range, the density of the catalyst particles is not too small, and thus the halogenated butene compound can be obtained with a higher selectivity. Additionally, it is also possible to further improve the conversion rate of the halogenated butyne compound.

In the step of reacting the halogenated butene compound and the hydrogen halide in the present disclosure, the lower limit of the reaction temperature is set to more efficiently proceed the addition reaction with the hydrogen halide, further improve the conversion rate, and increase the conversion rate to a higher level. From the viewpoint of obtaining selectivity, usually 180°C or higher is preferable, and 200°C or higher is more preferable. Additionally, when using a Lewis acid catalyst as a 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 butene compound with the hydrogen halide in the present disclosure allows the addition reaction with the hydrogen halide to proceed more efficiently, further improving the conversion rate, and obtaining the halogenated butene compound, which is the target compound, with a higher selectivity. From the viewpoint of being able to process the temperature and 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 still more preferable.

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

The reaction pressure for reacting the halogenated butyne compound with the hydrogen halide in the present disclosure is preferably -0.05 MPa to 2 MPa, and more preferably -0.01 MPa to 1 MPa, from the point of advancing the addition reaction with hydrogen halide more efficiently. And, normal pressure ~ 0.5 MPa is more preferable. In addition, in this disclosure, if there is no special indication regarding pressure, it is referred to as gauge pressure.

In the reaction between the halogenated butyne compound and the hydrogen halide in the present disclosure, the shape and structure of the reactor for reacting the halogenated butyne compound with the catalyst is not particularly limited as long as it can withstand the temperature and pressure mentioned above. Examples of the reactor include a vertical reactor, a horizontal reactor, and a tube-type reactor. Examples of the material of the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloy.

In the present disclosure, the reaction between a halogenated butyne compound and hydrogen halide (addition reaction with hydrogen halide) is performed in either a flow-through or batch-type method in which a substrate is continuously placed in a reactor and the target compound is continuously extracted from the reactor. It can also be done by: If the target compound remains in the reactor, further removal reaction may proceed, so it is preferable to carry out the flow-through method. In the process of reacting the halogenated butyne compound and the hydrogen halide in the present disclosure, it is preferably carried out in the gas phase, especially in the gas phase continuous flow method using a fixed bottom reactor. In the case of using the gas phase continuous distribution method, not only can equipment and operation be simplified, but it is also economically advantageous.

Regarding the atmosphere when performing the reaction between the halogenated butyne compound and hydrogen halide in the present disclosure, an inert gas atmosphere, a hydrogen fluoride gas atmosphere, etc. are preferable from the viewpoint of suppressing 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 reducing costs. 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 obtained in this way has the general formula (1):

^{CX 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 represent halogen atoms.]

It is a halogenated butene compound represented by .

X ¹ , X ² , ^{X 3 ,} X ^{7 ,} X ⁸ and X ⁹ in general formula (1) ^are Corresponds to ⁸ and X ⁹ . Moreover, in 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. For this reason, the halogenated butene compound represented by general formula (1) to be manufactured is, for example, specifically CF ₃ CF=CHCF ₃ , CCl ₃ CCl=CHCCl ₃ , CBr ₃ CBr=CHCBr ₃ , etc. You can.

After the reaction between the halogenated butene compound and the hydrogen halide (addition reaction with hydrogen halide) is completed, if necessary, purification is performed by a conventional method to obtain the target compound, the halogenated butene compound. In addition, according to the production method of the present disclosure, the addition of 2 moles of hydrogen halide to 1 mole of the halogenated butyne compound is suppressed, as described above, and 1 mole of hydrogen halide is added to 1 mole of the halogenated butyne compound. Compounds can be obtained selectively.

The halogenated butene compound obtained in this way can be effectively used in various applications such as an etching gas for forming cutting-edge fine structures of semiconductors, liquid crystals, etc.

2. Halogenated butene composition

As described above, a halogenated butene compound can be obtained. A halogenated butene compound in which 1 mole of hydrogen halide is added to 1 mole of a halogenated butene compound, and a halogenated butene compound in which 2 moles of hydrogen halide are added to 1 mole of a halogenated butene compound. It may also be obtained in the form of a halogenated butene composition containing the compound.

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

In general formulas (1) and ( ³ ), the halogen atoms represented by X ¹ , X ² , X ³ , X ⁴ , ^{X 5 ,} X ^{6 ,} , bromine atom, and iodine atom, and a fluorine atom is preferable.

When the total amount of the halogenated butene composition of this disclosure is 100 mol%, the content of the halogenated butene compound represented by General Formula (1) is preferably 91.00 to 99.99 mol%, and more preferably 92.00 to 99.98 mol%. Moreover, the content of the halogenated butane compound represented by General Formula (3) is preferably 0.01 to 9.00 mol%, and 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 general formula (1) as described above can be obtained with a high reaction conversion rate and high yield and high selectivity. Therefore, it is possible to reduce components other than the halogenated butene compound represented by general formula (1) in the halogenated butene composition, and thus the purification effort to obtain the halogenated butene compound represented by general formula (1) can be reduced.

The halogenated butene composition of the present disclosure can be effectively used for various purposes, such as an etching gas for forming cutting-edge microstructures of semiconductors, liquid crystals, etc., and as a building block for organic synthesis. Additionally, a building block for organic synthesis refers to a material that can be a precursor for a compound with a highly reactive skeleton. For example, when the halogenated butene composition of the present disclosure is reacted with a fluorinated organosilicon compound such as CF ₃ Si(CH ₃ ) ₃ , a fluoroalkyl group such as a CF ₃ group can be introduced to become a detergent or a fluorinated pharmaceutical intermediate. It is possible to convert it into a substance.

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.

Example

Examples are disclosed below to clarify the features of the present disclosure. The present disclosure is not limited to these examples.

^In the ^methods for producing halogenated butene ^compounds of Examples 1 to 6 and Comparative Examples 1 to 2, the raw material compound is a halogenated butene compound represented by general formula (2) ^, X ⁸ and X ⁹ are fluorine atoms, hydrogen halide is hydrogen fluoride, and the following reaction formula:

CF ₃ C≡CCH ₃ ＋HF→CH ₃ CF=CHCF ₃

Accordingly, a halogenated butene compound was obtained through a hydrogen fluoride addition reaction.

Example 1~4: Hydrogen fluoride addition reaction using activated carbon catalyst

10 g of activated carbon catalyst (manufactured by Osaka Gas Chemicals Co., Ltd.; specific surface area 1200 m ² /g) was added as a catalyst to the SUS pipe (outer diameter: 1/2 inch) as a reaction tube. After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure is adjusted to normal pressure, CF ₃ C≡CCF ₃ (substrate), and the contact time (W/F) between hydrogen fluoride and the activated carbon catalyst is 2g·sec/cc. CF ₃ C≡CCF ₃ (substrate) and hydrogen fluoride gas were distributed.

The reaction was carried out in a gas phase continuous distribution manner.

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

The molar ratio (HF/CF ₃ C≡CCF ₃ ratio) of hydrogen fluoride gas brought into contact with CF ₃ C≡CCF ₃ (substrate) is set to 150, and the contact time (W/F) is set to 2g·sec/cc. The flow rate of hydrogen fluoride gas was adjusted, and the effluent that passed through the removal tower 1 hour after the start of the reaction was collected.

Afterwards, mass spectrometry was performed by gas chromatography/mass spectrometry (GC/MS) using a gas chromatograph (manufactured by Shimadzu Corporation, brand name “GC-2014”), and NMR (manufactured by JEOL, brand name “400YH”) was performed. Structural analysis was performed using NMR spectra.

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 from CF ₃ CF=CHCF ₃ (target compound) was 99.85 mol%, and the selectivity from CF ₃ CF ₂ CH ₂ CF ₃ was 99.85 mol%. The selectivity of CF ₃ CFHCFHCF ₃ was 0.11 mol% and 0.01 mol%. In Example 2, the conversion rate from CF ₃ C≡CCF ₃ (substrate) was 100.00 mol%, the selectivity from CF ₃ CF=CHCF ₃ (target compound) was 99.36 mol%, and the selectivity from CF ₃ CF ₂ CH ₂ CF ₃ was The selectivity of CF ₃ CFHCFHCF ₃ was 0.34 mol% and 0.26 mol%. In Example 3, the conversion rate from CF ₃ C≡CCF ₃ (substrate) was 100.00 mol%, the selectivity from CF ₃ CF=CHCF ₃ (target compound) was 98.45 mol%, and the selectivity from CF ₃ CF ₂ CH ₂ CF ₃ was The selectivity of CF ₃ CFHCFHCF ₃ was 0.98 mol% and 0.10 mol%. In Example 4, the conversion rate from CF ₃ C≡CCF ₃ (substrate) was 100.00 mol%, the selectivity from CF ₃ CF=CHCF ₃ (target compound) was 99.15 mol%, and the selectivity from CF ₃ CF ₂ CH ₂ CF ₃ was The selectivity of CF ₃ CFHCFHCF ₃ was 0.80 mol% and 0.02 mol%.

Example 5~6: Hydrogen fluoride addition reaction using chromium oxide catalyst

Using a chromium oxide catalyst (Cr ₂ O ₃ ) as a catalyst, the reaction temperature was 350°C, and the contact time (W/F) of CF ₃ C≡CCF ₃ (substrate) and hydrogen fluoride gas with the chromium oxide catalyst was 4 g. Adjust the total flow rate of CF ₃ C≡CCF ₃ (substrate) and hydrogen fluoride gas so that it is sec/cc or 5g·sec/cc, and the molar ratio of hydrogen fluoride gas (HF) brought into contact with CF ₃ C≡CCF ₃ (substrate) /CF ₃ C≡CCF ₃ The reaction proceeded in the same manner as in Examples 1 to 4 except that the ratio) was set to 50 or 200.

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 rate from CF ₃ C≡CCF ₃ (substrate) was 97.59 mol%, the selectivity from CF ₃ CF=CHCF ₃ (target compound) was 99.98 mol%, and the selectivity from CF ₃ CF ₂ CH ₂ CF ₃ was 97.59 mol%. The selectivity of CF ₃ CFHCFHCF ₃ was 0.01 mol% and 0.00 mol%. In Example 6, the conversion rate from CF ₃ C≡CCF ₃ (substrate) was 80.90 mol%, the selectivity from CF ₃ CF=CHCF ₃ (target compound) was 99.96 mol%, and the selectivity from CF ₃ CF ₂ CH ₂ CF ₃ was 80.90 mol%. The selectivity of CF ₃ CFHCFHCF ₃ was 0.03 mol% and 0.00 mol%.

Comparative example 1~2: Hydrogen fluoride addition reaction without catalyst

Without using a catalyst, the reaction temperature was 200°C or 350°C, the contact time (W/F) between CF ₃ C≡CCF ₃ (substrate) and the catalyst of hydrogen fluoride gas was 20g·sec/cc, and CF ₃ The reaction proceeded in the same manner as in Examples 1 to 4, except that the molar ratio (HF/CF ₃ C≡CCF ₃ ratio) of hydrogen fluoride gas in contact with C≡CCF ₃ (substrate) was set to 200. In addition, in Comparative Examples 1 and 2, the W/F was set to 20 g·sec/cc at the same flow rate as when the W/F was set to 20 g·sec/cc in Examples 1 to 6 using a catalyst. CF ₃ C≡CCF ₃ means flowing (substrate).

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 compared to Examples 1 to 6, the conversion rate from CF ₃ C≡CCF ₃ (substrate) was 1.92 mol%, The selectivity of CF ₃ CF=CHCF ₃ (target compound) was 90.83 mol%, the selectivity of CF ₃ CF ₂ CH ₂ CF ₃ was 8.27 mol%, and the selectivity of CF ₃ CFHCFHCF ₃ was 0.82 mol%. In Comparative Example 2, although the flow rate of CF ₃ C≡CCF ₃ (substrate) was significantly increased compared to Examples 1 to 6, the conversion rate from CF ₃ C≡CCF ₃ (substrate) was 2.17 mol%, The selectivity of CF ₃ CF=CHCF ₃ (target compound) was 85.52 mol%, the selectivity of CF ₃ CF ₂ CH ₂ CF ₃ was 7.83 mol%, and the selectivity of CF ₃ CFHCFHCF ₃ was 0.62 mol%. For this reason, the conversion rate from CF ₃ C≡CCF ₃ (substrate) is significantly low, and a significant amount of CF ₃ CF ₂ CH ₂ CF ₃ as an impurity is generated, and the selectivity of CF ₃ CF=CHCF ₃ , the target compound. was also low.

The results are listed in Table 1.

[Table 1]

Claims (10)

General formula (1):
^{CX 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 represent halogen atoms.]
A method for producing a halogenated butene compound represented by,
In the presence of at least one catalyst selected from the group consisting of a fluorinated or non-fluorinated activated carbon catalyst and a fluorinated or non-fluorinated chromium oxide catalyst,
General formula (2):
^{CX 1 ​ ​ ​ ​}
[Wherein, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same as above.]
A process of reacting a halogenated butyne compound represented by and hydrogen halide.
A manufacturing method comprising: In claim 1,
A production method wherein X ⁴ in the general formula (1) is a fluorine atom, and the hydrogen halide is hydrogen fluoride. In claim 1 or claim 2,
A production method wherein the catalyst is a fluorinated or non-fluorinated chromium oxide catalyst. General formula (1):
^{CX 1 ​ ​ ​ ​ ​}
[In the formula, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same or different and represent a halogen atom. X ⁴ represents a fluorine atom.]
A method for producing a halogenated butene compound represented by,
In the presence of a catalyst,
General formula (2):
^{CX 1 ​ ​ ​ ​}
[Wherein, X ¹ , X ² , X ³ , X ⁷ , X ⁸ and X ⁹ are the same as above.]
A process of reacting a halogenated butyne compound represented by and hydrogen fluoride.
A manufacturing method comprising: In claim 4,
A production method wherein the catalyst includes 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. In claim 4 or claim 5,
A production method 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 method of any one of claims 1, 2, 4, and 5,
A production method wherein the halogenated butene compound represented by the general formula (1) is CF ₃ CF=CHCF ₃ , and the halogenated butene compound represented by the general formula (2) is CF ₃ C≡CCF ₃ . The method of any one of claims 1, 2, 4, and 5,
A production method comprising reacting 30 to 250 moles of hydrogen halide with respect to 1 mole of the halogenated butyne compound represented by the general formula (2). General formula (1):
^{CX 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 represent halogen atoms.]
A halogenated butene compound represented by
General formula (3):
^{CX 1 ​ ​ ​ ​ ​ ​ ​}
[In the formula, X ¹ , X ² , X ^{3 , X 4 ,} X ⁷ , X ⁸ and ]
A composition containing a halogenated butane compound represented by,
A composition in which the total amount of the composition is 100 mol% and the content of the halogenated butene compound represented by the general formula (1) is 91.00 to 99.99 mol%. In claim 9,
Compositions used as cleaning gases, etching gases or building blocks for organic synthesis.