KR102578063B1 - Method for producing cyclobutane - Google Patents

Abstract

The present disclosure aims to produce cyclobutane containing a fluorine atom with high selectivity.
General formula (1):

(In the formula ^, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and
As a method for producing cyclobutane represented by,
General formula (2):

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are the same as above.)
A production method comprising the step of reacting cyclobutene and hydrogen fluoride represented by in the gas phase in the presence of a catalyst.

Description

Method for producing cyclobutane

This disclosure relates to a method for producing cyclobutane.

Cyclobutane containing a halogen atom is a compound useful as a dry etching gas for semiconductors, as well as various refrigerants, foaming agents, and heat transfer media.

In Non-Patent Document 1, 1H is obtained from 3,3,4,4-tetrafluorocyclobutene by a fluorination reaction using a fluorine agent such as CoF ₃ , MnF ₃ , AgF ₂ , CeF ₄ or KCoF ₄ -Discloses a method for producing heptafluorocyclobutane.

In Non-Patent Document 2, 1Br,2H-hexafluorocyclobutane (cC ₄ F ₆ BrH) is obtained from hexafluorocyclobutene (cC ₄ F ₆ ) through an addition reaction using hydrogen bromide (HBr). A manufacturing method is disclosed.

Journal of Fluorine Chemistry, 2006, Vol.127, 79-84, “Fluorination of fluoro-cyclobutene with high-valency metal fluoride” Journal of American Chemistry, 1949, Vol.71, 2339-2340, “The Addition of Hydrogen Bromide to Fluorinated Olefins”

The present disclosure aims to produce cyclobutane containing a halogen atom with high selectivity.

This disclosure includes the following configurations.

Paragraph 1.

General formula (1):

(In the formula ^, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and

As a method for producing cyclobutane represented by,

General formula (2):

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

A production method comprising the step of reacting cyclobutene and hydrogen fluoride represented by in the gas phase in the presence of a catalyst.

Paragraph 2.

The production method according to item 1 above, wherein 0.1 mole to 100 mole of hydrogen fluoride is supplied to react with 1 mole of cyclobutene represented by the general formula (2).

Paragraph 3.

The production method according to item 1 or item 2, wherein the catalyst is at least one catalyst selected from the group consisting of activated carbon and chromium compounds.

Paragraph 4.

General formula (1):

(In the formula ^, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and

A composition containing cyclobutane represented by,

A composition in which the total amount of the composition is 100 mol% and the content of cyclobutane represented by the general formula (1) is 99 mol% or more.

Clause 5.

The composition according to item 4 above, used as a cleaning gas, etching gas, deposit gas or building block for organic synthesis.

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

As a result of extensive research, the present inventors have conducted an addition reaction with hydrogen fluoride on a raw material compound in the gas phase in the presence of a catalyst, thereby producing a cyclochloride compound containing a fluorine atom represented by the general formula (1) above. It was discovered that butane could be produced with high selectivity.

This disclosure was completed as a result of further research based on such knowledge.

This disclosure includes the following embodiments.

General formula (1) of the present disclosure:

(In the formula ^, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and

The method for producing cyclobutane represented by,

General formula (2):

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

It includes a process of reacting cyclobutene represented by and hydrogen fluoride.

In the present disclosure, the reaction is an addition reaction using hydrogen fluoride, and the reaction is carried out in the gas phase in the presence of a catalyst.

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

In the present disclosure, “selectivity” refers to the target compound (fluorine) contained in the effluent gas relative to the total molar amount of compounds other than the raw material compound (cyclobutane, etc. containing a fluorine atom) in the effluent gas from the reactor outlet. It means the ratio (mol%) of the total molar amount of cyclobutane containing atoms.

In the present disclosure, “conversion ratio” refers to the ratio of compounds other than the raw material compound (cyclobutane containing a fluorine atom, etc.) contained in the effluent gas from the reactor outlet to the molar amount of the raw material compound (cyclobutene) supplied to the reactor. It means the ratio (mol%) of the total molar amount.

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

(1) Raw material compounds

Cyclobutene represented by general formula (2)

In the present disclosure, the raw material compound has the general formula (2):

(In the formula ^, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and

Cyclobutene, and hydrogen fluoride, represented by .

X ¹ , ^{X 2 ,} X ³ , X ⁴ ,

Halogen atoms ^of X ¹ , ^{X 2} , X ³ , X ⁴ ,

^The perfluoroalkyl groups ^of X ¹ , X ² , X ³ , X ⁴ , The perfluoroalkyl group is, for example, 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, particularly preferably 1 to 3 carbon atoms. It is preferable that it is a perfluoroalkyl group. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. The perfluoroalkyl group is preferably a trifluoromethyl group (CF ₃ -) and a pentafluoroethyl group (C ₂ F ₅ -).

As cyclobutene represented by general formula (2), which is a raw material compound, cyclobutane containing a fluorine atom can be produced with high selectivity, and X ^{1 ,} X ^{2 ,} X ³ , X ⁴ , It is more preferable that they are the same or different and are a fluorine atom or a perfluoroalkyl group.

Cyclobutene represented by general formula (2), which is a raw material compound, is, for example, as follows:

Compounds such as these can be mentioned.

Cyclobutenes represented by these general formulas (2) may be used individually or in combination of two or more types. As such cyclobutene, known or commercially available products can be used.

In cyclobutene represented by general formula (2), cyclobutane containing a fluorine atom can be produced with high selectivity, and X ^{1 , X 2} , X ³ , X ⁴ , It is more preferable that it is an atom.

Cyclobutene and hydrogen fluoride molar ratio

Hydrogen fluoride (HF) is usually preferably supplied to the reactor in a gaseous state together with cyclobutene (raw material compound) represented by general formula (2). The amount of hydrogen fluoride supplied is preferably about 0.1 mole to 100 mole per mole 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, and 1 mol per mole of cyclobutene (raw material compound) represented by the general formula (2). About ∼20 mol is particularly preferred. By setting the supply amount of hydrogen fluoride in the above range, the addition reaction with hydrogen fluoride can proceed satisfactorily and the production of impurities can be reduced, so that the selectivity of cyclobutane containing fluorine atoms in the product is high and recovery can be achieved in high yield. You can.

(2) Addition reaction

The process of reacting cyclobutene and hydrogen fluoride in the present disclosure is an addition reaction using hydrogen fluoride, and is performed in the gas phase in the presence of a catalyst. In the process (addition reaction) of reacting cyclobutene with hydrogen fluoride in the present disclosure, it is preferably carried out in the gas phase, especially in the gas phase continuous flow method using a fixed bed reactor. In the case of carrying out the gas phase continuous distribution method, equipment, operation, etc. can be simplified and it is economically advantageous.

In the step of reacting cyclobutene and hydrogen ^fluoride in the present disclosure, for example, in cyclobutene represented ^by general formula ( ² ) as a ^raw material compound, X ¹ , It is more preferable that silver is a fluorine atom.

According to the reaction formula below, it is preferable that it is an addition reaction with hydrogen fluoride.

catalyst

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

The catalyst used in this process is preferably activated carbon.

The catalyst used in this process is preferably a metal catalyst. As metal catalysts, chromium catalysts such as chromium oxide, chromium fluoride, and chromium fluoride, aluminum catalysts such as aluminum oxide, aluminum fluoride, and aluminum fluoride, iron catalysts such as iron oxide, iron fluoride, and iron fluoride, nickel oxide, and nickel fluoride. , a metal catalyst such as a nickel catalyst such as nickel fluoride, or a magnesium catalyst such as magnesium oxide, magnesium fluoride, or magnesium fluoride. The catalyst is preferably at least one selected from the group consisting of the above metal catalysts.

The catalyst used in this process is preferably at least one selected from the group consisting of activated carbon and the above metal catalyst. Among these catalysts, chromium catalysts such as activated carbon, chromium oxide, chromium fluoride, and chromium fluoride are more preferable because the target compound can be obtained at a higher selectivity. In addition, it is also possible to further improve the conversion rate of the raw material compound.

In this process, when bringing the raw material compound into contact with the catalyst in the gas phase, it is preferable to bring the catalyst into contact with the raw material compound in a solid state (solid phase).

In this process, the catalyst may be in a powder form, but a pellet form is preferable for gas phase continuous flow reaction.

The specific surface area (hereinafter also referred to as BET specific surface area) of the catalyst measured by the BET method is usually 10 to 3,000 m ² /g, preferably 10 to 2,500 m ² /g, more preferably 20. It is ~2,000m ² /g, and more preferably 30~1,500m ² /g. When the BET specific surface area of the catalyst is in this range, the density of catalyst particles is not too small, and the target compound can be obtained with a high selectivity. Additionally, it is also possible to improve the conversion rate of the raw material compound. For example, as a catalyst, it is preferable to use activated carbon with a BET specific surface area of 800 m ² /g to 2,000 m ² /g.

When using activated carbon as a catalyst, it is preferable to use powdered activated carbon such as crushed carbon, coal carbon, granulated carbon, or nodular carbon. It is preferable to use powdered activated carbon that shows a particle size of 4 mesh (4.76 mm) to 100 mesh (0.149 mm) according to the JIS test. When using activated carbon as a catalyst, before use, for example, one that has been treated by flowing nitrogen for a certain period of time under temperature conditions of 300 to 500 ° C. (heat-treated activated carbon) can be used.

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 ), silica (SiO ₂ ), and titania (TiO ₂ ). As carbon, activated carbon, amorphous carbon, graphite, diamond, etc. can be used.

As an example of the catalyst in the present disclosure, chromium oxide and fluorinated chromium oxide will be described. For example, when chromium oxide is expressed as Cr ₂ O ₃ ·nH ₂ O, the n value is preferably 3 or less, and more preferably 1 to 1.5. In addition, in the composition formula: CrO _m , the chromium oxide is preferably in the range of m, which is usually 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 fluorocarbons, etc.

Fluorinated chromium oxide as a catalyst can be obtained, for example, according to the method described in Japanese Patent No. 3412165. Fluorinated chromium oxide can be obtained by fluorinating chromium oxide with hydrogen fluoride (HF treatment). The temperature of fluorination is preferably, for example, 100 to 460°C. The pressure for fluorination is preferably the pressure used for the catalytic reaction. In the present disclosure, it is particularly preferable to use a highly fluorinated chromium oxide catalyst with a high fluorine content. A highly fluorinated chromium oxide catalyst can be obtained by fluorinating chromium oxide at a higher temperature than usual for a long period of time.

The highly fluorinated chromium oxide catalyst preferably has a fluorine content of 30% by mass or more, and more preferably 30 to 45% by mass. The fluorine content can be measured by changing the mass of the catalyst or by a general quantitative analysis method of chromium oxide.

gas phase reaction temperature

In the step of reacting cyclobutene and hydrogen fluoride in the present disclosure, the lower limit of the reaction temperature is from the viewpoint of allowing the addition reaction with hydrogen fluoride to proceed more efficiently and obtaining the target compound at a higher selectivity, and lowering the conversion rate. From the viewpoint of suppressing, it is usually 50°C, preferably 200°C, more preferably 250°C, and even more preferably 300°C.

When using activated carbon as a catalyst, the reaction temperature is preferably 50°C to 400°C, more preferably 100°C to 350°C, and even more preferably 150°C to 300°C.

When using a chromium catalyst as a catalyst, the reaction temperature is preferably 50°C or higher, more preferably 250°C or higher, and even more preferably 300°C or higher.

The upper limit of the reaction temperature for reacting cyclobutene with hydrogen fluoride is from the viewpoint of allowing the addition reaction with hydrogen fluoride to proceed more efficiently and obtaining the target compound at a higher selectivity, as well as the selectivity due to decomposition or polymerization of the reaction product. From the viewpoint of suppressing the decline, the temperature is usually 500°C, preferably 450°C, and more preferably 400°C.

wake up reaction time

The reaction time for reacting cyclobutene and hydrogen fluoride is the contact time of the raw material compound with the catalyst (W/F ₀ ) [W: weight of metal catalyst (g), F ₀ : flow rate of raw material compound (cc/sec)] If you lengthen it, the conversion rate of the raw material compound can be increased, but the amount of catalyst increases and the equipment becomes larger, making it inefficient.

Therefore, the reaction time for reacting cyclobutene and hydrogen fluoride is 1 g in terms of improving the conversion rate of the raw material compound and suppressing equipment costs, and the contact time (W/F ₀ ) of the raw material compound with the catalyst is 1 g. ·sec/cc to 30g·sec/cc is preferable, 1.5g·sec/cc to 10g·sec/cc is more preferable, and 2.0g·sec/cc to 5.0g·sec/cc is still more preferable. do.

The contact time of the raw material compound with the catalyst means the time for which the raw material compound and the catalyst are in contact.

Cyclobutene and hydrogen fluoride molar ratio

When using activated carbon and a chromium catalyst as catalysts, the supply amount of hydrogen fluoride is 0.1 mol to 100 mol per mole of cyclobutene (raw material compound) represented by the general formula (2) from the viewpoint of reaction cost and productivity. It is preferable to react in an amount of about 0.5 mol to 75 mol, more preferably about 1 mol to 50 mol.

gas phase reaction pressure

The reaction pressure for reacting cyclobutene and hydrogen fluoride is preferably -0.05 MPa to 2 MPa, more preferably -0.01 MPa to 1 MPa, from the point of view of advancing the addition reaction with hydrogen fluoride more efficiently, and is from normal pressure to normal pressure. It is more preferable that it is 0.5 MPa. Additionally, in this disclosure, if there is no indication about pressure, it is referred to as gauge pressure.

In the reaction of cyclobutene and hydrogen fluoride, the shape and structure of the reactor that causes the reaction by contacting the raw material compound with a catalyst (activated carbon, chromium catalyst, etc.) is not particularly limited as long as it can withstand the above temperature and pressure. 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.

Examples of weather reactions

The reaction between cyclobutene and hydrogen fluoride (addition reaction with hydrogen fluoride) can be carried out by either a flow method or a batch method in which raw material compounds are continuously injected into a reactor and the target compound is continuously extracted from the reactor. You can. If the target compound remains in the reactor, further desorption reaction may proceed, so it is preferable to carry out the flow-through method. In the process of reacting cyclobutene and hydrogen fluoride in the present disclosure, it is preferably carried out in the gas phase, especially in the gas phase continuous flow method using a fixed bed reactor. In the case of carrying out the gas phase continuous distribution method, equipment, operation, etc. can be simplified and it is economically advantageous.

The atmosphere 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 deterioration of the catalyst (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 suppressing costs. The concentration of the inert gas is preferably 0 to 50 mol% of the gas component introduced into the reactor.

After the reaction between cyclobutene and hydrogen fluoride (addition reaction with hydrogen fluoride) is completed, if necessary, purification is performed according to a conventional method to obtain cyclobutane containing a fluorine atom represented by general formula (1). .

(3) Target compound

The target compound in the present disclosure has the general formula (1):

(In the formula ^, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and

It is a cyclobutane containing a fluorine atom represented by .

Cyclobutane containing a fluorine atom represented by general formula (1) to be manufactured is, for example, as follows:

Compounds such as these can be mentioned.

In cyclobutane containing a fluorine atom represented by general formula (1), X ¹ , X ² , X ³ , X ⁴ , X ^{5 and} Represents a Roalkyl group.

In the method for producing cyclobutane in the present disclosure, the raw material compound undergoes an addition reaction with hydrogen fluoride in the step of reacting cyclobutene represented by the general formula (2) with hydrogen fluoride, for example, raw material As a compound, in cyclobutene represented by general formula (2), it is more preferable that X ¹ , X ² , X ³ , X ⁴ and X ⁶ are fluorine atoms.

According to the reaction formula below, it is preferable that it is an addition reaction with hydrogen fluoride.

The target compound is cyclobutane containing a fluorine atom represented by general formula (1), and it is more preferable that 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, cyclobutane containing a fluorine atom represented by general formula (1) can be successfully produced as a target compound with a high selectivity at an industrial level.

(4) Compositions containing cyclobutane containing fluorine atoms

As described above, cyclobutane containing a fluorine atom represented by general formula (1) can be obtained. However, as described above, cyclobutane containing a fluorine atom represented by general formula (1) and general formula (2) ) It may be obtained in the form of a composition containing cyclobutene represented by ).

As cyclobutane containing a fluorine atom represented by general formula (1) contained in the composition, it is preferable that X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are fluorine atoms.

In the composition containing cyclobutane containing a fluorine atom represented by general formula (1) of the present disclosure, the total amount of the composition is 100 mol%, and the cyclobutane containing a fluorine atom represented by general formula (1) The content is preferably 99 mol% or more.

In the composition containing cyclobutane containing a fluorine atom represented by general formula (1) of the present disclosure, the total amount of the composition is 100 mol%, and the cyclobutane containing a fluorine atom represented by general formula (1) The content is preferably 1 mol% to 99.9 mol%, more preferably 5 mol% to 99.9 mol%, and even more preferably 10 mol% to 99.9 mol%.

According to the production method of the present disclosure, even if it is obtained as a composition containing cyclobutane containing a fluorine atom represented by general formula (1), the cyclobutane containing a fluorine atom represented by general formula (1) is particularly high. It can be obtained by selectivity, and as a result, it is possible to reduce components other than cyclobutane containing a fluorine atom represented by general formula (1) in the composition. According to the production method of the present disclosure, the purification effort for obtaining cyclobutane containing a fluorine atom represented by general formula (1) can be reduced.

The composition containing the cyclobutane containing the fluorine atom represented by the general formula (1) of the present disclosure is, like the case of only cyclobutane containing the fluorine atom represented by the general formula (1), a semiconductor, liquid crystal, etc. In addition to being an etching gas for forming cutting-edge fine structures, it can be effectively used for various purposes such as a deposit gas, a building block for organic synthesis, and a cleaning gas.

The deposit gas is a gas that deposits an etching-resistant polymer layer.

The building block for organic synthesis refers to a material that can be a precursor for a compound having a highly reactive skeleton. For example, when cyclobutane containing a fluorine atom represented by general formula (1) of the present disclosure and a composition containing it are reacted with a fluorinated organosilicon compound such as CF ₃ Si(CH ₃ ) ₃ , CF ₃ It is possible to convert it into a substance that can be a detergent or a fluorinated pharmaceutical intermediate by introducing a fluoroalkyl group such as a group.

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

The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited in any way to these examples.

Example

In the method for producing cyclobutane containing a fluorine atom in the examples, the raw material compound was cyclobutene represented by general formula (2), and X ¹ , X ² , X ³ and X ⁴ were fluorine atoms.

According to the reaction formula below, an addition reaction with hydrogen fluoride was performed on cyclobutene.

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

Example 1(1-1~1-5), catalyst: activated carbon

A SUS pipe (outer diameter: 1/2 inch) was used as a reaction tube, and 10 g of activated carbon was charged as a catalyst. The catalyst was used for addition reaction with hydrogen fluoride. The BET specific surface area of activated carbon was 850 m ² /g. 10 g of activated carbon was added as a catalyst to the SUS pipe (outer diameter: 1/2 inch) as a reactor.

After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure is adjusted to normal pressure so that the contact time (W/F ₀ ) between cyclobutene cC ₄ F ₆ (raw material compound) and activated carbon (catalyst) is 2.0 g·sec/cc, The raw material compound (cC ₄ F ₆ ) was distributed in the reactor.

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

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

The addition reaction with hydrogen fluoride was initiated by heating the reactor at 150°C, 200°C, 250°C, or 300°C. One hour after the start of the addition reaction with hydrogen fluoride, the effluent that passed through the removal tower 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. ) was used to analyze the structure using NMR spectra.

From the results of mass spectrometry and structural analysis, it was confirmed that cC ₄ F ₇ H was produced as the target compound. In Example 1-1, the conversion rate 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%.

In Example 1-2, conversion rate: 11.6 mol% and selectivity: 96.2 mol%.

In Example 1-3, conversion rate: 4.57 mol% and selectivity: 84.9 mol%.

In Example 1-4, conversion rate: 2.30 mol% and selectivity: 38.8 mol%.

In Example 1-5, conversion rate: 0.6 mol% and selectivity: 94.2 mol%.

Example 2(2-1~2-8), catalyst: chromium catalyst

A SUS pipe (outer diameter: 1/2 inch) was used as a reaction tube, and 10 g of chromium oxide containing Cr ₂ O ₃ as a main component was charged as a catalyst. As a pretreatment for using the catalyst in a desorption reaction (dehydrogen fluoride reaction), anhydrous hydrogen fluoride was passed through the reactor, and the temperature of the reactor was set to 200°C to 300°C to perform fluorination treatment. Fluorinated chromium oxide was taken out and used for dehydrogenation reaction. The BET specific surface area of fluorinated chromium oxide was 75 m ² /g. 10 g of fluorinated chromium oxide (fluorinated chromium oxide) was added as a catalyst to the SUS pipe (outer diameter: 1/2 inch) as a reactor.

After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure was adjusted to normal pressure, and the contact time (W/F ₀ ) between cyclobutene cC ₄ F ₆ (raw material compound) and fluorinated chromium oxide (catalyst) was 3.0 g·sec/cc. , the raw material compound (cC ₄ F ₆ H ₂ ) was distributed in the reactor so that the concentration was 4.0 g·sec/cc or 5.0 g·sec/cc.

The supply amount of hydrogen fluoride was 1 mole, 5 mole, or 20 mole per 1 mole of cyclobutene cC ₄ F ₆ (raw material compound).

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

The addition reaction with hydrogen fluoride was initiated by heating the reactor at 50°C, 200°C, 250°C, 300°C, or 350°C. One hour after the start of the addition reaction with hydrogen fluoride, the effluent that passed through the removal tower 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. ) was used to analyze the structure using NMR spectra.

From the results of mass spectrometry and structural analysis, it was confirmed that cC ₄ F ₇ H was produced as the target compound. In Example 2-1, the conversion rate 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%.

In Example 2-2, conversion rate: 0.183 mol% and selectivity: 1.6 mol%.

In Example 2-3, conversion rate: 0.506 mol% and selectivity: 2.4 mol%.

In Example 2-4, conversion rate: 0.396 mol% and selectivity: 0.7 mol%.

In Example 2-5, conversion rate: 0.924 mol% and selectivity: 4.2 mol%.

In Example 2-6, conversion rate: 1.37 mol% and selectivity: 3.0 mol%.

In Example 2-7, conversion rate: 1.62 mol% and selectivity: 2.0 mol%.

In Example 2-8, conversion rate: 2.87 mol% and selectivity: 0.2 mol%.

Comparative example 1 and 2

According to the experimental method of the above example, the reaction was performed by supplying hydrogen fluoride to cyclobutene cC ₄ F ₆ (raw material compound) without using a catalyst.

The supply amount of hydrogen fluoride was 20 moles per 1 mole of cyclobutene cC ₄ F ₆ (raw material compound).

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

The reactor was heated at 200°C or 350°C to initiate addition reaction with hydrogen fluoride. One hour after the start of the addition reaction with hydrogen fluoride, the effluent that passed through the removal tower 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. ) was used to analyze the structure using NMR spectra.

From the results of mass spectrometry 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 that of cC ₄ F ₇ H (target compound) Creation has not been confirmed.

The results of each example are shown in Table 1 below. In Table 1, the contact time (W/F ₀ ) indicates the speed at which the circulating raw material gas flows, that is, it means the time when the catalyst and the raw material gas are in contact. The molar ratio HF/cC ₄ F ₆ refers to the amount (mole) of HF used per mole of cC ₄ F ₆ .

Claims (5)

General formula (1):

(In the formula ^, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and
As a method for producing cyclobutane represented by,
General formula (2):

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are the same as above.)
A production method comprising the step of reacting cyclobutene and hydrogen fluoride represented by in the gas phase in the presence of a catalyst. In claim 1,
A production method in which 0.1 mole to 100 mole of hydrogen fluoride is supplied and reacted with respect to 1 mole of cyclobutene represented by the general formula (2). In claim 1 or claim 2,
A production method wherein the catalyst is at least one catalyst selected from the group consisting of activated carbon and chromium compounds. General formula (1):

(In ^the formula, X ¹ , X ^{2 ,} X ³ , X ⁴ ,
A composition containing cyclobutane represented by,
A composition in which the total amount of the composition is 100 mol% and the content of cyclobutane represented by the general formula (1) is 99 mol% or more. In claim 4,
Compositions used as cleaning gases, etching gases, deposit gases or building blocks for organic synthesis.