Method for producing halogenated alkene compounds and fluorinated alkyne compounds

Abstract

To produce a halogenated alkene compound and a halogenated alkyne compound at a high conversion rate and selectivity.SOLUTION: Any of the following methods (1) through (4) is employed: (1) a halogenated butane compound represented by CX1X2X3CHX4CFHCX5X6X7 (where X1, X2, X3, X4, X5, X6 and X7 are the same or different, and are halogen atoms) is subjected to a dehydrofluorination reaction; (2) a halogenated butene compound represented by CX1X2X3CX4=CHCX5X6X7 (where X1, X2, X3, X4, X5, X6 and X7 are the same as above) is subjected to a dehydrohalogenation reaction; (3) a halogenated alkane compound represented by CHX8A1CHX9A2 (where A1 and A2 are fluorine atoms or perfluoroalkyl groups, and X8 and X9 are the same or different, and are halogen atoms) is subjected to a dehydrohalogenation reaction in a vapor phase in the presence of a catalyst; and (4) a halogenated alkene compound represented by CX8A1=CHA2 (where A1, A2, and X8 are the same as above) is subjected to a dehydrohalogenation reaction in the presence of a catalyst.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to methods for producing halogenated alkene and fluorinated alkyne compounds. [Background technology]

[0002] As a method for producing a halogenated alkene compound, for example, Patent Document 1 discloses a method for producing a halogenated alkene compound by the process of CF 3 CHClCHClC Cl 3 , C.F. 3 CCl 2 CH 2 CCl 3 , C.F. 3 CClHCHFCCl 3 , C.F. 3 CClFCH 2 CCl 3 etc. as starting materials, React with hydrogen fluoride in the presence of a fluorinated chromium catalyst to fluorinate and dehydrofluorinate at the same time. So CF 3 CF=CHCF 3 has gained. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2012 / 067864 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure relates to a process for the synthesis of halogenated alkene compounds and halogenated alkyne compounds with high conversion and The object of the present invention is to provide a method which can achieve high selectivity. [Means for solving the problem]

[0005] The present disclosure encompasses the following configurations. Term 1. General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butene compound represented by the following formula: General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] The production method includes a step of subjecting a halogenated butane compound represented by the following formula (1): Term 2. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butyne compound represented by the following formula: General formula (2A): CX 1 X 2 X 3CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above. X 4 represents a halogen atom.] A step of dehydrohalogenating a halogenated butene compound represented by the following formula: A manufacturing method comprising: Term 3. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butyne compound represented by the following formula: (IA) General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above. X 4 represents a halogen atom.] The halogenated butane compound represented by the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] A step of producing a halogenated butene compound represented by the formula: (IIA) removing hydrogen fluoride after the step (IA); and (IIIA) After the above step (IIA), the obtained compound of general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] The halogenated butene compound represented by the general formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above.] A process for producing a halogenated butyne compound represented by the following formula: A manufacturing method comprising: Item 4. The dehydrofluorination reaction and / or the dehydrohalogenation reaction are carried out using a catalyst and / or a Item 4. The method according to any one of Items 1 to 3, wherein the reaction is carried out in the presence of a base. Item 5. The dehydrofluorination reaction and / or the dehydrohalogenation reaction are carried out in a liquid phase. Item 5. The method for producing the present invention according to any one of Items 1 to 4. Item 6. The dehydrofluorination reaction and / or the dehydrohalogenation reaction are carried out in a closed reaction system. Item 6. The method for producing a medicament according to Item 5, Item 7. The dehydrofluorination reaction and / or the dehydrohalogenation reaction are carried out in a gas phase. Item 5. The method for producing the present invention according to any one of Items 1 to 4. Item 8. The dehydrofluorination reaction and / or the dehydrohalogenation reaction are carried out using an activated carbon catalyst. a catalyst selected from the group consisting of a catalyst, a chromium oxide catalyst, a zeolite catalyst and a silica-alumina catalyst; Item 8. The method according to item 7, wherein the method is carried out in the presence of at least one catalyst. Term 9. General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. X 8 represents a halogen atom.] A method for producing a halogenated alkene compound represented by the following formula: General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 is the same as above. X 8 and X 9 are the same or different and represent a halogen atom. vinegar.] A halogenated alkane compound represented by the following formula is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst: A manufacturing method comprising the steps of: Section 10. General formula (3B): CA 1 ≡CA 2(3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. ] A method for producing a fluorinated alkyne compound represented by the following formula: General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 is the same as above. X 8 represents a halogen atom.] A step of subjecting a halogenated alkene compound represented by the following formula (1) to a dehydrohalogenation reaction in the presence of a catalyst. A manufacturing method comprising: Item 11. The method according to Item 10, wherein the dehydrohalogenation reaction is carried out in a gas phase. Term 12. General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. ] A method for producing a fluorinated alkyne compound represented by the following formula: (IB) General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 is the same as above. X 8 and X 9 are the same or different and represent a halogen atom. vinegar.] A halogenated alkane compound represented by the following formula is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst: , general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] A step of producing a halogenated alkene compound represented by the formula: (IIB) removing hydrogen halide after the step (IB); and (IIIB) After the above step (IIB), the obtained general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] A halogenated alkene compound represented by the following formula is subjected to a dehydrohalogenation reaction in the presence of a catalyst in a gas phase. , general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 is the same as above.] A process for producing a fluorinated alkyne compound represented by the following formula: A manufacturing method comprising: Item 13. The dehydrofluorination reaction and / or the dehydrohalogenation reaction step is carried out in a gas phase continuous reaction system. Item 13. The method according to any one of items 1 to 12, which is carried out in a continuous flow manner. Item 14. The dehydrofluorination reaction and / or the dehydrohalogenation reaction step is A ring in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound are replaced with halogen atoms. Item 14. The method according to any one of items 1 to 13, wherein the method is carried out in the presence of a cyclic halide hydrocarbon compound. Section 15. General formula (1A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (1A) [In the formula, X 1 , X2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A composition containing a halogenated butene compound represented by the formula: The total amount of the composition is taken as 100 mol %, and the content of the halogenated butene compound represented by the general formula (1A) is The composition has a content of 80.00 to 99.99 mol %. Item 16. The total amount of the composition is taken as 100 mol %, and the halogenated butenyl compound represented by the general formula (1A) is used. Item 16. The composition according to item 15, comprising 85.00 to 99.98 mol % of an (E)-halogenated butene compound. Composition. Section 17. General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. X 8 represents a halogen atom.] and a halogenated alkene compound represented by the formula: At least one hydrofluorocarbon (HFC) compound (represented by the general formula (2B) (excluding halogenated alkene compounds), composition. Item 18. The total amount of the composition is taken as 100 mol %, and the halogenated arsenic represented by the general formula (2B) is The content of the sapon compound is 80 mol % or more, and the hydrofluorocarbon (HFC) compound Item 18. The composition according to item 17, wherein the content of is 20 mol% or less. Item 19. The hydrofluorocarbon (HFC) compound is hexafluorobutene, hexafluorobutene, At least one selected from the group consisting of trifluorobutane and octafluorobutane. Item 19. The composition according to item 17 or 18. Section 20. General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. ] A fluorinated alkyne compound represented by the formula: At least one hydrofluorocarbon (HFC) compound (represented by the general formula (3B) Fluorinated alkyne compounds are excluded), composition. Section 21. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. and a halogenated butyne compound represented by the formula: At least one hydrofluorocarbon (HFC) compound (represented by the general formula (3A) (excluding halogenated butyne compounds), composition. Item 22. The total amount of the composition is taken as 100 mol %, and the fluorinated alkyne represented by the general formula (3B) is The content of the compound or the halogenated butyne compound represented by the general formula (3A) is 80 mol % or more. and the content of the hydrofluorocarbon (HFC) compound is 20 mol% or less. 22. The composition according to claim 20 or 21. Item 23. The hydrofluorocarbon (HFC) compound is trifluoromethane, difluoromethane, at least one selected from the group consisting of fluoromethane, tetrafluoromethane and monofluoromethane; 23. The composition according to any one of items 20 to 22, wherein both of the above are one type. Item 24. Cleaning gas, etching gas, refrigerant, heat transfer medium or building gas for organic synthesis 24. The composition according to any one of items 15 to 23, which is used as a bonding block. Effect of the Invention

[0006] According to the present disclosure, halogenated alkene compounds and halogenated alkyne compounds can be produced with high conversion. The synthesis can be carried out with high efficiency and high selectivity. [Brief description of the drawings]

[0007] [Figure 1] 1 is a schematic diagram showing a method for producing an alkene (a halogenated butene compound or a halogenated alkene compound) and an alkyne (a halogenated butyne compound or a fluorinated alkyne compound) according to the present disclosure. In FIG. 1, the generated hydrogen fluoride can be separated in a rectification tower. [Diagram 2] 2 is a schematic diagram showing a method for producing an alkene (a halogenated butene compound or a halogenated alkene compound) and an alkyne (a halogenated butyne compound or a fluorinated alkyne compound) according to the present disclosure. In FIG. 2, the generated hydrogen halide can be removed using a hydrogen halide remover (removal tower). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In this specification, "containing" means "comprise" or "consists essentially of" The term "consist essentially of" includes both "consist of" and "consist of only." In addition, in this specification, when a numerical range is indicated as "A to B", it means A or more and B or less. It means.

[0009] In this disclosure, "selectivity" refers to the ratio of compounds other than the raw material compounds in the effluent gas from the reactor outlet. The ratio of the total molar amount of the target compound contained in the effluent gas to the total molar amount of the compound (mol %).

[0010] In this disclosure, "conversion rate" refers to the molar amount of the raw material compound fed to the reactor. The ratio of the total molar amount of compounds other than the raw material compounds contained in the gas discharged from the reactor outlet (mol %).

[0011] Conventionally, in Patent Document 1, CF 3 CHClCHClCCl 3 , C.F. 3 CCl 2 CH 2 CCl 3 , C.F. 3 CClHCHFCCl 3 , C.F. 3 CC lFCH 2 CCl 3 etc. as starting materials, react with hydrogen fluoride in the presence of oxyfluorinated chromium catalyst. Fluorination and dehydrofluorination are performed to obtain CF 3 CF=CHCF 3 However, the yield is only 1 It was only 4.8%.

[0012] From the above, the yield of the conventional method was only 14.8%. In other words, the halogenated alkene compound and the halogenated alkyne compound can be produced at a high rate, compared with the conventional method. It can be synthesized with high conversion and high selectivity.

[0013] 1. Method for producing halogenated butene compounds and halogenated butyne compounds [1-1] A method for producing halogenated butene compounds from halogenated butane compounds The method for producing a halogenated butene compound according to the present disclosure includes the steps of: General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butene compound represented by the following formula: General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] The method includes a step of subjecting a halogenated butane compound represented by the following formula (1):

[0014] According to the present disclosure, the defluorination of a halogenated butane compound represented by the above general formula (1A) By carrying out the hydrogen reaction, 1 mole of the halogenated butane compound represented by the general formula (1A) can be obtained. Selectively remove the halogenated butene compound represented by the general formula (2A) from which 1 mole of hydrogen fluoride has been removed. and can be obtained continuously from the halogenated butene compound represented by the general formula (2A). In addition, HX 4 In addition, according to the present disclosure, the hydrogen halide elimination reaction represented by the following formula is unlikely to occur. For example, as a halogenated butene compound represented by the general formula (2A), among the geometric isomers, the E isomer is can be selectively synthesized. This is because CF 3 Electron absorption of trihalogenated methyl groups such as Due to the pull effect, CF 3 The carbon at the α-position of the trihalogenated methyl group, such as the phenyl group, is electron deficient, so Since halogenated anions such as fluorine anions are difficult to remove, halogenated butynes ​​are used. The E isomer is selectively produced by CF 3 Methyl trihalides such as the group This is because the steric hindrance of the group makes the trans configuration more stable energetically.

[0015] (1-1-1) Raw material compound (halogenated butane compound) The halogenated butane compound that can be used as a substrate in the production method of the present disclosure is As shown in the general formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. It is a halogenated butane compound represented by the formula:

[0016] In general formula (1A), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 As a halogen atom represented by can be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0017] As the substrate, halogenated butane compounds, especially halogenated butene compounds, are used, which have high conversion. In terms of the conversion rate, yield and selectivity of 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom.

[0018] The above X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 may be the same or different. good.

[0019] Specific examples of halogenated butane compounds that can serve as substrates and satisfy the above conditions include: , C.F. 3 CFHCFHCF 3 , CCl 3 CClHCFHCCl 3 , CBr 3 CBrHCFHCBr 3 These halogens include The chlorobutane compounds can be used alone or in combination of two or more. As such halogenated butane compounds, known or commercially available products can be used.

[0020] (1-1-2) Dehydrofluorination reaction In the process of dehydrofluorinating a halogenated butane compound according to the present disclosure, for example, In the case of a halogenated butane compound represented by the general formula (1A) as a substrate, X 1 , X 2 , X 3 , X 4 , X 5 , X 6and X 7 is more preferably a fluorine atom.

[0021] That is, the reaction is as follows: CF 3 CFHCFHCF 3 → CF 3 CF=CHCF 3 + HF Accordingly, the reaction is preferably a dehydrofluorination reaction.

[0022] The process of dehydrofluorinating a halogenated butane compound in the present disclosure is carried out in a liquid phase. From the viewpoint of productivity in particular, it is preferable to carry out the reaction in the gas phase. is preferred.

[0023] In the present disclosure, the step of dehydrofluorinating a halogenated butane compound is In view of being able to obtain the product with higher selectivity and higher conversion, the catalyst and / or salt More specifically, when a liquid phase reaction is adopted, it is preferable to carry out the reaction in the presence of a base and It is preferable to carry out the reaction in the presence of a catalyst as required. When a gas phase reaction is adopted, the presence of a catalyst is also preferable. The catalyst and base are preferably present in the presence of the catalyst and base.

[0024] (1-1-2-1) Liquid Phase Reaction The step of dehydrofluorinating a halogenated butane compound in the present disclosure is carried out in a liquid phase. In this case, the boiling point of the raw material is increased by applying pressure, for example by using a metal container. By increasing the amount of the liquid component, the yield of the target compound can be further improved.

[0025] The step of dehydrofluorinating a halogenated butane compound in the present disclosure is carried out in a liquid phase. In this case, first, a solution of a halogenated butane compound represented by the above general formula (1A) is prepared, It is then preferable to carry out the reaction in the presence of a base.

[0026] solvent The solvent in the solution of the above-mentioned halogenated butane compound may be either water or a non-aqueous solvent. As the non-aqueous solvent, dimethyl carbonate, ethyl methyl carbonate, dicarbonate, etc. can be used. Ethyl, methyl propyl carbonate, ethyl propyl carbonate and other carbonate esters; ethyl acetate, acetic acid Propyl, butyl acetate, methyl propionate, ethyl propionate, butyl propionate esters such as acetone, ethyl methyl ketone, diethyl ketone, etc.; γ-butyl lactolactone, γ-valerolactone, tetrahydrofuran, tetrahydropyran, etc. Diethyl ether, dibutyl ether, diisopropyl ether, 1,2-dimethoxy ether Ethers such as ethane, 1,2-diethoxyethane, and tetrahydrofuran; acetonitrile, Nitriles such as thionitrile and benzonitrile; amides such as N,N-dimethylformamide; di Preferred are sulfones such as methyl sulfoxide and sulfolane. The solvents can be used alone or in combination of two or more. However, it is preferable that the solvent has a high boiling point and does not easily decompose the base described below. Of these, non-aqueous solvents are preferred, ethers are more preferred, and dibutyl ether is particularly preferred.

[0027] base The step of dehydrofluorinating a halogenated butane compound in the present disclosure is carried out in a liquid phase. In this case, it is preferably carried out in the presence of a base, as described above.

[0028] The base is preferably selected from the viewpoints of the conversion rate of the reaction, the selectivity and the yield of the halogenated butene compound. The hydroxides or alkoxides of alkali metals or alkaline earth metals are preferred. More preferred are alkoxides of metal or alkaline earth metals. Specifically, sodium hydroxide , potassium hydroxide, sodium methoxide, potassium tert-butoxide, etc. Thorium methoxide, potassium tert-butoxide, etc. are preferred. It is preferable that the aqueous solution is an aqueous solution of hydroxide or alkoxide of metal or alkaline earth metal. More preferred is an aqueous solution of an alkoxide of an alkali metal or an alkaline earth metal. Sodium methoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide The use of such a base allows the target compound to be more efficiently reacted with the base. High selectivity and higher conversion can be obtained.

[0029] The content of the base in the reaction solution is not particularly limited. The content of the base in the reaction solution is preferably in the range of 10 to 60% by mass, and more preferably in the range of 40 to 55% by mass. By setting the above range, the target compound can be obtained with higher selectivity and higher conversion.

[0030] catalyst In this step, a catalyst can be used as necessary. The catalyst used in this step is carbon. Hydrocarbon alkoxides are preferred. Examples of hydrocarbon alkoxides include tetrahydrofuran. Methylammonium fluoride, tetramethylammonium chloride, tetramethylammonium ammonium bromide, tetramethylammonium iodide, tetraethylammonium fluoride Tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide Tetraethylammonium iodide, tetrapropylammonium fluoride, tetrapropyl ammonium chloride, tetrapropylammonium bromide, tetrapropylammonium ammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium chloride tetrabutylammonium bromide, tetrabutylammonium iodide, benzyl Benzyltriethylammonium fluoride, benzyltriethylammonium chloride, benzyl Benzyltriethylammonium bromide, benzyltriethylammonium iodide, benzyltriethylammonium Benzyltributylammonium fluoride, benzyltributylammonium chloride, benzyltributylammonium chloride Benzyltributylammonium bromide, benzyltributylammonium iodide, Tributylammonium fluoride, methyltributylammonium chloride, methyl Tributylammonium bromide, methyltributylammonium iodide, methyltributylammonium Trioctyl ammonium fluoride, methyltrioctyl ammonium chloride (trade name Al iquat336), methyltrioctylammonium bromide, methyltrioctylammonium The catalyst may be used alone or in combination of two or more. By using the catalyst, the target compound can be obtained with higher selectivity and more High conversion rates can be obtained.

[0031] Cyclic halocarbons In the present disclosure, the step of subjecting the halogenated butane compound to a dehydrofluorination reaction includes the steps of: It can also be carried out in the presence of a cyclic halocarbon compound, which is A ring in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound are replaced with halogen atoms. In other words, it means a halogen-containing hydrocarbon compound consisting only of carbon atoms and halogen atoms. The term "cyclic halocarbon compound" refers to a cyclic halocarbon compound which is formed from a cyclic halocarbon and does not contain hydrogen atoms.

[0032] The above-mentioned step of dehydrofluorinating the halogenated butane compound is carried out by using such a cyclic carbonized By carrying out the reaction in the presence of a halogen compound, it is possible to shift the reaction equilibrium to the product side. The target halogenated butene compound can be obtained with a high conversion and yield. Cut.

[0033] Examples of halogen atoms contained in the usable cyclic halogenated carbon compound include fluorine atoms, chlorine atoms, and the like. Among them, from the viewpoint of reaction efficiency, They reported that the halogen atoms (X) contained in the raw material halogenated butane compound 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 It is preferable that the halogen atom contains the same kind of halogen as that of the halogen atom. When a halogenated butane compound has multiple halogen atoms (X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 (when all of the above are not the same), the cyclic halocarbon compound is a halobutane compound. It is preferable that the halogenated butane compound contains one or more halogen atoms having the above structure. It is also preferred that the halogen atom is only one of the halogen atoms.

[0034] The number of carbon atoms in the cyclic halocarbon compound that can be used is not particularly limited. From the viewpoint of conversion, selectivity and yield of cyclic halocarbon compounds, The prime number is preferably 1 to 10, more preferably 2 to 7, and further preferably 3 to 5.

[0035] The cyclic halocarbon compounds that can be used are saturated cyclic halocarbon compounds that do not have unsaturated bonds. The compound may be an unsaturated cyclic halocarbon compound having an unsaturated bond. However, from the viewpoints of conversion rate, selectivity and yield of the target halogenated butene compound, Saturated cyclic halocarbon compounds are preferred.

[0036] From the above, the cyclic hydrocarbon halide compound is preferably a saturated cyclic hydrocarbon halide compound. Such saturated cyclic halocarbon compounds include those represented by the general formula (4):

[0037] [ka]

[0038] [In the formula, A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 are the same or different and each is a fluorine atom or a per It represents a fluoroalkyl group. Preferred are saturated cyclic halocarbon compounds represented by the following formula:

[0039] In the general formula (4), A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 Perfluoroa represented by An alkyl group is an alkyl group in which all hydrogen atoms have been replaced with fluorine atoms. The alkyl group may be, for example, an alkyl group having 1 to 20 carbon atoms, preferably having 1 to 12 carbon atoms, and more preferably having 1 Perfluoroalkyl having from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms, and particularly preferably from 1 to 3 carbon atoms. The perfluoroalkyl group is preferably a linear or branched perfluoro group. The perfluoroalkyl group is preferably a trifluoroalkyl group. Methyl group (CF 3 -), and pentafluoroethyl group (C 2 F 5 -) is preferred.

[0040] Specific examples of cyclic halocarbon compounds that meet the above conditions include:

[0041] [ka]

[0042] etc.

[0043] In the manufacturing method of the present disclosure, a halogen compound is added in the presence of a cyclic hydrocarbon halide in a liquid phase. In the dehydrofluorination of a halogenated butane compound, for example, The cyclic halocarbon compound may be blown into the solution of the mixture in a gaseous state or in a liquid state. (e.g. liquefied gas, etc.) may be introduced.

[0044] In the production method of the present disclosure, a halogenated butane compound is reacted in the presence of a cyclic halocarbon compound. When a substance is subjected to a dehydrofluorination reaction, the amount of the cyclic hydrocarbon halide compound used is not particularly limited. From the viewpoint of conversion rate, selectivity and yield of the target halogenated butene compound, It is preferable to use an excess amount relative to the halogenated butane compound as the raw material. The amount of the halogenated butane compound is preferably 1 to 20 moles, more preferably 2 to 10 moles. is more preferable, and 3 to 5 mol is even more preferable.

[0045] Closed reaction system In the present disclosure, the halogenated butene compound represented by the general formula (2A) is has a low boiling point and exists as a gas at room temperature. In the hydrogen reaction process, the reaction system is closed, and the pressure inside the closed reaction system is naturally The reaction can be carried out under pressurized conditions. The halogenated butene compound represented by the formula (I) can be obtained with higher selectivity and higher conversion. can.

[0046] In this way, the boiling point of the target compound is low, so the closed reaction system is pressurized and the reaction solution (salt The concentration of the substrate (raw material compound) in the base solution increases, improving reactivity. The closed reaction system is a batch-type pressure-resistant reaction vessel that is sealed to carry out the reaction. When the reaction is carried out in a batch system, the raw materials are placed in a pressure vessel such as an autoclave. Feed compound, base solution (alkaline aqueous solution), catalyst, etc. are charged, and the appropriate reaction temperature is maintained using a heater. The reaction is preferably carried out for a certain period of time under stirring at a temperature of 100° C. The reaction atmosphere is preferably nitrogen, The reaction is preferably carried out in an atmosphere of an inert gas such as helium or carbon dioxide.

[0047] In the dehydrofluorination reaction step of the present disclosure, the reaction temperature in a closed pressure reaction system is more efficient. From the viewpoint of efficiently proceeding with the elimination reaction and obtaining the target compound with a higher selectivity, From the viewpoint of suppressing the decrease in the rate, usually, 0°C or higher is preferable, 10°C or higher is more preferable, and 15°C or higher is more preferable. The above is even more preferable.

[0048] In the dehydrofluorination reaction step of the present disclosure, the reaction temperature in a closed reaction system is more efficient. The viewpoint of efficiently advancing the dehydrofluorination reaction and obtaining the target compound with a higher selectivity. and from the viewpoint of further suppressing a decrease in selectivity due to decomposition or polymerization of the reaction product, Generally, 100° C. or less is preferable, and 80° C. or less is more preferable.

[0049] Pressurized reaction system In the present disclosure, the dehydrofluorination reaction step is carried out at a reaction temperature of 10° C. or higher and a reaction pressure of By setting the pressure to 0 kPa or higher, the reaction can be carried out in a pressurized reaction system. The halogenated butene compound represented by the general formula (2A) can be produced with higher selectivity and higher conversion. When the reaction system is pressurized in this way, the reaction solution (base solution, alkali It is possible to increase the concentration of the substrate (raw material compound) in the aqueous solution and improve the reactivity. The pressurized reaction system is a batch-type pressure-resistant reaction vessel in which the reaction system is sealed and the reaction is carried out. When the reaction is carried out in a batch system, for example, in a pressure vessel such as an autoclave, The raw material compound, base solution (alkaline aqueous solution), catalyst, etc. are charged, and the appropriate reaction temperature is maintained using a heater. It is preferable to raise the temperature to 30° C. and react for a certain period of time while stirring.

[0050] In the elimination reaction step in the present disclosure, the pressurization conditions are such that the reaction pressure is 0 kPa or more. The reaction pressure is the pressure inside a reaction vessel used in a pressurized reaction system. In the dehydrofluorination reaction step, the reaction pressure is preferably 0 kPa or more, more preferably 5 kPa or more. The upper limit of the reaction pressure is preferably 10 kPa or more, more preferably 15 kPa or more. There is no particular limit, and it is usually about 2 MPa. If not possible, use gauge pressure.

[0051] Pressurization is achieved by pumping inert gases such as nitrogen, helium, and carbon dioxide into the reaction system. The pressure in the reaction system can be increased.

[0052] In the dehydrofluorination reaction step of the present disclosure, the reaction temperature in the pressurized reaction system is more efficient. The elimination reaction can be efficiently carried out to obtain the target compound with higher selectivity, and the conversion rate can be increased. From the viewpoint of suppressing the decrease in the temperature, the temperature is usually preferably 0°C or higher, more preferably 10°C or higher, and more preferably 15°C or higher. The top is even more preferable.

[0053] In the dehydrofluorination reaction step of the present disclosure, the reaction temperature in a closed reaction system is more efficient. The viewpoint of efficiently advancing the dehydrofluorination reaction and obtaining the target compound with a higher selectivity. and from the viewpoint of further suppressing a decrease in selectivity due to decomposition or polymerization of the reaction product, Generally, 100° C. or less is preferable, and 80° C. or less is more preferable.

[0054] Combination of closed and pressurized reaction systems In the dehydrofluorination reaction process of the present disclosure, the continuous phase tank reactor (CSTR) is also used. By connecting a pressure valve, etc., the liquid is removed or the product is gasified and removed. The reaction may also be carried out continuously under pressure while pumping out the reaction mixture.

[0055] After the dehydrofluorination reaction is completed, purification treatment is carried out according to a conventional method as necessary, and the product having the general formula ( A halogenated cyclobutene compound represented by the formula (2A) can be obtained.

[0056] (1-1-2-2) Gas Phase Reaction The step of dehydrofluorinating a halogenated butane compound in the present disclosure is carried out in a gas phase. In this case, there is an advantage that it is not necessary to use a solvent, no industrial waste is generated, and productivity is excellent.

[0057] The process for dehydrofluorinating a halogenated butane compound in the present disclosure is carried out in a gas phase, particularly It is preferable to carry out the reaction in a continuous gas phase flow system using a fixed bed reactor. In this case, the device, operation, etc. can be simplified and it is economically advantageous.

[0058] catalyst The process of dehydrofluorinating a halogenated butane compound in the present disclosure is carried out in the presence of a catalyst. It is preferable to carry out the procedure under the presence of

[0059] The catalyst used in the production method of the present disclosure includes an activated carbon catalyst, a chromium oxide catalyst, a zeolite catalyst, and the like. Preferred are fluoride catalysts, silica alumina catalysts, etc. These catalysts are not fluorinated. Both fluorinated and non-fluorinated catalysts can be employed.

[0060] The activated carbon catalyst is not particularly limited, and may be a powder activated carbon such as crushed carbon, shaped carbon, granular carbon, or spherical carbon. Powdered activated carbon is 4 mesh (4.75 mm) to 100 mesh according to the JIS test (JIS Z8801). It is preferable to use powdered activated carbon with a particle size of 0.150 mm. , publicly known or commercially available products can be used.

[0061] Activated carbon becomes more active when fluorinated, so it is recommended to use it in the reaction. Before use, fluorinated activated carbon obtained by previously fluorinating activated carbon can also be used as the activated carbon catalyst. That is, as the activated carbon catalyst, either non-fluorinated activated carbon or fluorinated activated carbon can be used.

[0062] As the fluorinating agent for fluorinating activated carbon, for example, in addition to inorganic fluorinating agents such as HF, hydrofluorocarbons (HFCs) such as hexafluoropropene, chlorofluorocarbons (CFCs) such as chlorofluoromethane, and organic fluorinating agents such as hydrochlorofluorocarbons (HCFCs) can also be used.

[0063] As a method for fluorinating activated carbon, for example, a method of flowing the above-mentioned fluorinating agent under atmospheric pressure under temperature conditions of about room temperature (25 °C) to 400 °C can be mentioned.

[0064] The chromium oxide catalyst is not particularly limited, but when chromium oxide is expressed as CrOm, 1.5 < m < 3 is preferable, 2 < m < 2.75 is more preferable, and 2 < m < 2.3 is even more preferable. Also, when chromium oxide is expressed as CrO m ·nH 2 O, it may be hydrated so that the value of n is 3 or less, particularly 1 to 1.5.

[0065] The fluorinated chromium oxide catalyst can be prepared by fluorinating the above-mentioned chromium oxide catalyst. This fluorination can be carried out using, for example, HF, fluorocarbon, etc. Such a fluorinated chromium oxide catalyst can be synthesized, for example, according to the method described in JP-A-05-146680.

[0066] An example of a method for synthesizing a chromium oxide catalyst and a fluorinated chromium oxide catalyst will be described below.

[0067] First, a solution of chromium salts (chromium nitrate, chromium chloride, chromium alum, chromium sulfate, etc.) ) and aqueous ammonia to obtain a precipitate of chromium hydroxide. The physical properties of chromium hydroxide can be controlled by the reaction rate of the precipitation reaction. The reaction rate is The reaction rate is preferably fast. The reaction rate depends on the reaction solution temperature, the ammonia water mixing method (mixing rate), It depends on the stirring conditions, etc.

[0068] The precipitate can be filtered, washed, and then dried. For example, drying can be performed in air at 70 to 200°C. The catalyst at this stage is sometimes called the chromium hydroxide state. The catalyst can then be crushed. From the standpoint of pellet strength, catalyst activity, etc. The crushed powder (for example, the particle size is 1000 μm or less, especially 46 to 1000 μm, 95% of the particles are The precipitation reaction rate is adjusted so that the powder density is 0.6 to 1.1 g / ml, preferably 0.6 to 1.0 g / ml. The specific surface area of ​​the powder (specific surface area by the BET method) is preferably 200° C. and 80 minutes of degassing. Item, 100m 2 / g or more is preferable, and 120m 2 The upper limit of the specific surface area is preferably 1 / g or more. For example, 220m 2 / g.

[0069] This chromium hydroxide powder is mixed with 3% by weight or less of graphite if necessary, and then pressed into a tablet press. Pellets can be formed. The size and strength of the pellets can be adjusted accordingly. do.

[0070] The molded catalyst is calcined in an inert atmosphere, for example, in a nitrogen stream, to form amorphous chromium oxide. The firing temperature is preferably 360° C. or higher, and from the viewpoint of suppressing crystallization, 380° C. to 50° C. The preferred temperature is 460° C. The firing time can be, for example, 1 to 5 hours.

[0071] The specific surface area of ​​the calcined catalyst is, for example, 170 m from the viewpoint of catalytic activity. 2 / g or more is preferable. , 180m 2 / g or more is more preferable, and 200m 2 / g or more is more preferable. , typically 240m 2 / g is preferable, and 220m 2 / g is more preferable.

[0072] Then, the chromium oxide is fluorinated to obtain a fluorinated chromium oxide. The fluorination temperature should be within a range where the water produced does not condense, and the reaction heat is The upper limit of the temperature is set to a temperature at which the catalyst does not crystallize. There is no restriction on the pressure during fluorination, but the pressure during catalytic reaction is It is preferable to do so.

[0073] As the zeolite catalyst, a wide variety of known types of zeolite can be used. For example, crystalline hydrous aluminosilicates of alkali metals or alkaline earth metals are preferred. The crystal form of the zeolite is not particularly limited, and examples thereof include A-type, X-type, and LSX-type. The alkaline metal or alkaline earth metal is not particularly limited, and may be potassium, sodium, calcium, Examples of such materials include lithium and zinc.

[0074] Zeolite catalysts become more active when fluorinated, so the reaction Before use in the reaction, the zeolite catalyst is fluorinated to prepare a fluorinated zeolite catalyst. It is possible.

[0075] The fluorinating agent for fluorinating the zeolite catalyst is, for example, F 2 Inorganic fluoride such as HF Fluorinating agents, fluorocarbon organic fluorinating agents such as hexafluoropropene, etc. are used. It is possible.

[0076] The method of fluorinating the zeolite catalyst is, for example, to fluorinate the catalyst at a temperature of about room temperature (25°C) to about 400°C. The fluorination method may be exemplified by a method in which the above-mentioned fluorinating agent is passed through the reaction vessel under atmospheric pressure and high temperature conditions. can.

[0077] Silica-alumina catalyst is a type of catalyst that contains silica (SiO 2 ) and alumina (Al 2 O 3 ) containing a composite oxide catalyst The total amount of silica and alumina is taken as 100 mass %, and the silica content is, for example, 20 to 90%. % by weight, particularly 50 to 80% by weight of the catalyst can be used.

[0078] Silica-alumina catalysts become more active when fluorinated. Before use in the reaction, the silica-alumina catalyst is fluorinated to obtain a fluorinated silica-alumina catalyst. It can also be used as a medium.

[0079] Examples of fluorinating agents for fluorinating silica-alumina catalysts include F 2 , HF etc. Fluorination agents such as organic fluorination agents and fluorocarbon organic fluorination agents such as hexafluoropropene are used. There can be.

[0080] The method of fluorinating the silica-alumina catalyst is, for example, to fluorinate the catalyst at room temperature (25°C) to about 400°C. The fluorination method includes a method in which the above-mentioned fluorinating agent is passed through the reaction vessel under the temperature condition of This can be done.

[0081] The above catalysts can be used alone or in combination of two or more kinds. Among these, from the viewpoints of conversion rate, selectivity and yield, activated carbon catalysts (activated carbon or fluorine) are preferred. fluorinated activated carbon), chromium oxide catalyst (chromium oxide or fluorinated chromium oxide), etc. are preferred. An activated carbon catalyst (activated carbon or fluorinated activated carbon) is preferable.

[0082] In addition, the above-mentioned chromium oxide catalyst, zeolite catalyst, silica alumina catalyst, etc. may be used as the catalyst. When used, it may be supported on a carrier. Examples of such carriers include , carbon, alumina (Al 2 O 3 ), zirconia (ZrO 2 ), silica (SiO 2 ), titania (TiO 2 ) Examples of carbon include activated carbon, amorphous carbon, graphite, diamond, etc. It can be used.

[0083] In the production method of the present disclosure, a halogenated butane compound is reacted in a gas phase in the presence of a catalyst. In carrying out the dehydrofluorination reaction, for example, the catalyst is halogenated in a solid state (solid phase). It is preferable to contact the catalyst with a butane compound. In this case, the catalyst may be in the form of a powder. However, the pellet form is preferred when it is used in a gas phase continuous flow reaction.

[0084] The specific surface area of ​​the catalyst measured by the BET method (hereinafter sometimes referred to as the "BET specific surface area") is , usually 10~3000m 2 / g is preferable, and 10 to 2500m 2 / g is more preferable, and 20 to 2000m 2 / g is more preferable. Preferably, 30 to 1500 m 2 / g is particularly preferable. When the BET specific surface area of ​​the catalyst is in such a range, The catalyst particles are not too dense, so the halogenated butenes can be produced with higher selectivity. In addition, the conversion rate of the halogenated butane compound can be further improved. is also possible.

[0085] Cyclic halocarbons In the present disclosure, the step of subjecting the halogenated butane compound to a dehydrofluorination reaction includes the steps of: It can also be carried out in the presence of a cyclic halocarbon compound, which is A ring in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound are replaced with halogen atoms. In other words, it means a halogen-containing hydrocarbon compound consisting only of carbon atoms and halogen atoms. The term "cyclic halocarbon compound" refers to a cyclic halocarbon compound which is formed from a cyclic halocarbon and does not contain hydrogen atoms.

[0086] The above-mentioned step of dehydrofluorinating the halogenated butane compound is carried out by using such a cyclic carbonized By carrying out the reaction in the presence of a halogen compound, it is possible to shift the reaction equilibrium to the product side. The target halogenated butene compound can be obtained with a high conversion and yield. Cut.

[0087] Such a cyclic halocarbon compound is (1-1-2-1) Liquid Phase Reaction In The above-described examples and amounts of the preferred compounds can be used.

[0088] In the manufacturing method of the present disclosure, a halogen compound is added in the presence of a cyclic hydrocarbon halide compound in a gas phase. In the dehydrofluorination of a cyclic butane compound, for example, a cyclic hydrocarbon halide may be used. It is preferred to contact the mixture with the halogenated butane compound in a gaseous state (vapor phase).

[0089] Reaction temperature In the step of subjecting a halogenated butane compound to a dehydrofluorination reaction in the present disclosure, the reaction temperature The dehydrofluorination reaction proceeds more efficiently, improving the conversion rate and obtaining the target compound. From the viewpoint of obtaining halogenated butene compounds with higher selectivity, the reaction temperature is usually 230°C or higher. The catalyst is preferably at least 280°C, more preferably at least 320°C. If activated carbon is used, and if no cyclic halocarbon compound is used, the reaction temperature is In order to make the dehydrofluorination reaction proceed more efficiently, it is preferable to use a higher temperature. ℃ or higher, more preferably 420 ℃ or higher. However, in the gas phase, the halogenated butane compounds can be defluorinated in the presence of cyclic halogenated hydrocarbon compounds. In the case of the hydrogen fluoride reaction, the dehydrofluorination reaction can proceed more efficiently. Therefore, the reaction temperature can be somewhat lower, and generally 230°C or higher is preferred, and 280°C or higher is preferred. More preferably, the temperature is 320° C. or higher.

[0090] The reaction temperature for dehydrofluorinating the halogenated butane compound in the present disclosure is more efficient. By efficiently advancing the dehydrofluorination reaction, the conversion rate is further improved, and the halogen From the viewpoint of obtaining the substituted butene compound with a higher selectivity, a temperature of 500° C. or less is usually preferred. The temperature is preferably 450° C. or lower.

[0091] Reaction time The reaction time for dehydrofluorinating the halogenated butane compound in the present disclosure is, for example, When using a gas-phase flow system, the contact time of the raw material compound with the catalyst (W / F) [W: catalyst The reaction conversion rate is particularly high and the halogen From the viewpoint of obtaining polybutane compounds with higher yield and higher selectivity, it is preferable to use a 5-100g·sec . / cc is preferred, 10 to 90 g·sec. / cc is more preferred, and 15 to 80 g·sec. / cc is even more preferred. In the gas phase, defluorination of halogenated butane compounds in the presence of cyclic halogenated hydrocarbon compounds When hydrogen is reacted, the dehydrofluorination reaction can proceed more efficiently, The lower limit of the contact time can be made smaller, and is preferably 1 to 100 g·sec. / cc. More preferably, the contact time is 90 g·sec. / cc or less, and even more preferably 3 to 80 g·sec. / cc. By "during" is meant the time during which the feed compound and the catalyst are in contact.

[0092] Reaction Pressure The reaction pressure for dehydrofluorinating the halogenated butane compound in the present disclosure is more efficient. By efficiently advancing the dehydrofluorination reaction, the conversion rate is further improved, and the halogen From the viewpoint of obtaining the substituted butene compound with a higher selectivity, the pressure is preferably 0 kPa or more, and more preferably 10 The pressure is preferably 20 kPa or more, more preferably 20 kPa or more, and particularly preferably 30 kPa or more. The upper limit of the pressure is not particularly limited, and is usually about 2 MPa. Unless otherwise specified, gauge pressure shall be used.

[0093] In the dehydrofluorination reaction of the halogenated butane compound in the present disclosure, a reactor in which the cyclic halogenated hydrocarbon compound is reacted with the catalyst; There are no particular limitations on the shape and structure of the container, so long as it can withstand the above-mentioned temperatures and pressures. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multi-tube reactor. Examples of materials for the vessel include glass, stainless steel, iron, nickel, and iron-nickel alloys. Can be obtained.

[0094] Example of dehydrofluorination reaction In the present disclosure, the dehydrofluorination reaction of a halogenated butane compound is carried out by adding a raw material compound to a reactor. A certain halogenated butane compound is continuously charged into the reactor, and the target compound, halogen, is extracted from the reactor. The process can be carried out by either a continuous flow system or a batch system, in which the fluorinated butene compound is continuously extracted. If the target compound, the halogenated butene compound, remains in the reactor, Since the elimination reaction can proceed smoothly, it is preferable to carry out the reaction in a flow manner. The process of dehydrofluorinating halogenated butane compounds is carried out in a gas phase, particularly in a fixed bed reactor. It is preferable to carry out the reaction in a continuous gas phase flow system using a vessel. This simplifies the operation and is economically advantageous. It is also possible to employ a closed reaction system or a pressurized reaction system as described above in the liquid phase reaction. .

[0095] Regarding the atmosphere in which the dehydrofluorination reaction of the halogenated butane compound is carried out in this disclosure In order to prevent the catalyst from deteriorating, it is preferable to carry out the reaction under an inert gas atmosphere or a hydrogen fluoride gas atmosphere. The inert gas is preferably nitrogen, helium, argon, or the like. Among the gases, nitrogen is preferred from the viewpoint of reducing costs. The concentration of the inert gas is as follows: It is preferable that the amount is 0 to 50 mol % of the gas components introduced into the reactor.

[0096] After the dehydrofluorination reaction is completed, purification treatment is carried out according to a conventional method as necessary, and the product having the general formula ( A halogenated butene compound represented by the formula (2A) can be obtained.

[0097] (1-1-3) Target compound (halogenated butene compound) The target compound of the present disclosure thus obtained has the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. It is a halogenated butene compound represented by the formula:

[0098] X in general formula (2A) 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 In the above general formula (1A), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 Therefore, the general formula ( The halogenated butene compound represented by 2A) is, for example, specifically, CF 3 CF=CHCF3 , CCl 3 CCl =CHCCl 3 , CBr 3 CBr=CHCBr 3 These compounds include both Z and E forms. Includes.

[0099] The halogenated butene compounds thus obtained are used in cutting-edge microstructures such as semiconductors and liquid crystals. Etching gases, cleaning gases, deposition gases, coolants, heat transfer gases for forming structures It can be effectively used for various purposes such as a medium and building blocks for organic synthesis. and building blocks for organic synthesis are described below.

[0100] [1-2] Manufacturing method for producing halogenated butyne compounds from halogenated butene compounds The method for producing the halogenated butyne compounds of the present disclosure includes the steps of: General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butyne compound represented by the following formula: General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 5 , X6 and X 7 is the same as above. X 4 represents a halogen atom.] The process includes a step of subjecting a halogenated butene compound represented by the following formula (1):

[0101] According to the present disclosure, the halogenated butene compound represented by the above general formula (2A) can be dehalogenated. By carrying out the hydrogen hydride reaction, it is possible to obtain A halogenated butyne compound represented by the general formula (3A) in which 1 mole of hydrogen halide has been eliminated. can be selectively obtained.

[0102] (1-2-1) Raw material compound (halogenated butene compound) The halogenated butene compound that can be used as a substrate in the production method of the present disclosure is As shown in the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. The halogenated butane compound [1-1] is represented by the formula: This corresponds to the target compound in the process for producing a halogenated butene compound from the above-mentioned reaction.

[0103] In the general formula (2A), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 As a halogen atom represented by The above-mentioned types can be used for the above. The preferred types are also the same.

[0104] Specific examples of halogenated butene compounds that can serve as substrates that satisfy the above conditions include: , C.F. 3 CF=CHCF 3 , CCl 3 CCl=CHCCl 3 , CBr 3 CBr=CHCBr 3 These compounds include Z These halogenated butene compounds include both the 2- and E-isomers. Such halogenated butene compounds can be used in combination of two or more. , publicly known or commercially available products can be used.

[0105] (1-2-2) Dehydrohalogenation reaction In the process of dehydrohalogenating a halogenated butene compound according to the present disclosure, for example, For example, in the case of a halogenated butene compound represented by the general formula (2A) as a substrate, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is more preferably a fluorine atom.

[0106] That is, the reaction is as follows: CF 3 CF=CHCF 3 → CF 3 C≡CCF 3 + HF Accordingly, the reaction is preferably a dehydrofluorination reaction.

[0107] The process for dehydrohalogenating a halogenated butene compound in the present disclosure is carried out in a liquid phase. From the viewpoint of productivity, it is preferable to carry out the reaction in the gas phase. It is preferable.

[0108] The step of dehydrohalogenating a halogenated butene compound in the present disclosure is From the viewpoint of obtaining compounds with higher selectivity and higher conversion, the catalyst and / or It is preferable to carry out the reaction in the presence of a base. More specifically, when a liquid phase reaction is adopted, It is preferable to carry out the reaction in the presence of a base and, if necessary, a catalyst. When a gas phase reaction is employed, the catalyst It is preferable to carry out the reaction in the presence of a solvent. (Conditions for closed and pressurized reaction systems, etc.) and details for gas-phase reactions For details on (catalyst, cyclic halide hydrocarbon compound, reaction temperature, reaction time, reaction pressure, etc.), please refer to A reaction to obtain a halogenated butene compound by dehydrofluorination of a halogenated butane compound. "The halogenated butene compound is converted into a halogenated butyne compound by a dehydrohalogenation reaction." The above [1-1] halogenated butane The method for producing a halogenated butene compound from a compound described above can be used. The preferred types and contents are also the same.

[0109] After the dehydrohalogenation reaction is completed, purification treatment is carried out according to conventional methods as necessary. A halogenated butyne compound represented by formula (3A) can be obtained.

[0110] (1-2-3) Target compound (halogenated butyne compound) The target compound of the present disclosure thus obtained has the general formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. It is a halogenated butyne compound represented by the formula:

[0111] X in general formula (3A) 1 , X 2 , X 3 , X 5 , X 6 and X 7 is X in the above general formula (2A). 1 , X 2 , X 3 , X 5 , X 6 and X 7 Therefore, the compound represented by the general formula (3A) to be produced is The halogenated butyne compounds to be used are, for example, specifically CF 3 C≡CCF 3 , CCl 3 C≡CCCl 3 , C.B. r 3 C≡CCBr 3 etc.

[0112] The halogenated butyne compounds thus obtained are used in cutting-edge microstructures such as semiconductors and liquid crystals. Etching gases, cleaning gases, deposition gases, coolants, heat transfer gases for forming structures It can be effectively used for various purposes such as a medium and building blocks for organic synthesis. and building blocks for organic synthesis are described below.

[0113] [1-3] From halogenated butane compounds, via halogenated butene compounds, Method for producing butyl nitrate compounds The method for producing the halogenated butyne compounds of the present disclosure includes the steps of: General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 are the same or different and represent a halogen atom. A method for producing a halogenated butyne compound represented by the following formula: (IA) General formula (1A): CX 1 X 2 X 3 CHX 4 CFHCX 5 X 6 X 7 (1A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above. X 4 represents a halogen atom.] The halogenated butane compound represented by the general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] A step of producing a halogenated butene compound represented by the formula: (IIA) removing hydrogen fluoride after the step (IA); and (IIIA) After the above step (IIA), the obtained compound of general formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [where, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as above.] The halogenated butene compound represented by the general formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above.] A process for producing a halogenated butyne compound represented by the following formula: Includes.

[0114] (1-3-1) Process (IA) In the method for producing a halogenated butyne compound according to the present disclosure, step (IA) is 1] The explanation of the production method from halogenated butane compounds to halogenated butene compounds is as it is. It can be adopted.

[0115] (1-3-2) Process (IIA) The method for producing a halogenated butyne compound of the present disclosure comprises the steps of: The halogenated butane compound is subjected to a dehydrofluorination reaction to produce a halogenated butene represented by the above general formula (2A). After producing the mixture (step (IA)), a mixture containing a halogenated butene compound and hydrogen fluoride is and removing hydrogen fluoride from the mixture (IIA).

[0116] In the method for producing a halogenated butyne compound according to the present disclosure, after step (IA), After separating and / or removing the hydrogen fluoride produced in the hydrogen fluoride reaction, the next step (IIIA) is By proceeding to the production of fluorinated butyne compounds, the target compound, halides, can be obtained by dehydrofluorination. The halogenated butyne compounds can be produced with high conversion (yield) and high selectivity.

[0117] From the mixture containing the halogenated butene compound and hydrogen fluoride obtained in step (IA), To remove hydrogen fluoride, there are two methods: separating hydrogen fluoride in a rectification tower (Figure 1), or using alkali or sec Hydrogen fluoride is removed using hydrogen halide removers (removal towers) such as fluoride, alumina, and silica. The method of removing the fluorine-containing compound (FIG. 2) can be preferably adopted.

[0118] In the method for producing a halogenated butyne compound disclosed herein, the unreacted raw material ( It is preferable to reuse the halogenated butane compound of the present disclosure. In the process for producing the compound, the unreacted halogenated butane compound separated by rectification is returned to the reactor. The resulting mixture can be reused and used for dehydrofluorination.

[0119] Method for separating hydrogen fluoride in a rectification column The boiling point of the separated hydrogen fluoride (HF) is 19.54°C.

[0120] From the mixture containing the halogenated butene compound and hydrogen fluoride obtained in step (IA), To remove hydrogen chloride, the boiling points of both compounds are used as a reference, and the difference between the boiling points of the two compounds is used as a basis for rectification. The halogenated butene compounds are separated from hydrogen fluoride in the tower, and the halogenated butene compounds are recovered. The hydrogen fluoride can be separated. In the manufacturing process, the content of hydrogen fluoride can be reduced, and the target compound, halogenated Butyne compounds can be produced with high conversion (yield) and high selectivity.

[0121] Method for removing hydrogen fluoride using a hydrogen halide remover The separated hydrogen fluoride can be removed by a hydrogen fluoride remover. Hydrogen removers include alkali, alumina, silica, zeolite, and hydrogen fluoride such as Sekado. It is preferable to use a remover. SEKADO is a substance called Allophane. A non-crystalline clay composed of amorphous or poorly crystalline hydrated aluminum silicates. It is an adsorbent (synthetic zeolite) whose main raw materials are earth-related minerals (alumina and silica gel).

[0122] From the mixture containing the halogenated butene compound and hydrogen fluoride obtained in step (IA), To remove hydrogen fluoride, use a hydrogen fluoride remover to remove hydrogen fluoride and bromine halide. The butyne compounds can be recovered. In the present invention, the content of hydrogen fluoride can be reduced, and the target compound, halogenated bromine, can be obtained. Tin compounds can be produced with high conversion (yield) and high selectivity.

[0123] Hydrogen fluoride concentration In the method for producing a halogenated butyne compound according to the present disclosure, after step (IA), After separating and / or removing the hydrogen fluoride produced by hydrogen fluoride, the halogen By proceeding to the production of halogenated butyne compounds, the target compound, halogenated butyne, can be obtained by dehydrofluorination. The substituted butyne compounds can be produced with high conversion (yield) and high selectivity.

[0124] In the next step (IIIA) of producing a halogenated butyne compound, the raw material is a compound represented by the above general formula: A halogenated butene compound represented by the general formula (2A) is used. In addition to the halogenated butene compounds, the mixture contains hydrogen fluoride produced by dehydrofluorination. This is sometimes carried over to the next step (IIIA), which is the production of halogenated butyne compounds.

[0125] In the method for producing a halogenated butyne compound according to the present disclosure, the halogenated butyne compound in the next step (IIIA) is In the production of the compound, the target compound, halogenated butyne compound, is obtained by dehydrofluorination. The compound is produced with high conversion (yield) and high selectivity, and is therefore suitable for use as a raw material in the next step (IIIA). The composition used as a fluorine-containing polymer comprises a halogenated butene compound represented by the general formula (2A) and a fluorinated The hydrogen fluoride content (concentration) is 50 mol% based on the mixture containing hydrogen (100 mol%). Preferably, the content is 20 mol % or less, more preferably 3 mol % or less, and even more preferably 0.1 mol % or less. The following is particularly preferred. The low content of hydrogen fluoride in the mixture containing the target compound, halogenated butyric acid, The compounds can be produced with high conversion (yield) and high selectivity.

[0126] (1-3-3) Process (IIIA) In the method for producing a halogenated butyne compound according to the present disclosure, step (IIIA) is -2] A method for producing a halogenated butyne compound from a halogenated butene compound is described as follows. It can also be adopted.

[0127] (1-3-4) Example of dehydrofluorination In the dehydrofluorination step of the present disclosure, the reaction is carried out by adding a raw material compound to a reactor in step (IA). The target compound (halogenated butane compound) is continuously charged into the reactor. The process can be carried out by either a continuous flow system, in which the oxidized butene compound is continuously extracted, or a batch system. Then, from the mixture containing the halogenated butene compound and hydrogen fluoride, Hydrogen fluoride is removed (step (IIA)), and in step (IIIA), a raw material compound (halogen The target compound (halogenated butene compound) is continuously charged into the reactor, and the target compound (halogenated butene compound) is discharged from the reactor. The method can be either a flow type in which the sample (product) is continuously extracted or a batch type. In each step, the target compound (halogenated butene compound or halogenated butyne compound) is reacted. Since the dehydrofluorination can proceed further without being retained in the reactor, it is preferable to carry out the process in a flow-through manner. I wish.

[0128] In the dehydrofluorination step of the present disclosure, the reaction is carried out in the gas phase, particularly using a fixed bed reactor. When the continuous gas phase flow system is used, the apparatus, operation, etc. This simplifies the process and is economically advantageous.

[0129] In the dehydrofluorination step of the present disclosure, the reaction atmosphere is In order to prevent deterioration of the catalyst (activated carbon, metal catalyst, etc.), it is preferable to use an inert gas. In the present disclosure, the inert gas is selected from the group consisting of nitrogen, helium, argon, and carbon dioxide. At least one selected from the following can be preferably used. However, nitrogen is more preferable from the viewpoint of cost reduction. The concentration of the inert gas is It is preferable that the amount is 0 to 50 mol % of the gas components introduced.

[0130] In the dehydrofluorination step of the present disclosure, after the reaction is completed, the reaction is carried out according to the usual method as described above. The target compound (halogenated butene compound or halogenated butyne compound) is obtained by purification. can be obtained.

[0131] 2. Method for producing halogenated alkene compounds and fluorinated alkyne compounds [2-1] A method for producing halogenated alkene compounds from halogenated alkane compounds The method for producing a halogenated alkene compound of the present disclosure comprises reacting a halogenated alkene compound with a compound represented by the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. X 8 represents a halogen atom.] A method for producing a halogenated alkene compound represented by the following formula: General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 is the same as above. X 8 and X 9 are the same or different and represent a halogen atom. vinegar.] A halogenated alkane compound represented by the following formula is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst: The method includes the step of:

[0132] According to the present disclosure, a halogenated aryl group represented by the above general formula (1B) is reacted in a gas phase in the presence of a catalyst. By carrying out a dehydrohalogenation reaction of the leucane compound, the halogenated compound represented by the general formula (1B) can be obtained. Represented by general formula (2B) in which 1 mole of hydrogen halide is eliminated for every 1 mole of alkane compound It is possible to selectively obtain a halogenated alkene compound, and moreover, it is possible to continuously produce a halogenated alkene compound represented by the general formula (2B). From the halogenated alkene compound represented by the formula HX 8 The elimination of hydrogen halide represented by According to the present disclosure, the halogenated alkene represented by the general formula (2B) As a compound, it is possible to selectively synthesize the E-isomer among the geometric isomers. This effect is , A 1 and A 2 This is more pronounced when the alkyl group is a perfluoroalkyl group, and CF 3 Trichloroethylene CF due to the electron-withdrawing effect of the halogenated methyl group 3 The carbon atom at the α-position of a trihalogenated methyl group such as Since the fluorine anion and other halogenated anions are difficult to remove, the halo This makes it easier to produce halogenated butenes instead of genbutynes. Also, the E isomer can be produced selectively. The one is A 1 and A 2 This is more pronounced when the alkyl group is a perfluoroalkyl group, and CF 3 Moto et al. The trans configuration is energetically more stable due to the steric hindrance of the rehalogenated methyl group. This is the case.

[0133] (2-1-1) Raw material compound (halogenated alkane compound) In the present disclosure, a method for producing a halogenated alkene compound from a halogenated alkane compound is provided. The starting compound of the method is represented by the general formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. X 8 and X 9 are the same or different and represent a halogen atom. It is a halogenated alkane compound represented by the formula:

[0134] In the general formula (1B), A 1 and A 2 A perfluoroalkyl group represented by the formula: 8 and X 9 Indicated by As the halogen atom to be used, those mentioned above can be used. The same applies to the preferred specific examples.

[0135] Examples of halogenated alkane compounds that satisfy these conditions include , C.F. 3 CHClCHClCF 3 (336mdd), CF 3 CHClCHFCl, CHFClCHFCl, CF 3 CHFCHFCF 3 (338mee), CF 3 CHFCHF 2 , CHF 2 CHF 2 , C.F. 3 CHClCHClC 2 F 5 , C 2 F 5 CHClCHClC 2 F 5 , C 2 F 5 CHClCHFCl, CF 3 CHFCHFC 2 F 5 , C 2 F 5 CHFCHFC 2 F 5 , C 2 F 5 CHFCHF 2 These halogenated alkane compounds include These halogen compounds may be used alone or in combination of two or more. The alkane compound may be a known or commercially available product.

[0136] (2-1-2) Dehydrohalogenation reaction In the step of dehydrohalogenating a halogenated alkane compound according to the present disclosure, The halogenated alkane compounds are converted to halogenated alkene compounds with high conversion (yield) and high yield. The present invention is advantageous in that it can be produced with high selectivity by using, for example, a halo represented by the general formula (1B) as a substrate. In alkane compounds, A 1 and A 2 Both are trifluoromethyl groups (CF 3 -) is preferred, and X 8 and X 9 is more preferably a fluorine atom or a chlorine atom.

[0137] That is, the reaction is as follows: CF 3 CHClCHClCF 3 (336mdd) → CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz) + HCl CF 3 CHFCHFCF 3 (338mee) → CF 3 CF=CHCF 3 ((Z) or (E)-1327myz) + HF Accordingly, the reaction is preferably a dehydrofluorination reaction or a dehydrochlorination reaction.

[0138] catalyst Dehalogenation of halogenated alkane compounds to halogenated alkene compounds in the present disclosure The hydrogen chloride reaction step is carried out in the gas phase in the presence of a catalyst.

[0139] The catalyst used in this step is preferably activated carbon and a metal catalyst from the viewpoints of conversion rate, selectivity and yield. It is preferable that the material is at least one selected from the group consisting of:

[0140] When a metal catalyst is used as the catalyst in this process, chromium oxide, chromium oxide fluoride, etc. Chromium fluoride, aluminum oxide, aluminum oxide fluoride, aluminum fluoride, Iron oxide, iron oxide fluoride, iron fluoride, nickel oxide, nickel oxide fluoride, nickel fluoride , magnesium oxide, magnesium oxide fluoride, and magnesium fluoride. It is preferable that at least one selected from the above be used.

[0141] In this process, the raw material halogenated alkane compound is reacted with a high conversion rate (yield). It is also possible to produce the target halogenated alkene compound with high selectivity. Among these catalysts, activated carbon, chromium oxide, fluorinated chromium oxide, and aluminum oxide are the most popular. Of these, aluminum oxide fluoride and aluminum oxide fluoride are more preferable.

[0142] In this step, when the raw material compound is contacted with the catalyst in the gas phase, the catalyst is solid. It is preferable to contact the starting compound in this state (solid phase).

[0143] In this step, the catalyst may be in powder form, but pellet form is more suitable for continuous gas-phase flow reactions. Preferred.

[0144] The specific surface area of ​​the catalyst measured by the BET method (hereinafter also referred to as the BET specific surface area) is usually 10~3000m 2 / g is preferable, and 100 to 2000m 2 / g is more preferable, and 500 to 1500m 2 / g is more preferred. 1000~1300m 2 When the BET specific surface area of ​​the catalyst is in this range, The density of the catalyst particles is not too small, so the target compound can be obtained with higher selectivity. It is also possible to further improve the conversion rate of the raw material compounds.

[0145] When using activated carbon as a catalyst, powdered activated carbon such as crushed carbon, formed carbon, granular carbon, or spherical carbon is used. It is preferable that the powdered activated carbon is 4 mesh (4.76 mm) to 100 mesh (0.1 It is preferable to use powdered activated carbon having a particle size of 49 mm.

[0146] When activated carbon is used as a catalyst, the activated carbon (for example, with a specific surface area of ​​1200 m 2 / g) is It is preferable to use either powder or granular activated carbon, and it is more preferable to use granular activated carbon. stomach.

[0147] When a metal catalyst is used as the catalyst, it is preferable that the metal catalyst is supported on a carrier. Examples of the material include carbon and alumina (Al 2 O 3 ), zirconia (ZrO 2 ), silica (SiO 2 ),blood Tania (TiO 2 ) and the like can be preferably used. In addition, as carbon, activated carbon, amorphous Carbon, graphite, diamond, etc. can be preferably used.

[0148] As an example of the catalyst in this disclosure, chromium oxide and fluorinated chromium oxide are Chromium oxide is, for example, Cr 2 O 3 nH 2 When expressed as O, the value of n is It is preferably 3 or less, and more preferably 1 to 1.5. is the composition formula: CrO mIn this case, it is preferable that m is usually in the range of 1.5 < m < 3. As the catalyst , fluorinated chromium oxide can be prepared by fluorinating chromium oxide. Examples of fluorination include fluorination with hydrogen fluoride (HF) and fluorination with fluorocarbons.

[0149] 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 fluorination temperature is preferably, for example, 100°C to 460°C. The fluorination pressure is preferably the pressure when used in 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 temperature higher than normal for a long time.

[0150] The highly fluorinated-chromium oxide catalyst preferably has a fluorine content of 30% by mass or more, more preferably 30% by mass to 45% by mass. The fluorine content can be measured by the mass change of the catalyst or a general quantitative analysis method for chromium oxides.

[0151] Cyclic halocarbons In the present disclosure, the process of dehydrogenating the above-described halogenated alkane compound can also be carried out in the presence of a cyclic carbon halogen compound. The cyclic carbon halogen compound means a cyclic carbon halogen compound in which all hydrogen atoms bonded to carbon atoms in the hydrocarbon compound are substituted with halogen atoms. In other words, it consists only of carbon atoms and halogen atoms. ​ The term "cyclic halocarbon compound" refers to a cyclic halocarbon compound which is composed of a cyclic halocarbon and does not contain hydrogen atoms.

[0152] The above-mentioned step of dehydrohalogenating a halogenated alkane compound is carried out by using such a ring By carrying out the reaction in the presence of a halogenated hydrocarbon compound, the target halogenated alkene compound can be obtained. The product can be obtained with higher conversion and yield.

[0153] The cyclic halocarbon compound may be any of those mentioned above. The same applies to the introduction method in the liquid phase reaction and the gas phase reaction.

[0154] Reaction temperature In the dehydrohalogenation reaction step of the present disclosure, the lower limit of the reaction temperature is more efficient. The dehydrohalogenation reaction proceeds in a more efficient manner to produce the target compound (halogenated alkene compound). From the viewpoint of obtaining high selectivity, conversion from raw material compounds (halogenated alkane compounds) From the viewpoint of suppressing a decrease in the rate, the temperature is usually 50° C., preferably 70° C., and more preferably It is 100 degrees Celsius.

[0155] In the dehydrohalogenation reaction step of the present disclosure, the upper limit of the reaction temperature is more efficient. The dehydrohalogenation reaction proceeds in a more efficient manner to produce the target compound (halogenated alkene compound). The viewpoint that the reaction can be performed with a high selectivity, and the selectivity due to decomposition or polymerization of the reaction product From the viewpoint of suppressing the decrease in It is 400℃.

[0156] Reaction time In the dehydrohalogenation reaction step of the present disclosure, the reaction time is determined by the amount of the raw material compound that is catalyzed. Contact time (W / F 0 ) [W: weight of catalyst (g), F 0 : Flow rate of raw material compound (cc / sec)] A longer reaction time can increase the conversion rate of the raw material, but it requires a larger amount of catalyst and larger equipment. This is large and inefficient.

[0157] Therefore, in the dehydrohalogenation reaction step in the present disclosure, the reaction time is From the viewpoints of improving the conversion rate of halogenated alkane compounds and reducing equipment costs The contact time of the raw material compound (halogenated alkane compound) with the catalyst (W / F 0 ) is 0.1 Preferably, the value is up to 200 g·sec / cc, and more preferably, the value is 0.2 to 150 g·sec / cc. It is more preferable that the viscosity is 0.4 to 100 g·sec / cc, and particularly preferable that the viscosity is 0.5 to 50 g·sec / cc. Preferred.

[0158] The contact time of the raw material compound with the catalyst means the time during which the raw material compound and the catalyst are in contact with each other. Taste.

[0159] In the present disclosure, when the dehydrohalogenation reaction is carried out in the gas phase in the presence of a catalyst, the catalyst By appropriately adjusting the reaction temperature and reaction time (contact time) according to the The product (a substituted alkene compound) can be obtained with higher selectivity.

[0160] In the dehydrohalogenation reaction of the present disclosure, when chromium oxide is used as a catalyst, The reaction temperature is preferably 300° C. or higher, and more preferably 350° C. or higher. The contact time is preferably 10 g·sec / cc or more, more preferably 20 g·sec / cc or more. It is more preferable that the hardness be 40 g·sec / cc or more, and further more preferable that the hardness be 40 g·sec / cc or more.

[0161] In the dehydrohalogenation reaction of the present disclosure, when alumina is used as a catalyst, the reaction The temperature is preferably 300°C or higher, and the contact time is 5 g·sec / cc or more. preferable.

[0162] In the dehydrohalogenation reaction of the present disclosure, when activated carbon is used as a catalyst, the reaction temperature The temperature is preferably 50 to 600°C, and more preferably 100 to 400°C. The contact time is preferably 0.2 to 100 g·sec / cc, more preferably 0.3 to 50 g·sec / cc. It is more preferable that the viscosity is 0.5 to 43 g·sec / cc, and further more preferable that the viscosity is 0.5 to 43 g·sec / cc.

[0163] Reaction Pressure In the dehydrohalogenation reaction step of the present disclosure, the reaction pressure is adjusted to more efficiently dehalogenate. From the viewpoint of proceeding with the hydrogenation reaction, the pressure is preferably from -0.05 to 2 MPa, and more preferably from -0.01 to 1 MPa. It is more preferable that the pressure is within a range from normal pressure to 0.5 MPa. If no pressure is specified, gauge pressure shall be used.

[0164] In the dehydrohalogenation reaction step of the present disclosure, The reactor for contacting and reacting a compound with a catalyst (activated carbon, metal catalyst, etc.) may be any of the above-mentioned reactors. There are no particular limitations on the shape and structure of the reactor as long as it can withstand the temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multi-tube reactor. Examples of the material include glass, stainless steel, iron, nickel, and iron-nickel alloys.

[0165] Example of dehydrohalogenation reaction In the present disclosure, the dehydrohalogenation reaction step is carried out by adding a raw material compound (halogenated a The target compound (halogenated alkene compound) is continuously charged into the reactor. The method can be either a flow type in which the sample (product) is continuously extracted or a batch type. The target compound (halogenated alkene compound) is not allowed to remain in the reactor, and is further dehalogenated. Since the hydrogenation reaction may proceed, it is preferable to carry out the reaction in a flow system.

[0166] The dehydrohalogenation reaction step in the present disclosure is carried out in the gas phase, particularly using a fixed bed reactor. When the continuous gas phase flow system is used, the apparatus, operation, etc. This simplifies the process and is economically advantageous.

[0167] In the dehydrohalogenation reaction step of the present disclosure, the reaction atmosphere is In order to prevent deterioration of catalysts (activated carbon, metal catalysts, etc.), it is necessary to use an inert gas. In the present disclosure, the inert gas is selected from the group consisting of nitrogen, helium, argon, and carbon dioxide. At least one selected from the group consisting of these inactive Among the gases, nitrogen is more preferable from the viewpoint of reducing costs. The concentration of the inert gas is as follows: It is preferable that the amount is 0 to 50 mol % of the gas components introduced into the reactor.

[0168] In the dehydrohalogenation reaction step of the present disclosure, after the reaction is completed, if necessary, The product is purified according to a conventional method to obtain the desired compound, a halogenated compound represented by the general formula (2B). An alkene compound can be obtained.

[0169] (2-1-3) Target compound (halogenated alkene compound) The target compound of the present disclosure thus obtained is represented by the general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. X 8 represents a halogen atom.] It is a halogenated alkene compound represented by the formula:

[0170] A in general formula (2B) 1 , A 2 and X 8 is A in the above general formula (1B). 1 , A 2 and X 8 and Therefore, the halogenated alkene represented by the general formula (2B) to be produced The compound is, for example, specifically CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz), CF 3 CCl=CHF, CF Cl=CHF, CF 3 CF=CHCF 3 ((Z) or (E)-1327myz), CF 3 CF=CHF, CF 2 =CHF, CF 3 CCl=CHC 2 F 5 , C 2 F 5 CCl=CHC 2 F 5 , C 2 F 5 CCl=CHF, CF 3 CF=CHC 2 F 5 , C 2 F 5 CF=CHC 2 F 5 , C 2 F 5 CF=CHF, etc. These compounds include both Z and E forms.

[0171] The halogenated alkene compounds thus obtained are used in cutting-edge microfabrication for semiconductors, liquid crystals, etc. Etching gases for forming structures, cleaning gases, deposition gases, coolants, heat transfer gases It can be effectively used for various purposes such as a liquid medium and a building block for organic synthesis. The building blocks for organic synthesis are described below.

[0172] [2-2] Method for producing fluorinated alkyne compounds from halogenated alkene compounds The method for producing a halogenated alkyne compound of the present disclosure comprises reacting a compound represented by the general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. ] A method for producing a fluorinated alkyne compound represented by the following formula: General formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 and A 2 is the same as above. X 8 represents a halogen atom.] A step of subjecting a halogenated alkene compound represented by the following formula (1) to a dehydrohalogenation reaction in the presence of a catalyst. Includes.

[0173] (2-2-1) Raw material compound (halogenated alkene compound) The halogenated alkene compound that can be used as a substrate in the production method of the present disclosure is As shown in the general formula (2B): CX 8 A 1 =CHA 2(2B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. X 8 represents a halogen atom.] The halogenated alkene compound is represented by the formula: This corresponds to the target compound in the production process for a halogenated alkene compound from the above-mentioned mixture.

[0174] In the general formula (2B), A 1 and A 2 A perfluoroalkyl group represented by the formula: 8 Denoted by As the halogen atom, those mentioned above can be used. The preferred types are also the same.

[0175] Specific examples of halogenated alkene compounds that can serve as substrates satisfying the above conditions include: CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz), CF 3 CCl=CHF, CFCl=CHF, CF 3 CF=CHCF 3 ((Z) again (E)-1327myz), CF 3 CF=CHF, CF 2 =CHF, CF 3 CCl=CHC 2 F 5 , C 2 F 5 CCl=CHC 2 F 5 , C 2 F 5 CCl=CHF , C.F. 3 CF=CHC 2 F 5 , C 2 F 5 CF=CHC 2 F 5 , C 2 F 5CF=CHF, etc. These compounds are Z-isomers and These halogenated alkene compounds may be used alone or in combination. Such halogenated alkene compounds can be used in combination of two or more. , publicly known or commercially available products can be used.

[0176] (2-2-2) Dehydrohalogenation reaction In the step of dehydrohalogenating a halogenated alkene compound according to the present disclosure, High conversion (yield) and high selectivity of fluorinated alkyne compounds from halogenated alkene compounds For example, the halogen compound represented by the general formula (2B) can be used as a substrate in terms of the fact that it can be produced at a high rate. In the case of alkene compounds, A 1 and A 2 Both are trifluoromethyl groups (CF 3 -) is preferred X 8 is more preferably a fluorine atom or a chlorine atom.

[0177] That is, the reaction is as follows: CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz) → CF 3 C≡CCF 3 (PF2B) + HCl CF 3 CF=CHCF 3 ((Z) or (E)-1327myz) → CF 3 C≡CCF 3 (PF2B) + HF Accordingly, the reaction is preferably a dehydrofluorination reaction or a dehydrochlorination reaction.

[0178] The process of dehydrofluorinating a halogenated butane compound in the present disclosure is carried out in a liquid phase. From the viewpoint of productivity in particular, it is preferable to carry out the reaction in the gas phase. is preferred.

[0179] The step of dehydrohalogenating a halogenated alkene compound in the present disclosure is In view of being able to obtain the target compound with higher selectivity and higher conversion, the catalyst and / or More specifically, when a liquid phase reaction is adopted, it is preferable to carry out the reaction in the presence of a base. It is preferable to carry out the reaction in the presence of a base and, if necessary, a catalyst. When a gas phase reaction is employed, It is preferable to carry out the reaction in the presence of a catalyst. Details of the liquid phase reaction (solvent, base, catalyst, etc.) are given below. For details on cyclic halogenated hydrocarbon compounds, closed reaction systems and pressurized reaction systems, see "Halogen "The reaction of obtaining halogenated butene compounds by dehydrofluorination of halogenated butane compounds" is called " Fluorinated alkyne compounds are obtained from halogenated alkene compounds by dehydrohalogenation. The above [1-1] halogenated butane compound is used except that the above [1-1] reaction is replaced with the above [1-1] reaction. The method for producing a halogenated butene compound from a gas can be adopted. Details of the two-phase reaction (catalyst, cyclic halocarbon compound, reaction temperature, reaction time, reaction pressure, etc.) ) is "a halogenated alkane compound that is dehydrohalogenated to a halogen "Reaction to obtain alkene compounds" is "Dehydrohalogenation reaction from halogenated alkene compounds" The above is the same as above, except that the above is replaced with "a reaction to obtain a fluorinated alkyne compound by [2-1] A method for producing a halogenated alkene compound from a halogenated alkane compound The preferred types and contents are also the same.

[0180] After the dehydrohalogenation reaction is completed, purification treatment is carried out according to conventional methods as necessary. A fluorinated butyne compound represented by formula (3B) can be obtained.

[0181] (2-2-3) Target compound (fluorinated butyne compound) The target compound of the present disclosure thus obtained is represented by the general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. ] It is a fluorinated butyne compound represented by the formula:

[0182] A in general formula (3B) 1 and A 2 is A in the above general formula (2B). 1 and A 2 Corresponding to For this reason, the fluorinated butyne compound represented by the general formula (3B) to be produced is, for example, For example, CF 3 C≡CCF 3 (PF2B), CF 3 C≡CF, CF≡CF, CF 3 C≡CC 2 F 5 , C 2 F 5 C≡CC 2 F 5 , C 2 F 5 Examples include C≡CF.

[0183] The fluorobutyne compounds obtained in this way are useful for creating cutting-edge microstructures in semiconductors, liquid crystals, etc. Etching gases for forming, cleaning gases, deposition gases, coolants, heat transfer media It can be effectively used for various applications such as building blocks for organic synthesis. Building blocks for organic synthesis are described below.

[0184] [2-3] From halogenated alkane compounds, via halogenated alkene compounds, Method for producing fluorinated alkyne compounds The method for producing a fluorinated alkyne compound of the present disclosure includes the steps of: General formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. ] A method for producing a fluorinated alkyne compound represented by the following formula: (IB) General formula (1B): CHX 8 A 1 CHX 9 A 2 (1B) [In the formula, A 1 and A 2 is the same as above. X 8 and X 9 are the same or different and represent a halogen atom. vinegar.] A halogenated alkane compound represented by the following formula is subjected to a dehydrohalogenation reaction in the gas phase in the presence of a catalyst: , general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] A step of producing a halogenated alkene compound represented by the formula: (IIB) removing hydrogen halide after the step (IB); and (IIIB) After the above step (IIB), the obtained general formula (2B): CX 8 A 1 =CHA 2 (2B) [In the formula, A 1 , A 2 and X 8 is the same as above.] A halogenated alkene compound represented by the following formula is subjected to a dehydrohalogenation reaction in the presence of a catalyst in a gas phase. , general formula (3B): CA 1 ≡CA 2 (3B) [In the formula, A 1 and A 2 is the same as above.] A process for producing a fluorinated alkyne compound represented by the following formula: Includes.

[0185] (2-3-1) Process (IB) In the method for producing a fluorinated butyne compound of the present disclosure, the step (IB) is the above-mentioned [2-1] The explanation of the production method from halogenated alkane compounds to halogenated alkene compounds is as it is. It can be adopted.

[0186] (2-3-2) Process (IIB) The method for producing a fluorinated alkyne compound of the present disclosure comprises the steps of: The alkane compound is subjected to a dehydrohalogenation reaction to obtain an alkane halide represented by the above general formula (2B). After producing the alkene compound (step (IB)), a halogenated alkene compound and a hydrogen halide are and removing hydrogen halide from the mixture (IIB).

[0187] In the method for producing a fluorinated alkyne compound according to the present disclosure, after step (IB), After separating and / or removing the hydrogen halide produced in the hydrogen halide reaction, the next step (IIIB) By proceeding to the production of fluorinated alkyne compounds, the target compound can be obtained by dehydrohalogenation reaction. The present invention relates to a method for producing a fluorinated alkyne compound, which is a compound of the present invention, with high conversion (yield) and high selectivity. can.

[0188] From the mixture containing the halogenated alkene compound and hydrogen halide obtained in step (IB), Regarding the method for removing hydrogen halide, the method for removing hydrogen halide from the above-mentioned halogenated butane compound is described below. A method for producing a halogenated butyne compound via a halogenated butene compound (1- 3-2) In the explanation of step (IIA), instead of separating hydrogen fluoride, hydrogen halide is separated. It can be adopted as is, except that it should be read so as to separate.

[0189] (2-3-3) Process (IIIB) In the method for producing a fluorinated alkyne compound according to the present disclosure, the step (IIIB) is 2] The explanation of the production method from halogenated alkene compounds to fluorinated alkyne compounds is as follows. It can be adopted.

[0190] (2-3-4) Example of dehydrohalogenation reaction In the dehydrohalogenation reaction step of the present disclosure, the reaction is carried out by adding, in step (IB), The raw material compound (halogenated alkane compound) is continuously charged, and the target compound is extracted from the reactor. (Halogenated alkene compounds) can be extracted continuously in either a flow system or batch system. Then, the halogenated alkene compound and the hydrogen halide are reacted with each other. From the mixture containing the above, hydrogen halide is removed (step (IIB)), and in step (IIIB), The raw material compound (halogenated alkene compound) is continuously charged into the reactor, and the target compound is extracted from the reactor. The product (fluorinated alkyne compound) is continuously extracted by either a flow method or a batch method. In each step, the target compound (halogenated alkene compound or fluorine compound) is obtained. The dehydrohalogenation reaction can proceed further without allowing the halogenated alkyne compound to remain in the reactor. Therefore, it is preferable to carry out the reaction in a flow-through manner.

[0191] In the dehydrohalogenation reaction step of the present disclosure, the reaction is carried out in a gas phase, particularly in a fixed bed reactor. It is preferable to carry out the reaction in a continuous gas phase flow system using a reactor. This simplifies the operations and is economically advantageous.

[0192] In the dehydrohalogenation reaction step of the present disclosure, the reaction atmosphere is In order to prevent deterioration of catalysts (activated carbon, metal catalysts, etc.), it is necessary to use an inert gas. In the present disclosure, the inert gas is selected from the group consisting of nitrogen, helium, argon, and carbon dioxide. At least one selected from the group consisting of these inactive Among the gases, nitrogen is more preferable from the viewpoint of reducing costs. The concentration of the inert gas is as follows: It is preferable that the amount is 0 to 50 mol % of the gas components introduced into the reactor.

[0193] In the dehydrohalogenation reaction step of the present disclosure, after the reaction is completed, the reaction is carried out in the usual manner as described above. The target compound (halogenated alkene compound or fluorinated alkyne compound) is obtained by purification according to the above. Compounds) can be obtained.

[0194] 3. Composition In the manner described above, the halogenated butene compounds, the halogenated butyne compounds, the halogenated a Although an alkene compound or a fluorinated alkyne compound can be obtained, a composition containing the target compound It may also be obtained in the form of

[0195] [3-1] Composition containing a halogenated butene compound or a halogenated alkene compound According to the production method of the present disclosure, for example, the above-mentioned [1-1] halogenated butane compound can be In the case of the method for producing a halogenated butene compound, for example, a halogenated butene compound represented by the general formula (2A) can be produced. The halogenated butene compound may be obtained as a composition containing both E and Z isomers. The composition also has the general formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [where, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above.] and halogenated butyne compounds represented by the formula: General formula (4): CX 1 X 2 =CX 4 CF=CX 5 X 6 (4) [where, X 1 , X 2 , X 4 , X 5 and X 6 is the same as above.] The halogenated butadiene compound may also be represented by the following formula:

[0196] In the general formulae (2A), (3A) and (4), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 Shown in Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. Fluorine and chlorine atoms are preferred, and fluorine atoms are more preferred.

[0197] The total amount of the composition of the present disclosure is taken as 100 mol %, and the halogenated butene represented by the general formula (2A) is The content of the aryl compound is preferably 80.00 to 99.99 mol %, more preferably 90.00 to 99.98 mol %, and even more preferably 92.0 More preferably, the content is 0 to 99.97 mol %. In addition, the halogenated butyne compound represented by the general formula (3A) The content is preferably 0.00 to 3.00 mol %, more preferably 0.01 to 2.00 mol %, but may vary depending on synthesis conditions. Therefore, the content may be 1.00 to 10.00 mol % (particularly, 2.00 to 8.00 mol %). The content of the halogenated butadiene compound represented by the formula (1) is preferably 0.00 to 0.50 mol %, and more preferably 0.01 It is more preferable that the halogenated butene compound represented by the general formula (2A) is E When both the isomer and the Z isomer are contained, the above content is the total amount thereof.

[0198] According to the production method of the present disclosure, a halogenated butene compound represented by general formula (2A) Therefore, it is possible to selectively synthesize the E-isomer. The content of (Z)-halogenated bromine is preferably 85.00 to 99.98 mol % (particularly, 86.00 to 99.00 mol %). The content of the thene compound is preferably 0.01 to 15.00 mol % (particularly, 1.00 to 14.00 mol %).

[0199] According to the production method of the present disclosure, a halogenated butene composition is obtained. However, as described above, the halogenated butene compound represented by the general formula (2A) is Since the halogenated butene composition can be obtained with high yield and high selectivity, It is possible to reduce components other than the halogenated butene compound represented by the general formula (2A). Therefore, the purification effort required to obtain the halogenated butene compound represented by the general formula (2A) is reduced. It is possible.

[0200] On the other hand, [2-1] A method for producing a halogenated alkene compound from a halogenated alkane compound According to the method, for example, a halogenated alkene compound represented by the general formula (2B) and at least In any case, one kind of hydrofluorocarbon (HFC) compound (halogen represented by the above general formula (2B) and at least one additional compound consisting of a cyclic alkene compound (excluding cyclic alkene compounds). can be generated.

[0201] The additional compounds are hexafluorobutene, hexafluorobutane and octafluoro. It is preferable that the solvent is at least one selected from the group consisting of butane.

[0202] Specifically, the production of halogenated alkene compounds from the halogenated alkane compounds of the present disclosure. In this method, the target substance is 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (1326mxz). When this is obtained, (Z)-1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz(Z)) is produced. It is possible.

[0203] The composition containing the halogenated alkene compound represented by the general formula (2B) of the present disclosure is The content of the halogenated alkene compound represented by the general formula (2B) is taken as 100 mol %. It is preferable that the content of the additional compound is 80 mol % or more, and the content of the additional compound is 20 mol % or less. In the disclosed composition containing a halogenated alkene compound represented by general formula (2B), The content of the halogenated alkene compound represented by the general formula (2B) is taken as 100 mol % of the total amount of the composition. The amount is preferably 85 mol % or more, more preferably 90 mol % or more, and It is more preferable that the halogenated alkanes represented by the general formula (2B) of the present disclosure have a content of 1.0% or more. In a composition containing an oxy compound, the total amount of the composition is taken as 100 mol %, and the compound represented by the general formula (2B) is The content of the halogenated alkene compound represented by the formula (I) is preferably 80 to 99.9 mol%, more preferably 85 to 99.9 mol%. is more preferable, 90 to 99.9 mol % is further preferable, and 95 to 99.9 mol % is particularly preferable.

[0204] [3-2] Composition containing a halogenated butyne compound or a fluorinated alkyne compound According to the production method of the present disclosure, for example, the above-mentioned [2-2] halogenated alkene compound can be In the case of the method for producing a fluorinated alkyne compound from the above-mentioned compound represented by the general formula (3B), for example, and at least one hydrofluorocarbon (HFC) compound ( At least one compound selected from the group consisting of fluorinated alkyne compounds represented by the general formula (3B) [1-2] A composition containing a halogenated butene compound and an additional compound can be produced. When the method for producing a genonated butyne compound is followed, the resulting composition has the general formula (3A) and a hydrofluorocarbon (HFC) compound (see above) At least one additional compound consisting of the halogenated butyne compound represented by the general formula (3A) A composition containing the additive may be formed.

[0205] The additional compounds are trifluoromethane, difluoromethane, tetrafluoromethane and It is preferable that the fluorocarbon is at least one selected from the group consisting of monofluoromethane. stomach.

[0206] The present disclosure relates to a method for producing a halogenated butyne compound from a halogenated butene compound, and In the process for obtaining a fluorinated alkyne compound from a fluorinated alkene compound, the target product is 1,1, When obtaining 1,4,4,4-hexafluoro-2-butyne (PF2B), trifluoromethane (HFC-23, R 23) can be generated.

[0207] The composition comprising the halogenated butyne compound or the fluorinated alkyne compound of the present disclosure is The content of halogenated butyne compounds or fluorinated alkyne compounds, based on the total amount of the composition being 100 mol % is preferably 80 mol % or more, and the content of the additional compound is preferably 20 mol % or less. In a composition containing a halogenated butyne compound or a fluorinated alkyne compound, The content of the halogenated butyne compound or the fluorinated alkyne compound is, with the total amount being 100 mol%, It is preferably 85 mol % or more, more preferably 90 mol % or more, and more preferably 95 mol % or more. It is more preferable that the halogenated butyne compound or the fluorinated alkyne compound of the present disclosure is the above. In the composition containing the halogenated butyne compound, the total amount of the composition is taken as 100 mol %. The content of the compound or fluorinated alkyne compound is preferably 80 to 99.9 mol %, more preferably 85 to 99.9 mol %. It is preferably from 90 to 99.9 mol %, more preferably from 95 to 99.9 mol %.

[0208] [3-3] Halogenated butene compounds, halogenated butyne compounds, halogenated alkenes Use of the composition containing the compound or fluorinated alkyne compound - Patents.com According to the manufacturing method of the present disclosure, a halogenated butene compound, a halogenated butyne compound, a halogenated In the case where the composition contains a fluorinated alkene compound or a fluorinated alkyne compound, However, halogenated butene compounds, halogenated butyne compounds, halogenated alkene compounds or can obtain a fluorinated alkyne compound with particularly high selectivity, and as a result, Halogenated butene compounds, halogenated butyne compounds, halogenated alkene compounds and fluorine compounds According to the production method of the present disclosure, it is possible to reduce components other than the substituted alkyne compound. , halogenated butene compounds, halogenated butyne compounds, halogenated alkene compounds or fulvene compounds. The purification effort required to obtain a fluorinated alkyne compound can be reduced.

[0209] The halogenated butene compounds, halogenated butyne compounds, and halogenated alkene compounds of the present disclosure The composition containing the compound or fluorinated alkyne compound is a halogenated butene compound, a halogenated butyric acid compound, Alkene compounds, halogenated alkene compounds, or fluorinated alkyne compounds, each of which is the same as the case of using them alone. In addition to etching gases for forming cutting-edge microstructures in semiconductors, liquid crystal, etc., Gases for heating, depositing, refrigerants, heat transfer media, building blocks for organic synthesis, etc. It can be effectively used for various purposes.

[0210] The deposition gas is a gas that deposits an etch-resistant polymer layer.

[0211] The building block for organic synthesis is a precursor of a compound having a highly reactive skeleton. For example, the composition of the present disclosure and CF 3 Si(CH 3 ) 3 Fluorine-containing organic ketones such as When reacted with isopropyl compounds, CF 3 By introducing fluoroalkyl groups such as fluorine-containing groups, cleaning agents and It is possible to convert them into substances that can become intermediates for pharmaceuticals.

[0212] Although the embodiments of the present disclosure have been described above, it is to be understood that the present disclosure is not limited to the above-mentioned embodiments. Various modifications of form and details are possible without departing from the spirit and scope of the invention. EXAMPLES

[0213] Examples are given below to clarify the features of the present disclosure. The present disclosure is limited to these examples. It's not something like that.

[0214] In the methods for producing halogenated butene compounds in Examples 1 to 7, the raw material compound is represented by the general formula (1A): In the halogenated butane compound represented by the formula: X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is a fluorine atom and the following reaction scheme: CF 3 CFHCFHCF 3 → CF 3 CF=CHCF 3 + HF According to the above, a halogenated butene compound was obtained by dehydrofluorination reaction.

[0215] In the method for producing a halogenated alkene compound and a fluorinated butyne compound in Example 8, The compound is a halogenated alkane compound represented by the general formula (1B), 8 and X 9 Chlorine source As a child, A 1 and A 2 is a trifluoromethyl group, and the reaction is as follows: CF 3 CHClCHClCF 3 (336mdd) → CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz) + HCl CF 3 CCl=CHCF 3 ((Z) or (E)-1326mxz) → CF 3 C≡CCF 3 (PF2B) + HCl According to the above, a halogenated alkene compound and a fluorinated butyne compound are obtained by a dehydrochlorination reaction. Got it.

[0216] In the methods for producing the halogenated alkene compounds and fluorinated butyne compounds of Examples 9 to 20, the raw materials are The starting compound is a halogenated alkane compound represented by the general formula (1B), 8 and X 9 Hafu fluorine atom, A 1 and A 2 is a trifluoromethyl group, and the reaction is as follows: CF 3 CHFCHFCF 3 (338mee) → CF 3 CF=CHCF 3 ((Z) or (E)-1327myz) + HF CF 3 CF=CHCF 3 ((Z) or (E)-1327myz) → CF 3 C≡CCF 3 (PF2B) + HF According to the above, a halogenated alkene compound and a fluorinated butyne compound are obtained by dehydrofluorination reaction. obtained.

[0217] Examples 1 to 3: Liquid Phase Reactions An autoclave (200 cc) was used as the reaction system.

[0218] By using an autoclave as a reaction system, the reaction system can be carried out in the following manner: (1) in the presence of a base (2) The reaction temperature is 10°C or higher, and the reaction pressure is 0 kPa or higher. This represents an embodiment of a pressurized reaction system carried out in the presence of a base. This involves:

[0219] In the autoclave, add 50 ml of KOH or potassium tert-butoxide (t-BuOK) as the reaction solution. Add 7.0 g of 100% aqueous solution of methyltrioctylammonium chloride as a catalyst if necessary. 0.28 g of CF336 (trade name) was added, and the raw material compound (CF 3 CFHCFHCF 3 ) and cover. After the system was sealed, nitrogen was pumped in. The pressure was 20 kPa. After that, the mixture was stirred at room temperature (25°C) to allow the reaction to proceed. Sampling was carried out as necessary, and the reaction was deemed to be complete when there was no change in the composition of the reaction system. The pressure at the end was 80 kPa.

[0220] After stirring was stopped, the mixture was cooled to 0°C and analyzed by gas chromatography (Shimadzu Corporation, product name Mass spectrometry was performed using a gas chromatography / mass spectrometry (GC / MS) The structure was analyzed by NMR spectroscopy using an NMR (JEOL, product name "400YH"). The results of mass spectrometry and structural analysis showed that the target compound was CF 3 CF=CHCF 3 What was generated The results are shown in Table 1.

[0221] Examples 4 to 6: Gas phase reactions (activated carbon) The reaction tube is a stainless steel pipe (outer diameter: 1 / 2 inch), and an activated carbon catalyst (Osaka Gas Chemicals) is used as a catalyst. Manufactured by Lubricants Co., Ltd.; specific surface area 1200m 2 After drying at 200°C for 2 hours under a nitrogen atmosphere, , pressure is normal pressure, CF 3 CFHCFHCF 3 The contact time (W / F) between the raw material compound and the activated carbon catalyst is 15g·se c / cc, 30g sec / cc or 47g sec / cc. 3 CFHCFHCF 3 (raw material combination The company circulated a wide range of products.

[0222] The reaction was carried out in a continuous gas phase flow mode.

[0223] The reaction tube was heated to 450° C. to initiate the dehydrofluorination reaction.

[0224] One hour after the start of the dehydrofluorination reaction, the distillate that had passed through the detoxification tower was collected.

[0225] Then, gas chromatography (Shimadzu Corporation, product name "GC-2014") was used. Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL The structure was analyzed by NMR spectroscopy using a 400YH (manufactured by Epson Corporation). From the results of structural analysis, CF 3 CF=CHCF 3 It was confirmed that was produced. As shown in Table 1.

[0226] Example 7: Gas phase reaction (chromium oxide catalyst) Chromium oxide catalyst (Cr 2 O 3 ) was used, the reaction temperature was 350°C, and CF 3 CFHCFHCF 3 (raw material The same procedure was repeated as in Example 4 to 6, except that the contact time (W / F) between the mixture and the chromium oxide catalyst was 47 g sec / cc. The reaction was carried out in the same manner as in 6. Mass spectrometry and structural analysis revealed that CF was the target compound. 3 CF =CHCF 3 The results are shown in Table 1.

[0227] [Table 1]

[0228] Example 8 (Dehydrochlorination) 336mdd(CF 3 CHClCHClCF3 ) → 1326mxz(CF 3 CCl=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) (1) 336mdd(CF 3 CHClCHClCF 3 ) → 1326mxz(CF 3 CCl=CHCF 3 ) The reaction tube is made of stainless steel (outer diameter: 1 / 2 inch) and the catalyst is activated carbon (comparison Surface area 1200m 2 After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure was reduced to normal pressure. , C.F. 3 CHClCHClCF 3 Contact time between the raw material compound and the activated carbon catalyst (W / F 0 ) is 5g·sec / cc or 2 CF was added to the reactor to achieve a flow rate of 5g·sec / cc. 3 CHClCHClCF 3 (Raw material compound) was distributed.

[0229] The reaction was carried out in a continuous gas phase flow system.

[0230] The reactor was heated to 300° C. or 400° C. to initiate dehydrochlorination.

[0231] (2) Removal of hydrogen chloride One hour after the start of dehydrochlorination, the distillate that had passed through the scavenging tower was collected.

[0232] Then, gas chromatography (Shimadzu Corporation, product name "GC-2014") was used. Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Structural analysis was carried out by NMR spectroscopy using a tertiary amine compound (manufactured by Epson Corporation, trade name "400YH").

[0233] From the results of mass spectrometry and structural analysis, it was found that the target compound was a halogenated alkene compound (1326 mxz:CF 3 CCl=CHCF 3 ) was confirmed to have been produced.

[0234] In addition, in the method for producing a halogenated alkene compound from a halogenated alkane compound, The target is 1326mxz (CF 3 CCl=CHCF 3 ), (Z)-1,1,1,4,4,4-hexafluorobuta-2- Ene (HFO-1336mzz(Z)) was produced.

[0235] [Table 2]

[0236] (3) 1326mxz(CF 3 CCl=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) The reaction tube is made of stainless steel (outer diameter: 1 / 2 inch) and the catalyst is activated carbon (comparison Surface area 1200m 2 / g) was filled in 10 g.

[0237] In this operation, the reaction gas containing the halogenated alkene compound produced by the above method is reacted again. The method is to return the wastewater to the first reactor, or to the next reactor (second reactor) filled with activated carbon catalyst. The reaction was carried out by passing it through.

[0238] The hydrogen chloride concentration in the reaction gas containing the halogenated alkene compound at that time was 50 mol%. The reaction gas coming out of the first reactor is rectified, alkali-treated, SEKADO-treated, and alumina-treated. The hydrogen chloride concentration was adjusted to 20 mol %, 3 mol %, or 0.1 mol % by the above method or other methods.

[0239] After drying at 200°C for 2 hours under nitrogen atmosphere, the pressure was reduced to normal pressure and CF 3 CCl=CHCF 3 (raw material compound) Contact time with activated carbon catalyst (W / F 0 ) is 0.5g·sec / cc, 20g·sec / cc or 43g·sec / cc The reactor was then filled with CF 3 CCl=CHCF 3 (Raw material compound) was distributed.

[0240] The reaction was carried out in a continuous gas phase flow system.

[0241] The reactor was heated to 400° C. to initiate dehydrochlorination.

[0242] One hour after the start of dehydrochlorination, the distillate that had passed through the scavenging tower was collected.

[0243] Then, gas chromatography (Shimadzu Corporation, product name "GC-2014") was used. Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Structural analysis was carried out by NMR spectroscopy using a tertiary amine compound (manufactured by Epson Corporation, trade name "400YH").

[0244] From the results of mass spectrometry and structural analysis, the target compound was identified as a fluorinated alkyne compound (PF2B(CF 3 C≡CCF 3 ) was confirmed to have been produced.

[0245] In the above-mentioned method for producing a fluorinated alkyne compound from a halogenated alkene compound, In addition to PF2B, trifluoromethane (HFC-23, R23) was also produced.

[0246] [Table 3]

[0247] Example 9 (Dehydrofluorination) 338mee(CF 3 CHFCHFCF 3 ) →1327myz(CF 3 CF=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) (1) 338mee(CF 3 CHFCHFCF 3 ) →1327myz(CF 3 CF=CHCF 3 ) The reaction tube is made of stainless steel (outer diameter: 1 / 2 inch) and the catalyst is activated carbon (comparison Surface area 1200m 2 / g) was filled in 10 g.

[0248] After drying at 200°C for 2 hours under nitrogen atmosphere, the pressure was reduced to normal pressure and CF 3 CHFCHFCF 3 (raw material compound) Contact time with activated carbon catalyst (W / F 0 ) is 5g·sec / cc or 25g·sec / cc. CF 3 CHFCHFCF 3 (Raw material compound) was distributed.

[0249] The reaction was carried out in a continuous gas phase flow system.

[0250] The reactor was heated to 100° C., 200° C., 300° C., or 400° C. to initiate dehydrofluorination.

[0251] (2) Removal of hydrogen fluoride One hour after the start of dehydrofluorination, the distillate that had passed through the removal tower was collected.

[0252] Then, gas chromatography (Shimadzu Corporation, product name "GC-2014") was used. Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Structural analysis was carried out by NMR spectroscopy using a tertiary amine compound (manufactured by Epson Corporation, trade name "400YH").

[0253] From the results of mass spectrometry and structural analysis, it was found that the target compound was a halogenated alkene compound (1327 myz:CF 3 CF=CHCF 3 ) was confirmed to have been produced.

[0254] (3) 1327myz(CF 3 CF=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) The reaction tube is made of stainless steel (outer diameter: 1 / 2 inch) and the catalyst is activated carbon (comparison Surface area 1200m 2 / g) was filled in 10 g.

[0255] In this operation, the reaction gas containing the halogenated alkene compound produced by the above method is reacted again. The method is to return the wastewater to the first reactor, or to the next reactor (second reactor) filled with activated carbon catalyst. The reaction was carried out by passing it through.

[0256] The hydrogen chloride concentration in the reaction gas containing the halogenated alkene compound at that time was 50 mol%. The reaction gas coming out of the first reactor is rectified, alkali-treated, SEKADO-treated, and alumina-treated. The hydrogen chloride concentration was adjusted to 20 mol %, 3 mol %, or 0.1 mol % by the above method or other methods.

[0257] After drying at 200°C for 2 hours under nitrogen atmosphere, the pressure was reduced to normal pressure and CF 3 CCl=CHCF 3 (raw material compound) Contact time with activated carbon catalyst (W / F 0 ) is 0.5g·sec / cc, 20g·sec / cc or 43g·sec / cc The reactor was then filled with CF 3 CF=CHCF 3 (Raw material compound) was distributed.

[0258] The reaction was carried out in a continuous gas phase flow system.

[0259] The reactor was heated to 400° C. to initiate dehydrofluorination.

[0260] One hour after the start of dehydrofluorination, the distillate that had passed through the removal tower was collected.

[0261] Then, gas chromatography (Shimadzu Corporation, product name "GC-2014") was used. Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Structural analysis was carried out by NMR spectroscopy using a tertiary amine compound (manufactured by Epson Corporation, trade name "400YH").

[0262] From the results of mass spectrometry and structural analysis, the target compound was identified as a fluorinated alkyne compound (PF2B(CF 3 C≡CCF 3 ) was confirmed to have been produced.

[0263] In the above-mentioned method for producing a fluorinated alkyne compound from a halogenated alkene compound, In addition to PF2B, trifluoromethane (HFC-23, R23) was also produced.

[0264] [Table 4]

[0265] Examples 10 to 16 (Dehydrofluorination) 338mee(CF 3 CHFCHFCF 3 ) →1327myz(CF 3 CF=CHCF 3 ) The reaction tube is made of stainless steel (outer diameter: 1 / 2 inch) and the catalyst is activated carbon (comparison Surface area 1200m 2 After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure was reduced to normal pressure. , C.F. 3 CHFCHFCF 3 Contact time between the raw material compound and the activated carbon catalyst (W / F 0 ) is 2 to 47 g·sec / cc The reactor was charged with CF 3 CHFCHFCF 3 (The raw material compound) was distributed. Then, Examples 10 to 13 So, CF 3 CHFCHFCF 3 (Raw material compound) 1 mole per 4 moles of octafluorocyclobutane ( cC 4 F 8 ; C318) was put into circulation.

[0266] The reaction was carried out in a continuous gas phase flow system.

[0267] The reactor was heated to 400° C. to initiate dehydrochlorination.

[0268] One hour after the start of dehydrochlorination, the distillate that had passed through the scavenging tower was collected.

[0269] Then, gas chromatography (Shimadzu Corporation, product name "GC-2014") was used. Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Structural analysis was carried out by NMR spectroscopy using a tertiary amine compound (manufactured by Epson Corporation, trade name "400YH").

[0270] From the results of mass spectrometry and structural analysis, it was found that the target compound was a halogenated alkene compound (1327 myz:CF 3 CF=CHCF 3 ) was confirmed to have been produced.

[0271] In addition, in the method for producing a halogenated alkene compound from a halogenated alkane compound, The target is 1327myz (CF 3 CF=CHCF 3 ), 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz), 1,1,1,4,4,4-hexafluoro-2-butyne (PF2B), etc. were produced.

[0272] [Table 5]

[0273] Examples 17 to 20 (Dehydrofluorination) 1327myz(CF 3 CF=CHCF 3 ) → PF2B(CF 3 C≡CCF 3 ) The reaction tube is made of stainless steel (outer diameter: 1 / 2 inch) and the catalyst is activated carbon (comparison Surface area 1200m 2 After drying at 200°C for 2 hours under a nitrogen atmosphere, the pressure was reduced to normal pressure. , C.F. 3 CF=CHCF 3 Contact time between the raw material compound and the activated carbon catalyst (W / F 0 ) is 2g·sec / cc, 2.8g· sec / cc or 10g sec / cc. 3 CF=CHCF3 (Raw material compound) was distributed Then, in Examples 17-18, CF 3 CF=CHCF 3 4 moles of octadecane per mole of raw material Fluorocyclobutane (cC 4 F 8 ; C318) was put into circulation.

[0274] The reaction was carried out in a continuous gas phase flow system.

[0275] The reactor was heated to 400° C. to initiate dehydrochlorination.

[0276] One hour after the start of dehydrochlorination, the distillate that had passed through the scavenging tower was collected.

[0277] Then, gas chromatography (Shimadzu Corporation, product name "GC-2014") was used. Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Structural analysis was carried out by NMR spectroscopy using a tertiary amine compound (manufactured by Epson Corporation, trade name "400YH").

[0278] From the results of mass spectrometry and structural analysis, the target compound was identified as a fluorinated alkyne compound (PF2B:CF 3 C≡CCF 3 ) was confirmed to have been produced.

[0279] In addition, in the method for producing a halogenated alkene compound from a halogenated alkane compound, The target substance is PF2B (CF 3 C≡CCF 3 In addition to trifluoromethane (HFC-23, R23), It was.

[0280] [Table 6]

Claims

1. General formula (3A): CX 1 X 2 X 3 C≡CCX 5 X 6 X 7 (3A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 and are the same or different and each represents a halogen atom. In the presence of at least one catalyst selected from the group consisting of an activated carbon catalyst and a chromium oxide catalyst, General formula (2A): CX 1 X 2 X 3 CX 4 =CHCX 5 X 6 X 7 (2A) [In the formula, X 1 , X 2 , X 3 , X 5 , X 6 and X 7 is the same as above. X 4 represents a halogen atom.] in a gas phase dehydrohalogenation reaction of the halogenated butene compound represented by the formula (1). A manufacturing method comprising:

2. The manufacturing method described in claim 1, wherein the dehydrohalogenation reaction process is carried out in a gas phase continuous flow system.

3. A method for producing a hydrocarbon compound according to claim 1 or 2, wherein the dehydrohalogenation reaction step is carried out in the presence of a cyclic hydrocarbon halide compound in which all hydrogen atoms bonded to carbon atoms in a hydrocarbon compound are replaced with halogen atoms.

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