KR20210113300A - Process for the preparation of cyclobutane - Google Patents

Abstract

(식 중, X¹, X², X³, X⁴, X⁵ 및 X⁶은, 동일 또는 상이하고, 수소 원자, 할로겐 원자, 또는 퍼플루오로알킬기를 나타낸다.)
로 표시되는 시클로부탄의 제조 방법으로서,
일반식 (2)：

(식 중, X¹, X², X³, X⁴, X⁵ 및 X⁶은, 상기와 같다.)
로 표시되는 시클로부텐과 불화수소를, 촉매의 존재 하에, 기상에서 반응시키는 공정을 포함하는, 제조 방법. An object of the present disclosure is 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 X ⁶ are the same or different and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group.)
As a method for producing cyclobutane represented by
General formula (2):

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

Description

Process for the preparation of cyclobutane

The present disclosure relates to a method for preparing cyclobutane.

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

In Non-Patent Document 1, 1H is obtained from 3,3,4,4,-tetrafluorocyclobutene by fluorination using a fluorine agent such as _{CoF 3 , MnF 3} , AgF _{2 , CeF 4} or KCoF _{4 .} - Disclosed is a process for preparing heptafluorocyclobutane.

In Non-Patent Document 2, a hexafluoro-cyclobutene (cC ₄ F ₆₎ from using a hydrogen bromide (HBr),, 1Br, cyclobutane (cC ₄ F ₆ BrH) in 2H- hexafluoro by addition reaction with 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”

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

This indication includes the following structures.

Section 1.

General formula (1):

(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.)

As a method for producing cyclobutane represented by

General formula (2):

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

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

Section 2.

The production method according to Item 1, wherein 0.1 to 100 moles of hydrogen fluoride is supplied and reacted with respect to 1 mole of cyclobutene represented by the general formula (2).

Section 3.

The 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 a chromium compound.

Section 4.

General formula (1):

(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.)

As a composition containing cyclobutane represented by

The composition, wherein the total amount of the composition is 100 mol%, and the content of the cyclobutane represented by the general formula (1) is 99 mol% or more.

Section 5.

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

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

As a result of intensive research, the present inventors have conducted an addition reaction of a raw material compound with hydrogen fluoride in the presence of a catalyst to react in the gas phase, whereby a cyclo containing a fluorine atom represented by the above general formula (1) It has been found that butane can be prepared with high selectivity.

The present disclosure has been completed as a result of further researches based on such knowledge.

The present 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 X ⁶ are the same or different and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group.)

The method for producing cyclobutane represented by

General formula (2):

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

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

In the present disclosure, the reaction is an addition reaction with hydrogen fluoride, and the step is reacted 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 a high selectivity.

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

In the present disclosure, "conversion rate" refers to the amount of compounds other than the raw material compound (cyclobutane containing fluorine atom, etc.) contained in the effluent gas from the reactor outlet relative 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 an 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 an 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 compound

Cyclobutene represented by the 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 X ⁶ are the same or different and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group.)

cyclobutene represented by , and hydrogen fluoride.

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.

Examples ^{of the halogen atom of X 1} , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an 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 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, 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 the cyclobutene represented by the general formula (2) as a raw material compound, since cyclobutane containing a fluorine atom can be produced with high selectivity, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ Silver is the same or different, and it is more preferable that they are a fluorine atom or a perfluoroalkyl group.

As the cyclobutene represented by the general formula (2) as the raw material compound, for example,

compounds, such as these are mentioned.

Cyclobutene represented by these general formula (2) may be used independently and may be used in combination of 2 or more type. As such cyclobutene, a well-known or a commercial item can be employ|adopted.

^{In the cyclobutene represented by the general formula (2), X 1} , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are fluorine from the viewpoint that cyclobutane containing a fluorine atom can be produced with high selectivity. It is more preferable that it is an atom.

cyclobutene and hydrogen fluoride molar ratio

It is preferable that hydrogen fluoride (HF) is normally supplied to a reactor in a gaseous state together with the cyclobutene (raw material compound) represented by General formula (2). It is preferable to make the hydrogen fluoride supply amount react in about 0.1 mol - 100 mol with respect to 1 mol of cyclobutene (raw material compound) represented by the said General formula (2). The amount of hydrogen fluoride supplied is more preferably about 0.5 mol to about 50 mol, still more preferably about 1 mol to about 30 mol, and 1 mol with respect to 1 mol of the cyclobutene (raw material compound) represented by the general formula (2). About 20 moles are particularly preferred. By setting the supply amount of hydrogen fluoride within the above range, the addition reaction by hydrogen fluoride can proceed favorably, the generation of impurities can be reduced, and the selectivity of cyclobutane containing fluorine atoms in the product is high and can be recovered in high yield. can

(2) addition reaction

The step of reacting cyclobutene with hydrogen fluoride in the present disclosure is an addition reaction with hydrogen fluoride, and is performed in the gas phase in the presence of a catalyst. In the step (addition reaction) of reacting cyclobutene with hydrogen fluoride in the present disclosure, it is preferably carried out in a gas phase, and particularly preferably carried out by a gas phase continuous flow type using a fixed bed reactor. When carrying out by a gas phase continuous flow type, while being able to simplify an apparatus, operation, etc., it is economically advantageous.

In the step of reacting cyclobutene with hydrogen fluoride in the present disclosure, for example, in the cyclobutene represented by the general formula (2) as a raw material compound, X ¹ , X ² , X ³ , X ⁴ and X ⁶ It is more preferable that silver is a fluorine atom.

According to the following reaction formula, it is preferable that it is an addition reaction by hydrogen fluoride.

catalyst

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

It is preferable that the catalyst used in this process is activated carbon.

It is preferable that the catalyst used at this process is a metal catalyst. Examples of the metal catalyst include chromium catalysts such as chromium oxide, chromium fluoride oxide and chromium fluoride, aluminum catalysts such as aluminum oxide, aluminum fluoride oxide, and aluminum fluoride, iron catalysts such as iron oxide, iron fluoride oxide and iron fluoride, nickel oxide, nickel fluoride oxide It is preferable that they are metal catalysts, such as nickel catalysts, such as nickel fluoride, and magnesium catalyst, such as magnesium oxide, magnesium fluoride oxide, and magnesium fluoride. It is preferable that a catalyst is at least 1 sort(s) chosen from the group which consists of the said metal catalyst.

It is preferable that the catalyst used in this process is at least 1 sort(s) chosen from the group which consists of activated carbon and the said metal catalyst. Among these catalysts, chromium catalysts such as activated carbon, chromium oxide, chromium fluoride and chromium fluoride are more preferable from the viewpoint that the target compound can be obtained with a higher selectivity. Moreover, it is also possible to further improve the conversion ratio of a raw material compound.

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

In this process, although powdery form may be sufficient as a catalyst, it is preferable for a gaseous-phase continuous flow-type reaction that it is pellet form.

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 ~2,000 m ² /g, more preferably 30 ~ 1,500 m ² /g. When the BET specific surface area of the catalyst is in such a range, the target compound can be obtained with high selectivity because the particle density of the catalyst is not too small. Moreover, it is also possible to improve the conversion ratio of a raw material compound. For example, as the catalyst, it is preferable to use activated carbon having 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 coal, coal briquettes, granular coal, and spheroidal coal. As the powdered activated carbon, it is preferable to use powdered activated carbon having a particle size of 4 mesh (4.76 mm) to 100 mesh (0.149 mm) in the JIS test. When activated carbon is used as a catalyst, it can be used (heat-treated activated carbon) treated by flowing nitrogen for a certain period of time under a temperature condition of, for example, 300 to 500°C before use.

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

As an example of the catalyst in this indication, chromium oxide and fluorinated chromium oxide are demonstrated. Chromium oxide, for example, in the case shown a chromium oxide as _{Cr 2 O 3 · nH 2 O} , and preferably the value of n greater than 3, more preferably from 1 to 1.5. Further, the chromium oxide has a composition formula: according to CrO _m, m is preferably in the range of usually 1.5 <m <3. As a catalyst, fluorinated chromium oxide can be prepared by fluorinating chromium oxide. As fluorination, fluorination by hydrogen fluoride (HF), fluorination by fluorocarbon, etc. are mentioned.

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 fluorination of chromium oxide with hydrogen fluoride (HF treatment). As for the temperature of fluorination, 100-460 degreeC is preferable, for example. The pressure of the fluorination is preferably a pressure applied to the catalytic reaction. In the present disclosure, it is particularly preferable 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 period of time.

It is preferable that fluorine content is 30 mass % or more, and, as for the highly fluorinated-chromium oxide catalyst, it is more preferable that it is 30-45 mass %. The fluorine content can be measured by a change in the mass of the catalyst or a general quantitative analysis 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 a viewpoint that the addition reaction with hydrogen fluoride can proceed more efficiently and the target compound can be obtained with a higher selectivity, a decrease in the conversion rate From a viewpoint of suppressing , it is normally 50 degreeC, Preferably it is 200 degreeC, More preferably, it is 250 degreeC, More preferably, it is 300 degreeC.

When using activated carbon as a catalyst, 50 degreeC - 400 degreeC are preferable, as for reaction temperature, 100 degreeC - 350 degreeC are more preferable, and 150 degreeC - 300 degreeC are still more preferable.

When using a chromium catalyst as a catalyst, 50 degreeC or more is preferable, as for reaction temperature, 250 degreeC or more is more preferable, and 300 degreeC or more is still more preferable.

The upper limit of the reaction temperature for reacting cyclobutene with hydrogen fluoride is from the viewpoint of more efficiently advancing the addition reaction with hydrogen fluoride to obtain the target compound with a higher selectivity, and the selectivity due to decomposition or polymerization of the reaction product From a viewpoint of suppressing the fall of this, it is 500 degreeC normally, Preferably it is 450 degreeC, More preferably, it is 400 degreeC.

weather reaction time

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

_{Therefore, the reaction time for reacting cyclobutene with hydrogen fluoride is 1 g of the contact time (W/F 0} ) of the raw material compound to the catalyst from the viewpoint of improving the conversion rate of the raw material compound and suppressing the equipment cost. · It is preferable that it is sec/cc - 30 g · sec/cc, It is more preferable that it is 1.5 g · sec/cc - 10 g · sec/cc, It is still more preferable that it is 2.0 g · sec/cc - 5.0 g · sec/cc do.

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

cyclobutene and hydrogen fluoride molar ratio

The supply amount of hydrogen fluoride is 0.1 mol to 100 mol per 1 mol of the cyclobutene (raw material compound) represented by the general formula (2) from the viewpoint of reaction cost and productivity when activated carbon and a chromium catalyst are used as catalysts. It is preferable to make it react to such an extent, 0.5 mol - about 75 mol are more preferable, and 1 mol - about 50 mol are still more preferable.

gas phase reaction pressure

The reaction pressure for reacting cyclobutene with hydrogen fluoride is preferably -0.05 MPa to 2 MPa, more preferably -0.01 MPa to 1 MPa, from the viewpoint of more efficiently advancing the addition reaction with hydrogen fluoride, atmospheric pressure It is more preferable that it is 0.5 MPa. In addition, in this indication, when there is no indication about a pressure, let it be a gauge pressure.

In the reaction of cyclobutene and hydrogen fluoride, the reactor in which the raw material compound and the catalyst (activated carbon, chromium catalyst, etc.) are brought into contact 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 shell-and-tube reactor. As a material of a reactor, glass, stainless steel, iron, nickel, an iron-nickel alloy etc. are mentioned, for example.

Examples of gaseous reactions

The reaction between cyclobutene and hydrogen fluoride (addition reaction with hydrogen fluoride) can be carried out either by flow-through or batch-type methods in which the raw material compound is continuously injected into the reactor and the target compound is continuously extracted from the reactor. can When the target compound stays in the reactor, it is preferable to carry out the flow-through type from the viewpoint that the desorption reaction may proceed further. In the step of reacting cyclobutene with hydrogen fluoride in the present disclosure, it is preferably carried out in a gas phase, and particularly preferably carried out in a gas phase continuous flow type using a fixed bed reactor. When carrying out by a gas phase continuous flow type, while being able to simplify an apparatus, operation, etc., it is economically advantageous.

The atmosphere for the reaction of cyclobutene with 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.). It is preferable that the said inert gas is at least 1 sort(s) chosen from the group which consists of nitrogen, helium, argon, and carbon dioxide. Among these inert gases, nitrogen is more preferable from the viewpoint of reducing cost. The concentration of the inert gas is preferably 0 to 50 mol% of the gas component introduced into the reactor.

After completion of the reaction between cyclobutene and hydrogen fluoride (addition reaction with hydrogen fluoride), if necessary, purification is performed according to a conventional method to obtain cyclobutane containing a fluorine atom represented by the 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 X ⁶ are the same or different and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group.)

It is a cyclobutane containing a fluorine atom represented by.

Cyclobutane containing a fluorine atom represented by the general formula (1) to be produced is, for example,

compounds, such as these are mentioned.

In the cyclobutane containing a fluorine atom represented by the general formula (1), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are the same or different, and are a hydrogen atom, a halogen atom, or perfluoro represents a roalkyl group.

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

According to the following reaction formula, it is preferable that it is an addition reaction by hydrogen fluoride.

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

According to the manufacturing method of this indication, the cyclobutane containing the fluorine atom represented by General formula (1) can be manufactured favorably with high selectivity at an industrial level as a target compound.

(4) a composition comprising cyclobutane containing a fluorine atom

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

As the cyclobutane containing a fluorine atom represented by the 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 a fluorine atom.}

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

In the composition containing the cyclobutane containing a fluorine atom represented by the general formula (1) of the present disclosure, the total amount of the composition is 100 mol%, and the cyclobutane containing the fluorine atom represented by the general formula (1) 1 mol% - 99.9 mol% are preferable, as for content of, 5 mol% - 99.9 mol% are more preferable, 10 mol% - 99.9 mol% are still more preferable.

According to the production method of the present disclosure, even when obtained as a composition containing a cyclobutane containing a fluorine atom represented by the general formula (1), the cyclobutane containing a fluorine atom represented by the general formula (1) is particularly high. It can be obtained by selectivity, and as a result, it is possible to reduce components other than the cyclobutane containing the fluorine atom represented by General formula (1) in the said composition. According to the manufacturing method of this indication, the effort of refinement|purification for obtaining the cyclobutane containing the 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 similar to the case of the cyclobutane containing the fluorine atom represented by the general formula (1) alone, such as semiconductors, liquid crystals, etc. In addition to the etching gas for forming the most advanced microstructure, 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 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 skeleton. For example, when cyclobutane containing a fluorine atom represented by the general formula (1) of the present disclosure and a composition containing the same are reacted with a fluorinated 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 scope of a claim.

Example

Hereinafter, although an Example is given and this indication is demonstrated concretely, this indication is not limited at all by these Examples.

Example

In the manufacturing method of the cyclobutane containing a fluorine atom in the Example, in the cyclobutene represented by General formula (2) as a raw material compound, X ¹ , X ² , X ³ and X ⁴ were a fluorine atom.

According to the following reaction formula, addition reaction with hydrogen fluoride was performed with respect to cyclobutene.

The target compound was cyclobutane containing a fluorine atom represented by the 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 filled as a catalyst. The catalyst was used for addition reaction with hydrogen fluoride. The BET specific surface area of the activated carbon was 850 m ² /g. 10 g of activated carbon was added as a catalyst to the SUS piping (outer diameter: 1/2 inch) which is a reactor.

In a nitrogen atmosphere, after drying at 200 ° C. for 2 hours, the pressure is adjusted to atmospheric pressure, _{and 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 passed through the reactor.

The supply amount of hydrogen fluoride was 1 mol or 15 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 method.

The reactor was heated at 150° C., 200° C., 250° C. or 300° C. to initiate the addition reaction with hydrogen fluoride. One hour after starting the addition reaction with hydrogen fluoride, the effluent that passed through the decontamination tower was collected.

Then, mass spectrometry is 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 for structural analysis by NMR spectrum.

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 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, it was conversion ratio: 11.6 mol%, and selectivity: 96.2 mol%.

In Example 1-3, it was a conversion ratio: 4.57 mol%, and a selectivity: 84.9 mol%.

In Example 1-4, it was conversion ratio: 2.30 mol%, and selectivity: 38.8 mol%.

In Example 1-5, it was a conversion ratio: 0.6 mol%, and a selectivity: 94.2 mol%.

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

A SUS pipe (outer diameter: 1/2 inch) was used as the 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 in which the catalyst is used for the desorption reaction (dehydrofluorination reaction), anhydrous hydrogen fluoride was passed through the reactor, and the temperature of the reactor was set to 200°C to 300°C, and the fluorination treatment was performed. The fluorinated chromium oxide was taken out and used for 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 for 2 hours at 200°C in a nitrogen atmosphere, the pressure was reduced to atmospheric pressure, _{and the contact time (W/F 0 ) of 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 flowed through the reactor so as to be 4.0 g·sec/cc or 5.0 g·sec/cc.

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 method.

The reactor was heated at 50° C., 200° C., 250° C., 300° C. or 350° C. to initiate the addition reaction with hydrogen fluoride. One hour after the start of the addition reaction with hydrogen fluoride, the effluent that passed through the detoxification tower was collected.

Then, mass spectrometry is 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 for structural analysis by NMR spectrum.

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 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, it was a conversion rate:0.183 mol%, and a selectivity: 1.6 mol%.

In Example 2-3, it was conversion ratio:0.506 mol%, and selectivity:2.4 mol%.

In Example 2-4, it was conversion ratio:0.396 mol%, and selectivity: 0.7 mol%.

In Example 2-5, it was conversion ratio:0.924 mol%, and selectivity:4.2 mol%.

In Example 2-6, it was conversion ratio: 1.37 mol%, and selectivity: 3.0 mol%.

In Example 2-7, it was conversion ratio:1.62 mol%, and selectivity: 2.0 mol%.

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

comparative example 1 and 2

According to the experimental method of the above example _{, hydrogen fluoride was supplied to cyclobutene cC 4} F ₆ (raw material compound) without using a catalyst, and the reaction was carried out.

The supply amount of hydrogen fluoride was set to 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 method.

The reactor was heated at 200°C or 350°C to initiate an addition reaction with hydrogen fluoride. One hour after the start of the addition reaction with hydrogen fluoride, the effluent that passed through the detoxification tower was collected.

Then, mass spectrometry is 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 for structural analysis by NMR spectrum.

From the results of mass spectrometry and structural analysis, _{the conversion rate from cC 4} F ₆ (raw compound) was 0.801 mol% (Comparative Example 1) or 0.695 mol% (Comparative Example 2), but cC ₄ F ₇ H (target compound) was Creation was not confirmed.

The results of each Example are shown in Table 1 below. In Table 1, the contact time (W/F ₀ ) represents the rate at which the flowing raw material gas flows, ie, the contact time between the catalyst and the raw material gas. The molar ratio HF/cC ₄ F ₆ is the amount (mol) of HF used with respect to 1 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 X ⁶ are the same or different and represent a hydrogen atom, a halogen atom, or a perfluoroalkyl group.)
As a method for producing cyclobutane represented by
General formula (2):

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

(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.)
As a composition containing cyclobutane represented by
The composition, wherein the total amount of the composition is 100 mol%, and the content of the cyclobutane represented by the general formula (1) is 99 mol% or more. 5. The method according to claim 4,
A composition for use as a cleaning gas, etching gas, deposit gas or building block for organic synthesis.