TWI798518B - The production method of cyclobutane - Google Patents

Abstract

(式中，X¹ 、X² 、X³ 、X⁴ 、X⁵ 及X⁶ 係相同或相異地表示氫原子、鹵素原子，或全氟烷基)，其包含 使一般式(2)所表示之環丁烯與氟化氫在觸媒的存在下，在氣相下反應之步驟，

(式中，X¹ 、X² 、X³ 、X⁴ 、X⁵ 及X⁶ 係與前述相同)。The object of the present invention is to produce cyclobutane containing fluorine atoms with high selectivity. The production method is a production method of cyclobutane represented by the general formula (1),

(wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ represent hydrogen atoms, halogen atoms, or perfluoroalkyl groups identically or differently), which includes the general formula (2) The step of reacting cyclobutene and hydrogen fluoride in the gas phase in the presence of a catalyst,

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are the same as above).

Description

The production method of cyclobutane

The present invention relates to a method for producing cyclobutane.

Cyclobutane containing a halogen atom is not only used as a dry etching gas for semiconductors, but also as a compound useful as various refrigerants, foaming agents, and heat transfer media.

In Non _- Patent Document ₁ , _{it is} disclosed that 1H _- 7 The method of fluorocyclobutane.

Non-Patent Document 2 discloses the production of 1Br,2H-hexafluorocyclobutane (cC ₄ F ₆ BrH) from hexafluorocyclobutene (cC ₄ F ₆ ) by addition reaction using hydrogen bromide (HBr). method. [Prior art literature] [Non-patent literature]

[Non-Patent Document 1] Journal of Fluorine Chemistry, 2006, Vol.127, 79-84, "Fluorination of fluoro-cyclobutene with high-valency metal fluoride" [Non-Patent Document 2] Journal of American Chemistry, 1949, Vol.71, 2339-2340, "The Addition of Hydrogen Bromide to Fluorinated Olefins"

[Problem to be solved by the invention]

The purpose of this disclosure is to produce cyclobutanes containing halogen atoms with high selectivity. [Means to solve the problem]

This disclosure includes the following constitutions.

Item 1. A method for producing cyclobutane represented by general formula (1),

(wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ represent hydrogen atoms, halogen atoms, or perfluoroalkyl groups identically or differently), wherein, including the general formula (2) Represents the step of reacting cyclobutene and hydrogen fluoride in the gas phase in the presence of a catalyst,

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are the same as above).

Item 2. The production method described in item 1 above is to supply 0.1 mol to 100 mol of hydrogen fluoride to 1 mol of cyclobutene represented by the aforementioned general formula (2) to react.

Item 3. The production method described in item 1 or 2 above, wherein the catalyst is at least one catalyst selected from the group consisting of activated carbon and chromium compounds.

Item 4. A composition containing cyclobutane represented by general formula (1),

(wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ represent hydrogen atoms, halogen atoms, or perfluoroalkyl groups identically or differently), wherein, the total amount of the composition is defined as 100mol% , the content of cyclobutane represented by the aforementioned general formula (1) is 99 mol% or more.

Item 5. The composition described in item 4 above is used as a cleaning gas, etching gas, deposition gas, or a building block for organic synthesis. [Invention effect]

According to the present disclosure, cyclobutane containing a halogen atom can be produced with high selectivity.

As a result of intensive research by the inventors of the present invention, it has been found that the compound represented by the above general formula (1) can be produced with high selectivity by performing the reaction in the gas phase in the presence of a catalyst in the step of carrying out the addition reaction of hydrogen fluoride to the raw material compound. Cyclobutane with fluorine atom.

This disclosure is based on further repetition of research results based on this knowledge.

This disclosure includes the following embodiments.

A method for producing cyclobutane represented by general formula (1),

(wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ represent hydrogen atoms, halogen atoms, or perfluoroalkyl groups identically or differently), wherein, including the general formula (2) The steps of the reaction of cyclobutene and hydrogen fluoride,

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are the same as above).

In the present disclosure, the aforementioned reaction is performed by the addition reaction of hydrogen fluoride, and the aforementioned steps are reacted in the gas phase in the presence of a catalyst.

In the present disclosure, by satisfying the above requirements, cyclobutane containing fluorine atoms can be produced with high selectivity.

In this disclosure, the so-called "selectivity" means the target contained in the effluent gas relative to the total molar amount of compounds other than the raw material compounds (cyclobutane containing fluorine atoms, etc.) in the effluent gas from the outlet of the reactor. The ratio (mol%) of the total molar amount of the compound (cyclobutane containing fluorine atom).

In this disclosure, the so-called "conversion rate" means the compound (containing fluorine atom) other than the raw material compound (containing fluorine atom) contained in the effluent gas from the outlet of the reactor relative to the molar amount of the raw material compound (cyclobutene) supplied to the reactor. The ratio (mol%) of the total molar amount of cyclobutane).

The manufacturing method of cyclobutane disclosed in this disclosure is suitable for industrial grade production. The method for producing cyclobutane of the present disclosure uses cyclobutene and hydrogen fluoride as raw materials, and these raw materials are available in industrial grade. The method for producing cyclobutane disclosed herein can achieve high selectivity when 1H-heptafluorocyclobutane is used as the target compound.

(1) Raw material compound Cyclobutene represented by general formula (2) In this disclosure, the raw material compounds are cyclobutene and hydrogen fluoride represented by the general formula (2),

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ represent hydrogen atom, halogen atom, or perfluoroalkyl group identically or differently).

X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are the same or different representations of a hydrogen atom, a halogen atom, or a perfluoroalkyl group.

The halogen atoms of X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are exemplified by fluorine atom, chlorine atom, bromine atom and iodine atom.

The perfluoroalkyl groups of X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are alkyl groups in which all hydrogen atoms are replaced by fluorine atoms. The perfluoroalkyl group is, for example, a perfluoroalkyl group having 1 to 20 carbons, preferably 1 to 12 carbons, more preferably 1 to 6 carbons, more preferably 1 to 4 carbons, particularly preferably 1 to 3 carbons. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. As the aforementioned perfluoroalkyl group, trifluoromethyl (CF ₃ -) and pentafluoroethyl (C ₂ F ₅ -) are preferable.

The cyclobutene represented by the general formula (2) as a raw material compound is more preferably X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X from the viewpoint of producing cyclobutane containing fluorine atoms with high selectivity. ⁶ represents a fluorine atom or a perfluoroalkyl group either identically or differently.

The cyclobutene represented by the general formula (2) as a raw material compound includes, for example, the following compounds.

These cyclobutenes represented by the general formula (2) may be used alone or in combination of two or more. As these cyclobutenes, known or commercially available items can be used.

The cyclobutene represented by the general formula (2) is more preferably X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ from the viewpoint of producing cyclobutane containing fluorine atoms with high selectivity. fluorine atom.

Molar ratio of cyclobutene to hydrogen fluoride Hydrogen fluoride (HF) is usually preferably supplied to the reactor in a gas phase state together with cyclobutene (raw material compound) represented by the general formula (2). The supply amount of hydrogen fluoride is preferably about 0.1 mol to 100 mol for 1 mol of cyclobutene (raw material compound) represented by the general formula (2). The supply amount of hydrogen fluoride is more preferably about 0.5 mol to 50 mol, more preferably about 1 mol to 30 mol, especially preferably 1 mol of cyclobutene (raw material compound) represented by the general formula (2). About 1 mole to 20 moles. When the supply amount of hydrogen fluoride is within the above-mentioned range, the addition reaction of hydrogen fluoride can proceed favorably, the formation of impurities can be reduced, the selectivity of cyclobutane containing fluorine atoms in the product can be increased, and high yield recovery can be achieved.

(2) Addition reaction The step of reacting cyclobutene and hydrogen fluoride in the present disclosure utilizes the addition reaction of hydrogen fluoride to be carried out in the gas phase in the presence of a catalyst. The step of reacting cyclobutene with hydrogen fluoride (addition reaction) in the present disclosure is carried out in the gas phase, and is particularly preferably carried out in a gas phase continuous flow method using a fixed bed reactor. When it is carried out in a gas-phase continuous flow system, the equipment and operation can be simplified, and it is also economically advantageous.

The step of reacting cyclobutene and hydrogen fluoride in this disclosure is, for example, as a raw material compound, more preferably in cyclobutene represented by the general formula (2), X ¹ , X ² , X ³ , X ⁴ and X ⁶ are fluorine atoms .

It is preferable to utilize the addition reaction of hydrogen fluoride according to the following reaction formula.

catalyst The step of reacting cyclobutene with hydrogen fluoride in the present disclosure is carried out in the gas phase in the presence of a catalyst in the addition reaction using hydrogen fluoride.

The catalyst used in this step is preferably activated carbon.

The catalyst used in this step is preferably a metal catalyst. As metal catalysts, chromium catalysts such as chromium oxide, fluorinated chromium oxide, and chromium fluoride, aluminum catalysts such as aluminum oxide, fluorinated alumina, and aluminum fluoride, iron oxide, fluorinated iron oxide, and fluorine catalysts are preferred. Metal catalysts such as iron catalysts such as iron oxide, nickel catalysts such as nickel oxide, fluorinated nickel oxide, and nickel fluoride, and magnesium catalysts such as magnesium oxide, fluorinated magnesium oxide, and magnesium fluoride. The catalyst is preferably at least one selected from the group consisting of the aforementioned metal catalysts.

The catalyst used in this step is preferably at least one selected from the group consisting of activated carbon and the aforementioned metal catalysts. Among these catalysts, chromium catalysts such as activated carbon, chromium oxide, fluorinated chromium oxide, and chromium fluoride are more preferable from the viewpoint of obtaining the target compound with higher selectivity. In addition, the conversion rate of the raw material compound can be further improved.

In this step, when the raw material compound is brought into contact with the catalyst in a gas phase, it is preferable that the catalyst is brought into contact with the raw material compound in a solid state (solid phase).

In this step, the catalyst may be in the form of powder, but the reaction in the gas phase continuous flow mode is better when the catalyst is in the form of particles.

The specific surface area of the aforementioned catalyst measured by the BET method (hereinafter also referred to as the BET specific surface area) is usually 10~3,000m ² /g, preferably 10~2,500m ² /g, more preferably 20~2,000m ² /g, more preferably 30~1,500m ² /g. When the BET specific surface area of the catalyst is within these ranges, the target compound can be obtained with high selectivity because the density of the catalyst particles will not be too small. Moreover, the conversion rate of a raw material compound can also be improved. For example, activated carbon with a BET specific surface area of 800-2,000 m ² /g is preferably used as a catalyst.

When activated carbon is used as a catalyst, powdered activated carbon such as crushed carbon, formed carbon, granular carbon, spherical carbon, etc. is preferably used. As the powdered activated carbon, it is preferable to use the powdered activated carbon whose particle size is 4 meshes (4.76 mm) to 100 meshes (0.149 mm) according to the JIS test. When activated carbon is used as a catalyst, it can be treated by flowing nitrogen gas at a temperature of, for example, 300-500°C for a period of time before use (heat-treated activated carbon).

When using a metal catalyst as a catalyst, it is preferably supported on a carrier. Examples of the carrier include carbon, alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), silicon oxide (SiO ₂ ), titanium oxide (TiO ₂ ), and the like. Activated carbon, amorphous carbon, graphite, diamond, etc. can be used as carbon.

As an example of the catalyst of the present disclosure, chromium oxide and fluorinated chromium oxide will be described. For example, when chromium oxide is represented by Cr ₂ O ₃ ·nH ₂ O, the value of n is preferably 3 or less, more preferably 1 to 1.5. In addition, the aforementioned chromium oxide is preferably the composition formula: CrO _m , where m is usually in the range of 1.5<m<3. As a catalyst, fluorinated chromium oxide can be prepared by fluorinating chromium oxide. Examples of fluorination include fluorination with hydrogen fluoride (HF), fluorination with fluorocarbon, and the like.

Fluorinated chromium oxide as a catalyst can be obtained by the method described in Japanese Patent No. 3412165, for example. Fluorinated chromium oxide can be obtained by fluorinating chromium oxide with hydrogen fluoride (HF treatment). The fluorination temperature is preferably, for example, 100 to 460°C. The pressure of fluorination is preferably the pressure supplied during the catalyst reaction. In this disclosure, it is particularly preferred to use a high fluorinated-chromium oxide catalyst with a high fluorine content. Highly fluorinated chromium oxide catalysts can be obtained by fluorinating chromium oxide at higher temperatures than usual for prolonged periods of time.

The high fluoride-chromium oxide catalyst preferably has a fluorine content of 30% by mass or more, more preferably 30-45% by mass. The fluorine content can be determined by the mass change of the catalyst or the quantitative analysis method of general chromium oxide.

gas phase reaction temperature In the step of reacting cyclobutene and hydrogen fluoride in this disclosure, the lower limit of the reaction temperature is based on the view that the addition reaction by hydrogen fluoride can be carried out more efficiently and the target compound can be obtained with a higher selectivity, and based on the idea of suppressing the decrease in conversion rate From a viewpoint, it is usually 50°C, preferably 200°C, more preferably 250°C, and still more preferably 300°C.

When activated carbon is used as the catalyst, the reaction temperature is preferably 50°C-400°C, more preferably 100°C-350°C, and more preferably 150°C-300°C.

When a chromium catalyst is used as the catalyst, the reaction temperature is preferably above 50°C, more preferably above 250°C, and more preferably above 300°C.

The upper limit of the reaction temperature for the reaction of cyclobutene and hydrogen fluoride is based on the viewpoint that the addition reaction by hydrogen fluoride can be carried out more efficiently and the target compound can be obtained with a higher selectivity, and is based on the suppression of decomposition of the reaction product or From the viewpoint of selectivity reduction due to polymerization, it is usually 500°C, preferably 450°C, more preferably 400°C.

The gas phase reaction time is the reaction time for the reaction between cyclobutene and hydrogen fluoride, if the contact time of the raw material compound to the catalyst (W/F ₀ ) [W: metal catalyst weight (g), F ₀ : the flow rate of the raw material compound ( cc/sec)] increase can improve the conversion rate of raw material compounds, but the amount of catalyst increases and the equipment becomes larger and inefficient.

Therefore, the reaction time for reacting cyclobutene and hydrogen fluoride is preferably 1 g·sec for the contact time (W/F ₀ ) of the raw material compound with the catalyst from the viewpoint of increasing the conversion rate of the raw material compound and suppressing the cost of equipment. /cc~30g·sec/cc, more preferably 1.5g·sec/cc~10g·sec/cc, more preferably 2.0g·sec/cc~5.0g·sec/cc.

The above-mentioned contact time of the raw material compound with the catalyst means the time during which the raw material compound and the catalyst are in contact.

Molar ratio of cyclobutene to hydrogen fluoride The supply amount of hydrogen fluoride, in the case of using activated carbon and chromium catalyst as a catalyst, is based on the viewpoint of reaction cost and productivity, relative to 1 mol of cyclobutene (raw material compound) represented by the above general formula (2) , preferably about 0.1 mol to 100 mol, more preferably about 0.5 mol to 75 mol, and more preferably about 1 mol to 50 mol.

gas phase reaction pressure The reaction pressure for reacting cyclobutene with hydrogen fluoride is preferably -0.05MPa~2MPa, more preferably -0.01MPa~1MPa, and more preferably normal Pressure ~0.5MPa. In addition, in this disclosure, when there is no description about pressure, it is gauge pressure.

In the reaction between cyclobutene and hydrogen fluoride, the shape and structure of the reactor are not particularly limited as long as they can withstand the above-mentioned temperature and pressure as a reactor for contacting and reacting the raw material compound with a catalyst (activated carbon, chromium catalyst, etc.) . Examples of the reactor include, for example, a vertical reactor, a horizontal reactor, a multi-tubular reactor, and the like. Examples of materials for the reactor include glass, stainless steel, iron, nickel, iron-nickel alloy, and the like.

Example of gas phase reaction The reaction between cyclobutene and hydrogen fluoride (by the addition reaction of hydrogen fluoride) can be carried out by either a flow method or a batch method in which the raw material compound is continuously fed into the reactor and the target compound is continuously extracted from the reactor. When the target compound stays in the reactor, since it can further undergo detachment reaction, it is more carried out in a flow-through method. The step of reacting cyclobutene and hydrogen fluoride in the present disclosure is carried out in the gas phase, and is preferably carried out in a gas phase continuous flow method using a fixed bed reactor. When it is carried out in the gas phase continuous flow method, the equipment and operation can be simplified, which is economically advantageous.

The environment for the reaction between cyclobutene and hydrogen fluoride is preferably in the presence of an inert gas and/or in the presence of hydrogen fluoride from the viewpoint of suppressing degradation of catalysts (activated carbon, chromium catalyst, etc.). The inert gas is preferably at least one selected from the group consisting of nitrogen, helium, argon and carbon dioxide. Among these inert gases, nitrogen is more preferable from the viewpoint of cost suppression. The concentration of the inert gas is preferably 0-50 mol% of the gas components introduced into the reactor.

After the reaction between cyclobutene and hydrogen fluoride (by the addition reaction of hydrogen fluoride), if necessary, it can be purified according to the usual method to obtain cyclobutane containing fluorine atoms represented by the general formula (1).

(3) Target compound The target compound of this disclosure is a fluorine-containing cyclobutane represented by the general formula (1):

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ represent hydrogen atom, halogen atom, or perfluoroalkyl group identically or differently).

The fluorine atom-containing cyclobutane represented by the general formula (1) as produced is exemplified, for example, by the following compounds.

In the cyclobutane containing fluorine atom represented by the general formula (1), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ represent hydrogen atom, halogen atom, or perfluoroalkane identically or differently. base.

In the method for producing cyclobutane disclosed in the present disclosure, in the step of reacting cyclobutene and hydrogen fluoride represented by the general formula (2), the raw material compound is subjected to an addition reaction by hydrogen fluoride, for example, as a raw material compound, the general formula (2) ) represents cyclobutene, preferably X ¹ , X ² , X ³ , X ⁴ and X ⁶ are fluorine atoms.

Preferably, it is based on the following reaction, by addition reaction of hydrogen fluoride.

The target compound is a fluorine atom-containing cyclobutane represented by the general formula (1), more preferably X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are fluorine atoms.

According to the production method of the present disclosure, the fluorine atom-containing cyclobutane represented by the general formula (1) can be produced satisfactorily at an industrial grade with high selectivity as the target compound.

(4) Compositions of cyclobutane containing fluorine atoms As above, the fluorine-containing cyclobutane represented by the general formula (1) can be obtained, but as mentioned above, there are also cyclobutanes containing the fluorine-containing atoms represented by the general formula (1) and the general formula (2) ) represents the state of cyclobutene composition obtained.

As the fluorine atom-containing cyclobutane represented by the general formula (1) contained in the composition, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are preferably fluorine atoms.

In the composition of the fluorine atom-containing cyclobutane represented by the general formula (1) of the present disclosure, when the total amount of the aforementioned composition is defined as 100 mol%, the amount of the fluorine atom-containing cyclobutane represented by the general formula (1) The content is preferably more than 99 mol%.

In the composition of the fluorine atom-containing cyclobutane represented by the general formula (1) of the present disclosure, when the total amount of the aforementioned composition is defined as 100 mol%, the amount of the fluorine atom-containing cyclobutane represented by the general formula (1) The content is preferably 1 mol%~99.9 mol%, more preferably 5 mol%~99.9 mol%, and more preferably 10 mol%~99.9 mol%.

According to the production method of the present invention, when the composition of cyclobutane containing fluorine atoms represented by the general formula (1) is obtained, the fluorine-containing cyclobutane represented by the general formula (1) can be obtained with a particularly high selectivity. Atomic cyclobutane, as a result, can reduce the components other than the fluorine atom-containing cyclobutane represented by the general formula (1) in the aforementioned composition. According to the production method of the present disclosure, it is possible to reduce the purification effort for obtaining the fluorine atom-containing cyclobutane represented by the general formula (1).

The composition of the present disclosure including the fluorine atom-containing cyclobutane represented by the general formula (1) is the same as the case of the fluorine atom-containing cyclobutane represented by the general formula (1) alone, except that it can be effectively used in semiconductors In addition to etching gases for forming the most advanced microstructures such as liquid crystals, etc., it can also be effectively used for various purposes such as deposition gases, building blocks for organic synthesis, and cleaning gases.

The aforementioned deposition gas system is a gas for depositing an etch-resistant polymer layer.

A 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 fluorine atom-containing cyclobutane represented by the general formula (1) of the present disclosure and the composition containing it react with a fluorine-containing organosilicon compound such as CF ₃ Si(CH ₃ ) ₃ , CF ₃ groups, etc. can be introduced The fluoroalkyl groups can be transformed into substances that can become detergents or fluorine-containing pharmaceutical intermediates.

The embodiments of the present disclosure have been described above, but various changes can be made in the embodiments and details as long as they do not deviate from the spirit and scope of the claims. [Example]

The following examples are given to illustrate the present invention in detail, but the present disclosure is not limited to these examples.

EXAMPLES In the method for producing cyclobutane containing fluorine atoms, the raw material compound is cyclobutene represented by the general formula (2), and X ¹ , X ² , X ³ and X ⁴ are fluorine atoms.

Addition reaction of cyclobutene by hydrogen fluoride is carried out according to the following reaction formula.

The target compound is a fluorine atom-containing cyclobutane represented by general formula (1), wherein X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are fluorine atoms.

Example 1 (1-1~1-5), catalyst: activated carbon SUS piping (outer diameter: 1/2 inch) was used as a reaction tube, and 10 g of activated carbon as a catalyst was filled. The aforementioned catalyst is used in the addition reaction by hydrogen fluoride. The BET specific surface area of activated carbon is 850m ² /g. 10 g of activated carbon as a catalyst was added to the SUS pipe (outer diameter: 1/2 inch) of the reactor.

Under nitrogen atmosphere, after drying at 200°C for 2 hours, so that the pressure is normal pressure, the contact time (W/F ₀ ) of cyclobutene cC ₄ F ₆ (raw material compound) and activated carbon (catalyst) is 2.0g・In the form of sec/cc, the raw material compound (cC ₄ F ₆ ) was circulated in the reactor.

The supply amount of hydrogen fluoride was 1 mole or 15 moles relative to 1 mole of cyclobutene cC ₄ F ₆ (raw material compound).

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

The reactor is heated at 150°C, 200°C, 250°C or 300°C to start the addition reaction by hydrogen fluoride. One hour after the start of the addition reaction by hydrogen fluoride, the distillate passing through the detoxification tower was collected.

Subsequently, mass analysis was performed by gas chromatography/mass spectrometry (GC-MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and NMR (manufactured by JEOL Corporation, trade name "GC-2014") was used for mass analysis. 400YH") for structural analysis using NMR spectroscopy.

From the results of mass analysis and structural analysis, it was confirmed that cC ₄ F ₇ H was produced as the target compound. In Example 1-1, the conversion from cC ₄ F ₆ (raw material compound) was 0.364 mol%, and the selectivity (yield) of cC ₄ F ₇ H (target compound) was 18.6 mol%.

Embodiment 1-2 is conversion: 11.6mol%, selectivity: 96.2mol%.

Embodiment 1-3 is conversion: 4.57mol%, selectivity: 84.9mol%.

Embodiment 1-4 is conversion: 2.30mol%, selectivity: 38.8mol%.

Embodiment 1-5 series conversion rate: 0.6mol%, selectivity: 94.2mol%.

Example 2 (2-1~2-8), catalyst: chromium catalyst uses SUS pipe (outer diameter: 1/2 inch) as _the reaction tube, filled with _Cr2O3 as the main component of oxidation catalyst Chromium 10g. Anhydrous hydrogen fluoride is passed through the reactor as a pretreatment before using the above-mentioned catalyst in the dehydrogenation reaction (dehydrofluorination reaction), and the fluorination treatment is performed by setting the temperature of the reactor at 200°C to 300°C. The fluorinated chromium oxide is taken out and used for dehydrofluorination reaction. The BET specific surface area of fluorinated chromium oxide is 75 m ² /g. To the SUS pipe (outer diameter: 1/2 inch) of the reactor, 10 g of fluorinated chromium oxide (fluorinated chromium oxide) was added as a catalyst.

The contact time of cyclobutene cC ₄ F ₆ (raw material compound) and fluorinated chromium oxide (catalyst) (W/F ₀ ) In the form of 3.0g·sec/cc, 4.0g·sec/cc or 5.0g·sec/cc, the raw material compound (cC ₄ F ₆ H ₂ ) is circulated in the reactor.

The supply amount of hydrogen fluoride was 1 mol, 5 mol or 20 mol with respect to 1 mol of cyclobutene cC ₄ F ₆ (raw material compound).

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

The reactor is heated at 50°C, 200°C, 250°C, 300°C or 350°C to start the addition reaction by hydrogen fluoride. One hour after the start of the addition reaction by hydrogen fluoride, the distillate passing through the detoxification tower was collected.

Subsequently, mass analysis was performed by gas chromatography/mass spectrometry (GC-MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and NMR (manufactured by JEOL Corporation, trade name "GC-2014") was used for mass analysis. 400YH") for structural analysis using NMR spectroscopy.

From the results of mass analysis and structural analysis, it was confirmed that cC ₄ F ₇ H was produced as the target compound. In Example 2-1, the conversion from cC ₄ F ₆ (raw material compound) was 0.942 mol%, and the selectivity (yield) of cC ₄ F ₇ H (target compound) was 0.7 mol%.

Embodiment 2-2 is conversion: 0.183mol%, selectivity: 1.6mol%.

Embodiment 2-3 is conversion: 0.506mol%, selectivity: 2.4mol%.

Embodiment 2-4 is conversion: 0.396mol%, selectivity: 0.7mol%.

Embodiment 2-5 is conversion rate: 0.924mol%, selectivity: 4.2mol%.

Embodiment 2-6 is conversion rate: 1.37mol%, selectivity: 3.0mol%.

Embodiment 2-7 is conversion: 1.62mol%, selectivity: 2.0mol%.

Embodiment 2-8 is conversion: 2.87mol%, selectivity: 0.2mol%.

Comparative Examples 1 and 2 Following the experimental method of the previous examples, without using a catalyst, hydrogen fluoride was supplied to cyclobutene cC ₄ F ₆ (raw material compound) to react.

The supply amount of hydrogen fluoride was set at 20 mol with respect to 1 mol of cyclobutene cC ₄ F ₆ (raw material compound).

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

The reactor is heated at 200°C or 350°C to start the addition reaction by hydrogen fluoride. One hour after the start of the addition reaction by hydrogen fluoride, the distillate passing through the detoxification tower was collected.

Subsequently, mass analysis was performed by gas chromatography/mass spectrometry (GC-MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and NMR (manufactured by JEOL Corporation, trade name "GC-2014") was used for mass analysis. 400YH") for structural analysis using NMR spectroscopy.

From the results of mass analysis and structural analysis, the conversion rate from cC ₄ F ₆ (raw material compound) was 0.801 mol% (comparative example 1) or 0.695 mol% (comparative example 2), but it was not confirmed that cC ₄ F ₇ H (objective compound).

The results of each example are shown in Table 1 below. In Table 1, the so-called contact time (W/F ₀ ) represents the flow velocity of the raw material gas, which means the contact time between the catalyst and the raw material gas. The so-called molar ratio HF/cC ₄ F ₆ refers to the amount of HF used (in moles) for 1 mole of cC ₄ F ₆ .

Claims (7)

A method for producing cyclobutane represented by general formula (1),

(wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ represent hydrogen atoms, halogen atoms, or perfluoroalkyl groups identically or differently), including the general formula (2) Represents the step of reacting cyclobutene and hydrogen fluoride in the gas phase in the presence of a catalyst,

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are the same as above), and the above reaction is a reaction of adding hydrogen fluoride. The production method as described in Claim 1 is to supply 0.1 mol to 100 mol of hydrogen fluoride to react with 1 mol of cyclobutene represented by the general formula (2). The production method as described in claim 1 or 2, wherein the aforementioned catalyst is supported by carbon; alumina (Al ₂ O ₃ ); zirconia (ZrO ₂ ); silicon oxide (SiO ₂ ); and titanium oxide The catalyst of the carrier selected from the group consisting of (TiO ₂ ), and the aforementioned carbon is carbon selected from the group consisting of activated carbon, amorphous carbon, graphite, and diamond. The manufacturing method as described in claim 1 or 2, wherein the aforementioned catalyst is activated carbon; a chromium catalyst selected from chromium oxide, fluorinated chromium oxide, and chromium fluoride; aluminum oxide, fluorinated oxidized Aluminum, and aluminum catalysts selected from aluminum fluoride; iron catalysts selected from iron oxide, fluorinated iron oxide, and iron fluoride; iron catalysts selected from nickel oxide, fluorinated nickel oxide, and nickel fluoride the selected nickel catalyst; and at least one catalyst selected from the group consisting of magnesium oxide, magnesia fluoride, and magnesium fluoride. The production method as described in claim 1 or 2, wherein the aforementioned catalyst is selected from the group consisting of activated carbon; and a chromium catalyst selected from chromium oxide, fluorinated chromium oxide, and chromium fluoride of at least one catalyst. A use of a composition containing cyclobutane represented by general formula (1),

(wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ represent fluorine atoms or perfluoroalkyl groups identically or differently), wherein the total amount of the composition is defined as 100 mol%, and the aforementioned general The content of cyclobutane represented by the formula (1) is 99 mol% or more, and it is used as a cleaning gas or an etching gas. As the use of the composition described in claim 6, wherein the cyclobutane represented by the aforementioned general formula (1) is composed of

Cyclobutanes containing fluorine atoms selected from .