KR102566765B1 - Method for producing cyclobutene - Google Patents

Abstract

An object of the present disclosure is to produce cyclobutene containing a halogen atom with high selectivity.
Formula (1):

(In the formula, X ¹ , X ² , X ³ and X ⁴ are the same or different and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group. Y represents a halogen atom.)
As a method for producing cyclobutene represented by
General formula (2):

(In the formula, X ¹ , X ² , X ³ , X ⁴ and Y are as described above. X ⁵ and X ⁶ are the same or different and represent a hydrogen atom, a halogen atom or a perfluoroalkyl group.)
A manufacturing method comprising a step of subjecting the cyclobutane represented by to a desorption reaction, and performing the desorption reaction step in a gaseous phase.

Description

Method for producing cyclobutene

The present disclosure relates to a method for producing cyclobutene.

Cyclobutene 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.

Among cyclobutenes containing halogen atoms, a method for producing 1H-pentafluorocyclobutene from 1H,2H-hexafluorocyclobutane by dehydrofluorination reaction is known for 1H-pentafluorocyclobutene. (eg, Non-Patent Documents 1 and 2). In this technology, 1H-pentafluorocyclobutene is synthesized in an open reaction system using a glass apparatus.

Buxton; Tatlow; Journal of the Chemical Society; (1954); p. 1177-1179 Fuller, G.; Tatlow, J. C.; Journal of the Chemical Society; (1961); p. 3198-3203

An object of the present disclosure is to produce cyclobutene containing a halogen atom with high selectivity.

This indication includes the following structures.

Section 1.

Formula (1):

(In the formula, X ¹ , X ² , X ³ and X ⁴ are the same or different and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group. Y represents a halogen atom.)

As a method for producing cyclobutene represented by

Formula (2):

(In the formula, X ¹ , X ² , X ³ , X ⁴ and Y are as described above. X ⁵ and X ⁶ are the same or different and represent a hydrogen atom, a halogen atom or a perfluoroalkyl group.)

Including a step of desorbing the cyclobutane represented by

A manufacturing method in which the step of causing the desorption reaction is performed in a gaseous phase.

clause 2.

The production method according to item 1, wherein the X ⁵ is a hydrogen atom, the X ⁶ is a halogen atom, and the desorption reaction is a dehydrohalogenation reaction.

clause 3.

Formula (1):

(In the formula, X ¹ , X ² , X ³ and X ⁴ are the same or different and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group. Y represents a halogen atom.)

A composition containing cyclobutene represented by

A composition in which the content of the cyclobutene represented by the general formula (1) is 95 mol% or more, with the total amount of the composition as 100 mol%.

clause 4.

Item 3 above, wherein the content of 1H-perfluorocyclobutene (1H-cC ₄ F ₅ H) is 99 mol% or more and the content of 3H-perfluorocyclobutene (3H-cC ₄ F ₅ H) is 1 mol% or less. The composition described in.

Section 5.

The composition according to item 3 or 4, which is used as a cleaning gas, etching gas, deposit gas or building block for organic synthesis.

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

As a result of intensive research, the inventors of the present invention have found that cyclobutene containing a halogen atom represented by the general formula (1) can be produced with a high selectivity by performing the step of subjecting the raw material compound to a desorption reaction in the gas phase. .

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

This indication includes the following embodiment.

General formula (1) of the present disclosure:

(In the formula, X ¹ , X ² , X ³ and X ⁴ are the same or different and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group. Y represents a halogen atom.)

The method for producing cyclobutene represented by

Formula (2):

(In the formula, X ¹ , X ² , X ³ , X ⁴ and Y are as described above. X ⁵ and X ⁶ are the same or different and represent a hydrogen atom, a halogen atom or a perfluoroalkyl group.)

It includes a step of subjecting the cyclobutane represented by to a desorption reaction.

In the present disclosure, the desorption reaction step is performed in a gaseous phase.

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

In the present disclosure, "selectivity" means the target compound (halogen It means the ratio (mol%) of the total molar amount of cyclobutene containing atoms).

In the present disclosure, "conversion rate" refers to compounds other than the raw material compound contained in the effluent gas from the outlet of the reactor (containing a halogen atom) relative to the molar amount of the raw material compound (cyclobutane containing a halogen atom) supplied to the reactor. Cyclobutene, etc.) means the ratio (mol%) of the total molar amount.

In addition, since the method for producing cyclobutene of the present disclosure is not a batch reaction but a gas phase reaction in a distribution system, there is no need to use a solvent and there is an advantage that industrial waste is not generated.

(1) raw material compound

In the present disclosure, the raw material compound is General Formula (2):

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are the same or different and represent a hydrogen atom, a halogen atom or a perfluoroalkyl group. Y represents a halogen atom. )

It is cyclobutane represented by

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

Y represents a halogen atom.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , The halogen atom of X ⁶ and Y includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The perfluoroalkyl group of X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ is an alkyl group in which all hydrogen atoms are substituted with fluorine atoms. The perfluoroalkyl group has, for example, 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and 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. As the perfluoroalkyl group, a trifluoromethyl group (CF ₃ -) and a pentafluoroethyl group (C ₂ F ₅ -) are preferable.

As a cyclobutane containing a halogen atom represented by the general formula (2) as a raw material compound, since cyclobutene containing a halogen atom can be produced with high selectivity, X ¹ , X ² , X ³ and X ⁴ are , identical or different, represents a hydrogen atom, a halogen atom, or a perfluoroalkyl group, X ⁵ is a hydrogen atom, It is more preferable that X ⁶ is a fluorine atom and Y is a fluorine atom.

As cyclobutane represented by general formula (2) which is a raw material compound, for example,

Compounds, such as these, are mentioned.

Cyclobutane represented by these general formula (2) may be used independently or may be used in combination of 2 or more types. Commercially available products can be employed as such cyclobutane.

In the cyclobutane containing a halogen atom represented by the general formula (2), since cyclobutene containing a halogen atom can be produced with a high selectivity, X ¹ , X ² , X ³ , X ⁴ and X ⁶ are , a fluorine atom, X ⁵ is a hydrogen atom, and Y is more preferably a fluorine atom.

(2) tally reaction

In the step of making the desorption reaction in the present disclosure, the desorption reaction is performed in a gaseous phase. In the step of causing the desorption reaction in the present disclosure, it is carried out in a gas phase, and it is particularly preferable to carry out in a gas phase continuous flow type using a fixed bed reactor. In the case of carrying out in a gaseous phase continuous flow type, while being able to simplify equipment, operation, etc., it is economically advantageous.

In the step of causing the desorption reaction in the present disclosure, it is preferable that the X ⁵ is a hydrogen atom, the X ⁶ is a halogen atom, and the desorption reaction is a dehydrogenation reaction. In the step of causing the desorption reaction in the present disclosure, it is preferable that the X ⁵ is a hydrogen atom, the X ⁶ is a fluorine atom, and the desorption reaction is a dehydrofluorination reaction.

For example, in cyclobutane containing a halogen atom represented by general formula (2) as a raw material compound, X ¹ , X ² , X ³ , X ⁴ and X ⁶ are fluorine atoms, and X ⁵ is a hydrogen atom And, Y is preferably a fluorine atom.

According to the following reaction formula, the desorption reaction is preferably a dehydrofluorination reaction.

catalyst

In the step of causing the desorption reaction in the present disclosure, it is preferable to perform the desorption reaction in the presence of a catalyst and in a gas phase.

It is preferable that the catalyst used in this process is activated carbon. It is preferable that the catalyst used in this process is a metal catalyst. As the metal catalyst, chromium oxide, chromium fluoride oxide, chromium fluoride, aluminum oxide, aluminum oxide fluoride, aluminum fluoride, iron oxide, iron oxide fluoride, iron fluoride, nickel oxide, nickel fluoride oxide, nickel fluoride, magnesium oxide, magnesium oxide fluoride and fluoride It is preferable that it is at least 1 sort(s) selected from the group which consists of magnesium.

Among these catalysts, activated carbon, chromium oxide, chromium oxide fluoride, aluminum oxide, and aluminum oxide fluoride are more preferable in that the target compound can be obtained with a higher selectivity. Moreover, it is also possible to further improve the conversion rate of the raw material compound.

In this step, in contacting the raw material compound and the catalyst in the gaseous phase, it is preferable to bring the catalyst into contact with the raw material compound in a solid state (solid phase).

In this step, the catalyst may be in the form of a powder, but a pellet form is preferable for the gaseous phase continuous flow type reaction.

The specific surface area of the catalyst measured by the BET method (hereinafter also referred to as BET specific surface area) is usually 10 to 3,000 m ² /g, preferably 10 to 400 m ² /g, and more preferably 20 to 3,000 m 2 /g. It is 375 m ² /g, more preferably 30 to 350 m ² /g. When the BET specific surface area of the catalyst is within this range, the target compound can be obtained with high selectivity because the density of catalyst particles is not too small. Moreover, it is also possible to improve the conversion rate of a raw material compound.

When using activated carbon as a catalyst, it is preferable to use powdered activated carbon such as crushed coal, briquette coal, granular coal, or spherical coal. As the powdered activated carbon, it is preferable to use powdered activated carbon showing a particle size of 4 mesh (4.76 mm) to 100 mesh (0.149 mm) according to the JIS test.

When a metal catalyst is used as the 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 chromium oxide, for example, when chromium oxide is represented by Cr ₂ O ₃ ·nH ₂ O, the value of n is preferably 3 or less, and more preferably 1 to 1.5. In the chromium oxide, in the composition formula: CrO _m , it is preferable that m is usually in the range of 1.5 < m < 3. As a catalyst, fluorinated chromium oxide can be prepared by fluorinating chromium oxide. As fluorination, fluorination with hydrogen fluoride (HF), fluorination with fluorocarbon, etc. are mentioned.

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

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

tally reaction temperature

In the step of causing the desorption reaction in the present disclosure, the lower limit of the reaction temperature is usually 50° C. , preferably 200°C, more preferably 250°C, still more preferably 300°C, and particularly preferably 350°C.

The upper limit of the reaction temperature in the desorption reaction is from the viewpoint of allowing the dehydrofluorination reaction to proceed more efficiently and obtaining the target compound with a higher selectivity, and also to suppress the decrease in selectivity due to decomposition or polymerization of the reaction product. From the viewpoint, it is usually 500°C, preferably 450°C, and more preferably 400°C.

tally reaction time

The reaction time of the desorption reaction is determined by lengthening 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 compound (cc/sec)] It is possible to increase the conversion rate, but the amount of catalyst increases and the equipment becomes large, which is inefficient.

_Therefore , the reaction time of the dehydrofluorination reaction is 5 g·sec/ It is preferably cc to 300 g sec/cc, more preferably 10 g sec/cc to 200 g sec/cc, still more preferably 15 g sec/cc to 150 g sec/cc, and 20 g sec/cc to It is particularly preferable that it is cc - 100 g·sec/cc.

The contact time of the raw material compound with the catalyst means the contact time between the raw material compound and the catalyst.

In the desorption reaction in the present disclosure, the target compound can be obtained with a higher selectivity by appropriately adjusting the reaction temperature and reaction time (contact time) in accordance with the catalyst, especially when carried out in the presence of a catalyst in a gaseous phase.

When using chromium oxide as a catalyst, the reaction temperature is preferably 300°C or higher, more preferably 350°C or higher. Further, the contact time is preferably 10 g·sec/cc or more, more preferably 20 g·sec/cc or more, and still more preferably 40 g·sec/cc or more.

When using alumina as a catalyst, the reaction temperature is preferably 300°C or higher, and the contact time is preferably 5 g·sec/cc or higher.

When using activated carbon as a catalyst, the reaction temperature is preferably 300°C or higher, more preferably 350°C or higher, and still more preferably 400°C or higher. In addition, the contact time is preferably 5 g·sec/cc to 55 g·sec/cc, more preferably 5 g·sec/cc to 50 g·sec/cc, and 5 g·sec/cc to 40 g·sec/cc. it is more preferable

tally reaction pressure

The reaction pressure of the desorption reaction is preferably -0.05 MPa to 2 MPa, more preferably -0.01 MPa to 1 MPa, and even more preferably normal pressure to 0.5 MPa from the viewpoint of advancing the desorption reaction more efficiently. In addition, in this indication, when there is no indication about pressure, it is set as gauge pressure.

In the desorption reaction, the reactor in which the raw material compound and the catalyst (such as a metal catalyst) are contacted and reacted is not particularly limited in shape and structure as long as it can withstand the above temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a tubular reactor. As a material of a reactor, glass, stainless steel, iron, nickel, an iron-nickel alloy etc. are mentioned, for example.

tally Examples of Reactions

The desorption reaction can be carried out by either a flow-through method or a batch method in which a raw material compound is continuously injected into a reactor and a target compound is continuously extracted from the reactor. When the target compound stays in the reactor, the desorption reaction can proceed further, and therefore, it is preferable to carry out the flow-through method. In the step of causing the desorption reaction in the present disclosure, it is carried out in a gas phase, and it is particularly preferable to carry out in a gas phase continuous flow type using a fixed bed reactor. In the case of carrying out in a gaseous phase continuous flow type, while being able to simplify equipment, operation, etc., it is economically advantageous.

About the atmosphere at the time of carrying out a desorption reaction, it is preferable that it is in the presence of an inert gas and/or the presence of hydrogen fluoride from the point of suppressing deterioration of a catalyst (metal catalyst etc.). It is preferable that the said inert gas is at least 1 sort(s) selected from the group which consists of nitrogen, helium, argon, and carbon dioxide. Among these inert gases, nitrogen is more preferable from the viewpoint of cost reduction. The concentration of the inert gas is preferably 0 to 50 mol% of the gas components introduced into the reactor.

After completion of the elimination reaction, if necessary, a purification treatment is performed according to a conventional method to obtain cyclobutene containing a halogen atom represented by the general formula (1).

(3) target compound

The target compound in the present disclosure is General Formula (1):

(In the formula, X ¹ , X ² , X ³ and X ⁴ are the same or different and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group. Y represents a halogen atom.)

It is a cyclobutene containing a halogen atom represented by

X ¹ , X ² , X ³ and X ⁴ , and Y are as described above.

Cyclobutene represented by the general formula (1) to be produced is, for example, the following

Compounds, such as these, are mentioned.

In the cyclobutene containing a halogen atom represented by General Formula (1), X ¹ , X ² , X ³ and X ⁴ are the same or different and represent a hydrogen atom, a halogen atom or a perfluoroalkyl group, and Y is preferably a fluorine atom. In the cyclobutene containing a halogen atom represented by General Formula (1), X ¹ , X ² , X ³ and X ⁴ are fluorine atoms, and it is more preferable that Y is a fluorine atom.

In the method for producing cyclobutene containing a halogen atom in the present disclosure, the raw material compound is cyclobutane containing a halogen atom represented by the general formula (2), X ¹ , X ² , X ³ , X ⁴ and It is preferable that X ⁶ is a fluorine atom, X ⁵ is a hydrogen atom, and Y is a desorption reaction in the case of a fluorine atom.

According to the following reaction formula, the desorption reaction is preferably a dehydrofluorination reaction.

The target compound is a cyclobutene containing a halogen atom represented by the general formula (1), X ¹ , X ² , X ³ and X ⁴ are fluorine atoms, and Y is preferably a fluorine atom.

(4) containing a halogen atom cyclobutene composition comprising

As described above, cyclobutene containing a halogen atom represented by the general formula (1) can be obtained, but as described above, cyclobutene containing a halogen atom represented by the general formula (1) and ) may be obtained in the form of a composition containing cyclobutane containing a halogen atom represented by

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

In the composition containing cyclobutene containing a halogen atom represented by the general formula (1) of the present disclosure, the total amount of the composition is 100 mol%, cyclobutene containing a halogen atom represented by the general formula (1) It is preferable that it is 95 mol% or more, and, as for content, it is more preferable that it is 99 mol% or more.

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

In the method for producing cyclobutene containing a halogen atom according to the present disclosure, the following compounds may be produced as impurities in the elimination reaction.

In the composition containing cyclobutene containing a halogen atom represented by the general formula (1) of the present disclosure, the total amount of the composition is 100 mol%, and 1H-perfluorocyclobutene (1H-cC ₄ F ₅ H ) is 99 mol% or more, and the content of 3H-perfluorocyclobutene (3H-cC ₄ F ₅ H) is preferably 1 mol% or less.

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

The composition containing cyclobutene containing a halogen atom represented by the general formula (1) of the present disclosure is similar to the case of cyclobutene alone containing a halogen atom represented by the general formula (1), such as semiconductors and liquid crystals. In addition to etching gas for forming the most advanced microstructure, it can be effectively used for various purposes such as deposit gas, building block for organic synthesis, and cleaning gas.

The deposit gas is a gas for depositing an etching resistant polymer layer.

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

As mentioned above, although embodiment of this indication was described, various changes of a form and detail are possible, without deviating from the meaning and range of a claim.

Example

Examples are given below to specifically describe the present disclosure, but the present disclosure is not limited at all by these examples.

Example

In the method for producing cyclobutene containing a halogen atom of the examples, the raw material compound is X ¹ , X ² , X ³ , X ⁴ and X ⁶ in the cyclobutane containing a halogen atom represented by the general formula (2) is a fluorine atom, X ⁵ is a hydrogen atom, and Y is a fluorine atom.

According to the following reaction formula, the desorption reaction was a dehydrofluorination reaction.

In the target compound, X ¹ , X ² , X ³ and X ⁴ are fluorine atoms, and Y is a fluorine atom in cyclobutene containing a halogen atom represented by Formula (1).

In addition, in the elimination reaction, the following compounds may be produced as impurities.

Example 1 to 3 (chromium oxide 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 filled as a catalyst. As a pretreatment for using the catalyst for a desorption reaction (dehydrofluorination reaction), anhydrous hydrogen fluoride was passed through the reactor, and the temperature of the reactor was set at 200°C to 300°C to perform fluorination treatment. The fluorinated chromium oxide was taken out and used for the dehydrofluorination reaction. The BET specific surface area of the fluorinated chromium oxide was 75 m ² /g.

10 g of fluorinated chromium oxide (chromium fluoride oxide) was added as a catalyst to a SUS pipe (outer diameter: 1/2 inch) serving as a reactor. After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure is reduced to normal pressure, and the contact time (W/F ₀ ) between cC ₄ F ₆ H ₂ (raw material compound) and fluorinated chromium oxide (catalyst) is 20 g·sec/cc or The raw material compound (cC ₄ F ₆ H ₂ ) was passed through the reactor so as to be 40 g·sec/cc.

The reaction was carried out in a gas phase continuous flow mode.

The dehydrofluorination reaction was initiated by heating the reactor at 250 °C or 350 °C.

One hour after the start of the defluorination reaction, the effluent that passed through the decontamination tower was collected.

Then, mass spectrometry was performed by gas chromatography/mass spectrometry (GC/MS) using gas chromatography (manufactured by Shimadzu Corporation, trade name "GC-2014"), and NMR (manufactured by JEOL Corporation, trade name "400YH"). ) was used to analyze the structure by NMR spectrum.

From the results of mass spectrometry and structural analysis, it was confirmed that cC ₄ F ₅ H was produced as the target compound. In Example 1, the conversion rate from cC ₄ F ₆ H ₂ (raw compound) was 3.34 mol%, and the selectivity (yield) of cC ₄ F ₅ H (target compound) was 45.9 mol%. In Example 2, conversion rate: 29.1 mol% and selectivity: 98.6 mol%. In Example 3, conversion rate: 26.1 mol% and selectivity: 97.2 mol%.

Example 4 and 5 (alumina catalyst)

According to the experimental method of Example 1, alumina containing Al ₂ O ₃ as a main component was used as a catalyst. According to the experimental method of Example 1, the contact time (W/F ₀ ) of cC ₄ F ₆ H ₂ (raw material compound) and alumina (catalyst) is 10 g·sec/cc or 40 g·sec/cc, The raw material compound was distributed to Following the experimental method of Example 1 above, the dehydrofluorination reaction was initiated by heating the reactor at 400°C. Dehydrofluorination reaction, mass spectrometry, and structural analysis were performed in the same manner as in Example 1 except for the above conditions.

From the results of mass spectrometry and structural analysis, it was confirmed that cC ₄ F ₅ H was produced as the target compound. In Example 4, the conversion rate from cC ₄ F ₆ H ₂ (raw compound) was 7.92 mol%, and the selectivity of cC ₄ F ₅ H (target compound) was 45.1 mol%. In Example 5, conversion rate: 4.11 mol% and selectivity: 35.0 mol%.

Example 6 to 10 (activated carbon catalyst)

Following the experimental method of Example 1 above, activated carbon was used as a catalyst. According to the experimental method of Example 1, the contact time (W/F ₀ ) of cC ₄ F ₆ H ₂ (raw material compound) and activated carbon (catalyst) was 10 g·sec/cc, 27 g·sec/cc or 47 g·sec The raw material compound was passed through the reactor so as to be /cc. Following the experimental method of Example 1 above, the dehydrofluorination reaction was initiated by heating the reactor at 300 °C, 350 °C or 400 °C. Dehydrofluorination reaction, mass spectrometry, and structural analysis were performed in the same manner as in Example 1 except for the above conditions.

From the results of mass spectrometry and structural analysis, it was confirmed that cC ₄ F ₅ H was produced as the target compound. In Example 6, the conversion rate from cC ₄ F ₆ H ₂ (raw compound) was 57.6 mol%, and the selectivity of cC ₄ F ₅ H (target compound) was 95.3 mol%. In Example 7, conversion rate: 97.7 mol% and selectivity: 68.3 mol%. In Example 8, conversion rate: 84.1 mol% and selectivity: 83.8 mol%. In Example 9, conversion rate: 72.3 mol% and selectivity: 94.6 mol%. In Example 10, conversion rate: 84.7 mol% and selectivity: 95.7 mol%.

The results of each Example are shown in Table 1 below. In Table 1, the contact time (W/F ₀ ) means at what speed the flowing source gas flows, that is, the contact time between the catalyst and the source gas.

Claims (5)

Formula (1):

(In the formula, X ¹ , X ² , X ³ and X ⁴ are the same or different and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group. Y represents a halogen atom.)
As a method for producing cyclobutene represented by
Formula (2):

(In the formula, X ¹ , X ² , X ³ , X ⁴ and Y are as described above. X ⁵ and X ⁶ are the same or different and represent a hydrogen atom, a halogen atom or a perfluoroalkyl group.)
Including a step of desorbing the cyclobutane represented by
A manufacturing method in which the step of causing the desorption reaction is performed in a gaseous phase. The method of claim 1,
The X ⁵ is a hydrogen atom, the X ⁶ is a halogen atom, and the desorption reaction is a dehydrohalogenation reaction. delete delete delete