Method for producing fluorine-containing aromatic compound

Abstract

To provide a novel method that makes it possible to efficiently produce a fluorine-containing aromatic compound, such as perfluorotoluene.SOLUTION: According to a method herein, a compound represented by general formula (2) [where X3 may be the same or different, each representing a hydrogen atom or a halogen atom other than a fluorine atom. Provided that, in the group -CX33, at least one of the three X3s is a halogen atom other than a fluorine atom. X4 may be the same or different, each representing a hydrogen atom or a halogen atom. Provided that, among the n X4, at least one is a fluorine atom. n is an integer from 1 to 5] is reacted with a metal fluoride, thereby fluorinating at least one X3 in the group -CX33.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a fluorine-containing aromatic compound. [Background technology]

[0002] As a method for producing perfluorotoluene, which is expected to be used as a next-generation etching gas, for example, it is known that (trichloromethyl)pentafluorobenzene synthesized by a specific method is reacted with anhydrous potassium fluoride in dimethylformamide (DMF) in the presence of hexamethylguanidinium fluoride as a catalyst to perform fluorination (see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] China Patent Application Publication No. 112441876 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a novel method for efficiently producing a fluorine-containing aromatic compound such as perfluorotoluene. [Means for solving the problem]

[0005] The present disclosure encompasses the following configurations.

[0006] Term 1. General formula (1):

[0007] [ka]

[0008] [In the formula, X 1 are the same or different and represent a hydrogen atom or a halogen atom, provided that the group -CX1 In 3, 3 X's 1 At least one of the groups is a fluorine atom. X 2 are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 2 At least one of these is a fluorine atom. n represents an integer of 1 to 5. A method for producing a compound represented by the following formula: General formula (2):

[0009] [ka]

[0010] [In the formula, n is the same as above. X 3 are the same or different and each represents a hydrogen atom or a halogen atom other than a fluorine atom, provided that the group -CX 3 In 3, 3 X's 3 At least one of these is a halogen atom other than a fluorine atom. X 4 are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 4 At least one of these is a fluorine atom. and a compound represented by the formula: and reacting with a metal fluoride to form at least one group, -CX 3 One or more X's in 3 3 to produce a compound represented by the general formula (1) A manufacturing method comprising:

[0011] Item 2. Said X 1 are all fluorine atoms.

[0012] Item 3. The method according to item 1 or 2, wherein the reaction is carried out in a solvent.

[0013] Item 4. The method according to Item 3, wherein the solvent is an aprotic polar solvent.

[0014] Item 5. The method according to any one of Items 1 to 4, wherein the metal fluoride is a fluoride of an alkali metal and / or an alkaline earth metal.

[0015] Item 6. The method according to any one of Items 1 to 5, wherein the reaction is carried out in the presence of a phosphonium salt.

[0016] Item 7. The method according to any one of Items 1 to 6, wherein the reaction temperature in the reaction is 0 to 130° C.

[0017] Section 8. General formula (1A):

[0018] [ka]

[0019] [In the formula, X 2 are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 2 At least one of these is a fluorine atom. n represents an integer of 1 to 5. and a compound represented by the formula: General formula (1B):

[0020] [ka]

[0021] [In the formula, X 1a are the same or different and represent a hydrogen atom or a halogen atom, provided that the group -CX 1a In 3, 3 X's 1a One or two of these are fluorine atoms, and the remaining two or one are hydrogen atoms or halogen atoms other than fluorine atoms. X 2 are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 2 At least one of these is a fluorine atom. n represents an integer of 1 to 5. A composition comprising a compound represented by the formula:

[0022] Item 9. Furthermore, the general formula (3):

[0023] [ka]

[0024] [where, X 2 and n is the same as above.] A compound represented by the formula: General formula (4):

[0025] [ka]

[0026] [where, X 1 and n is the same as above. X 2a are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 2a At least one of them is a fluorine atom and at least one of them is a hydrogen atom. At least one additional compound selected from the group consisting of compounds represented by Item 9. The composition according to item 8, comprising:

[0027] Item 10. The composition according to item 8 or 9, wherein the content of the compound represented by general formula (1B) is 0.01 to 15.00 mol %, relative to 100 mol % of the total amount of the composition.

[0028] Item 11. The composition according to item 9 or 10, wherein the content of the additional compound is 0.01 to 2.00 mol % relative to 100 mol % of the total amount of the composition.

[0029] Section 12. Said X 1 Item 12. The composition according to any one of items 9 to 11, wherein each of the is a fluorine atom.

[0030] Item 13. The composition according to any one of items 8 to 12, which is used as an etching gas, a cleaning gas, or a deposit gas. Effect of the Invention

[0031] According to the present disclosure, a novel method for efficiently producing a fluorine-containing aromatic compound can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] In this specification, the term "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of."

[0033] In this specification, when a numerical range is indicated as "A to B," it means A or more and B or less.

[0034] In the present disclosure, "selectivity" means the ratio (mol %) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the total molar amount of compounds other than the raw material compound in the effluent gas.

[0035] In the present disclosure, the term "conversion rate" means the ratio (mol %) of the total molar amount of compounds other than the raw material compounds contained in the effluent gas from the reactor outlet to the molar amount of the raw material compounds supplied to the reactor.

[0036] In the present disclosure, the term "yield" refers to the ratio (mol %) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the molar amount of the raw material compounds supplied to the reactor.

[0037] 1. Method for producing fluorine-containing aromatic compounds The manufacturing method of the present disclosure includes: General formula (1):

[0038] [ka]

[0039] [In the formula, X 1 are the same or different and represent a hydrogen atom or a halogen atom, provided that the group -CX 1 In 3, 3 X's 1 At least one of the groups is a fluorine atom. X 2 are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 2 At least one of these is a fluorine atom. n represents an integer of 1 to 5. A method for producing a compound represented by the following formula: General formula (2):

[0040] [ka]

[0041] [In the formula, n is the same as above. X 3 are the same or different and each represents a hydrogen atom or a halogen atom other than a fluorine atom, provided that the group -CX 3 In 3, 3 X's 3 At least one of these is a halogen atom other than a fluorine atom. X 4 are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 4 At least one of these is a fluorine atom. and a compound represented by the formula: and reacting with a metal fluoride to form at least one group, -CX 3 One or more X's in 3 3 to produce a compound represented by the general formula (1) Equipped with.

[0042] In addition, X 4 At least one of X must be a fluorine atom. 4When all of are hydrogen atoms or halogen atoms other than fluorine atoms, the reaction hardly proceeds, and even if the temperature is increased, the target compound represented by general formula (1) is hardly obtained.

[0043] (1-1) Starting compound (general formula (2)) In the production method of the present disclosure, the compound represented by general formula (2) is represented by general formula (2):

[0044] [ka]

[0045] [In the formula, X 3 are the same or different and each represents a hydrogen atom or a halogen atom other than a fluorine atom, provided that the group -CX 3 In 3, 3 X's 3 At least one of these is a halogen atom other than a fluorine atom. X 4 are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 4 At least one of these is a fluorine atom. n represents an integer of 1 to 5. It is a compound represented by the formula:

[0046] In the general formula (2), X 3 The halogen atom other than the fluorine atom represented by the formula (I) is not particularly limited and examples thereof include a chlorine atom, a bromine atom, an iodine atom, etc. Among these, a chlorine atom is preferred from the viewpoints of conversion rate, selectivity, yield, etc.

[0047] X 3 may be a hydrogen atom or a halogen atom other than a fluorine atom, but X 3 When all of the -CX groups are hydrogen atoms, the reaction hardly proceeds and the target compound represented by general formula (1) is hardly obtained even if the temperature is increased. 3 In 3, 3 X's 3At least one of these is a halogen atom other than a fluorine atom.

[0048] In the general formula (2), X 4 The halogen atom represented by the formula (I) is not particularly limited and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among these, a fluorine atom is preferred from the viewpoints of conversion rate, selectivity, yield, etc.

[0049] However, as mentioned above, X 4 When all of the X's are hydrogen atoms or halogen atoms other than fluorine atoms, the reaction hardly proceeds and the target compound represented by general formula (1) is hardly obtained even if the temperature is increased. 4 At least one of the X's is a fluorine atom. For example, when n is 5, there are five X's. 4 Among these, the number of fluorine atoms is 1 to 5, and from the viewpoints of conversion rate, selectivity, yield, etc., 2 to 5 is preferable, 3 to 5 is more preferable, and 4 to 5 is even more preferable.

[0050] In the general formula (2), n is an integer of 1 to 5. From the viewpoints of conversion rate, selectivity, yield, etc., n is preferably an integer of 2 to 5, more preferably an integer of 3 to 5, and even more preferably an integer of 4 to 5.

[0051] In addition, X 4 When n, which is the number of substitutions, is 5, the compound represented by general formula (2) is represented by general formula (2A):

[0052] [ka]

[0053] [In the formula, R 3 and X 4 is the same as above.] It is a compound represented by the formula:

[0054] In the present disclosure, the compound represented by the general formula (2) used as a substrate preferably does not contain a nitro group. When a compound having a nitro group is used as a substrate, the group -CX 3 The reactivity of 3 is extremely high, and side reactions occur, which tends to reduce the selectivity of the target product. .

[0055] Specific examples of the compound represented by the general formula (2) that satisfies the above conditions include

[0056] [ka]

[0057] [ka]

[0058] etc.

[0059] The compound represented by the above general formula (2) may be a known or commercially available product. The compound represented by the above general formula (2) may be used alone or in combination of two or more kinds.

[0060] (1-2) Reaction In the reaction of the present disclosure, in the compound represented by the above general formula (2), at least the group -CX 3 One or more X's in 3 3 is fluorinated to produce the compound represented by the above general formula (1). In particular, in the compound represented by the above general formula (2), at least the group -CX 3 All X's in 3 3 is fluorinated, and X 1 In this case, the compound represented by the above general formula (1), in which each of

[0061] In this case, X 4 When X is a hydrogen atom or a fluorine atom, it remains unchanged after the reaction of the present disclosure. 4When is a hydrogen atom or a fluorine atom, X 2 is also a hydrogen atom or a fluorine atom.

[0062] On the other hand, X 4 When is a halogen atom other than a fluorine atom, the fluorine atom is converted by the reaction of the present disclosure. It is easy to simplify. That is, X 4 When is a halogen atom other than a fluorine atom, X 2 tends to become a fluorine atom.

[0063] From the above, in the reaction of the present disclosure, in the compound represented by the above general formula (2), X 4 If contains halogen atoms other than fluorine atoms, one or more X 4 Halogen atoms other than the fluorine atom represented by the formula (1) are also easily fluorinated to produce the compound represented by the formula (1). 4 If contains halogen atoms other than fluorine atoms, all X 4 is fluorinated, and X 2 In this case, the compound represented by the above general formula (1), in which each of

[0064] On the other hand, in the compound represented by the above general formula (2), X 4 When contains a hydrogen atom or a fluorine atom, the hydrogen atom or the fluorine atom remains unchanged after the reaction of the present disclosure.

[0065] As a result, a compound represented by general formula (1) is obtained.

[0066] The reaction of the present disclosure can be carried out in either a batch system in which the raw materials are charged into a reactor all at once, or a flow system in which the raw materials are continuously fed into a reactor while the product is withdrawn from the reactor.

[0067] The above reaction can be carried out without using a catalyst other than the above metal fluoride, but the reaction can be carried out without using a catalyst other than the above metal fluoride.When the reaction is carried out without using a catalyst other than the above metal fluoride, compared with the case where a catalyst other than the above metal fluoride is used, the decomposition product derived from the catalyst is not generated, so that the reaction rate can be easily improved, and the target product can be obtained with a higher conversion rate, a higher selectivity, a higher yield, and a higher purity.

[0068] The above reaction can be carried out in either a liquid phase or a gas phase, and is preferably carried out in a liquid phase, since it does not require heating for vaporization and therefore does not require extra energy or cost.

[0069] (1-3) Metal fluorides As the metal fluoride, at least one X in the compound represented by the general formula (2) is 3 , preferably all X 3 There is no particular limitation as long as it can fluorinate X. 4 If contains halogen atoms other than fluorine atoms, X 4 At least one halogen atom other than a fluorine atom represented by the formula: 4 In particular, from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., fluorides of an alkali metal or an alkaline earth metal are preferred, and fluorides of an alkali metal are more preferred.

[0070] Therefore, examples of metals constituting metal fluorides include alkali metals such as lithium, sodium, potassium, cesium, etc., and alkaline earth metals such as magnesium, calcium, barium, etc. These metals can be used alone or in combination of two or more.

[0071] Specific examples of metal fluorides that satisfy these conditions include alkali metal fluorides such as lithium fluoride, sodium fluoride, potassium fluoride, and cesium fluoride; and alkaline earth metal fluorides such as magnesium fluoride, calcium fluoride, and barium fluoride. Among these, the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), and the reaction temperature of the compound represented by the general formula (1) are particularly preferred. From the viewpoint of the yield of the compound represented by the formula (I), alkali metal fluorides such as lithium fluoride, sodium fluoride, potassium fluoride, and cesium fluoride are preferred, with potassium fluoride being more preferred.

[0072] These metal fluorides may be publicly known or commercially available products. The above metal fluorides may be used alone or in combination of two or more kinds.

[0073] The form of these metal fluorides is not particularly limited. When the manufacturing method of the present disclosure is carried out in a liquid phase, it is preferable that the metal fluorides are dissolved or dispersed in a solvent described below. On the other hand, when the manufacturing method of the present disclosure is carried out in a gas phase, it is preferable to use a pellet-shaped metal fluoride or to support the metal fluoride on a carrier such as activated carbon, zeolite, or alumina.

[0074] In the reaction of the present disclosure, the amount of metal fluoride used is not particularly limited, but is preferably 0.01 to 30 mol, more preferably 0.1 to 20 mol, and even more preferably 1 to 15 mol, relative to 1 mol of the compound represented by general formula (2) from the viewpoints of reaction conversion rate, selectivity of the compound represented by general formula (1), yield of the compound represented by general formula (1), etc. When multiple metal fluorides are used, it is preferable to adjust the total amount to be within the above range.

[0075] (1-4) Solvent As mentioned above, the reactions of the present disclosure are preferably carried out in a solvent.

[0076] The solvent used in the reaction of the present disclosure is not particularly limited, but is preferably an aprotic polar organic solvent, which dissolves the compound represented by the general formula (2), a metal fluoride, and optionally a phosphonium salt, and is excellent in the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), and the yield of the compound represented by the general formula (1). In addition, from the viewpoint of dissolving the compound represented by the general formula (2), a metal fluoride, and optionally a phosphonium salt, and is excellent in the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), and the yield of the compound represented by the general formula (1), an aprotic polar organic solvent containing a nitrogen-containing organic compound and / or a sulfur-containing organic compound is preferable, and a nitrogen-containing aprotic polar organic solvent and / or a sulfur-containing aprotic polar organic solvent is more preferable. Examples of such solvents include amide compounds (N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric acid triamide, etc.), amine compounds (triethylamine, 1-methylpyrrolidine, etc.), pyridine compounds (pyridine, methylpyridine, etc.), quinoline compounds (quinoline, methylquinoline, etc.), sulfone compounds (sulfolane, dimethylsulfone, etc.), and the like.Among these, from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), and the like, amide compounds, pyridine compounds, sulfone compounds, and the like are preferred, and N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric acid triamide, pyridine compounds, and the like are preferred. More preferred are N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, pyridine, sulfolane, and the like, and further more preferred are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, pyridine, and the like, and particularly preferred are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and pyridine.

[0077] These solvents may be known or commercially available products. These solvents may be used alone or in combination of two or more.

[0078] The amount of the solvent used is not particularly limited as long as it is a solvent amount, and can be an excess amount. From the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), the yield of the compound represented by general formula (1), and the like, the amount is preferably 80 to 10,000 parts by mass, more preferably 100 to 1,000 parts by mass, and even more preferably 150 to 800 parts by mass, relative to 100 parts by mass of the compound represented by general formula (2).

[0079] (1-5) Phosphonium salts The reaction of the present disclosure can also be carried out in the presence of a phosphonium salt. The use of a phosphonium salt can particularly easily improve the selectivity of the compound represented by formula (1), the yield of the compound represented by formula (1), and the like, and can particularly easily reduce the amount of impurities produced.

[0080] The phosphonium salt that can be used in the reaction of the present disclosure is preferably a phosphonium salt having one or more alkyl groups, from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), the yield of the compound represented by general formula (1), and the like.

[0081] The phosphonium salt is, for example, a compound represented by the general formula (5):

[0082] [ka]

[0083] [In the formula, R 1 , R 2 , R 3 and R 4 are the same or different and represent a hydrocarbon group. 1 , R 2 , R 3 and R 4 At least one of the groups is an alkyl group. Y represents a counter anion. Examples of the phosphonium salt include those represented by the following formula:

[0084] In the general formula (5), R 1 , R 2 , R 3 and R 4 The hydrocarbon group represented by the formula (I) is not particularly limited, and examples thereof include alkyl groups, aryl groups, and groups formed by any combination thereof (for example, aralkyl groups, alkylaryl groups, and alkylaralkyl groups).

[0085] In the general formula (5), R 1 , R 2 , R 3 and R 4The alkyl group as the hydrocarbon group represented by the formula (I) includes any of linear, branched, or cyclic (preferably linear or branched, more preferably linear). The number of carbon atoms in the alkyl group (in the case of linear or branched) is not particularly limited, and from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., it is preferably, for example, 1 to 20, more preferably 3 to 15, and even more preferably 5 to 10. The number of carbon atoms in the alkyl group (in the case of cyclic) is not particularly limited, and from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., it is preferably, for example, 3 to 8, and more preferably 4 to 7.

[0086] Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the alkyl group include a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, a 3-methylpentyl group, an n-heptyl group, an n-octyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

[0087] In the general formula (5), R 1 , R 2 , R 3 and R 4 The aryl group as the hydrocarbon group represented by is not particularly limited, but from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), the yield of the compound represented by general formula (1), etc., it is preferable that the number of carbon atoms is 6 to 20, more preferably 6 to 12, and further preferably 6 to 10. The aryl group may be either monocyclic or polycyclic (e.g., bicyclic, tricyclic, etc.), but is preferably monocyclic.

[0088] Specific examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a pentalenyl group, an indenyl group, an anthranyl group, a tetracenyl group, a pentacenyl group, a pyrenyl group, a perylenyl group, a fluorenyl group, and a phenanthryl group.

[0089] In the general formula (5), R 1 , R 2 , R 3 and R 4 The aralkyl group as the hydrocarbon group represented by the formula (I) is not particularly limited, but from the viewpoint of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., examples thereof include aralkyl groups in which hydrogen atoms (e.g., 1 to 3, preferably 1 hydrogen atom) of a linear or branched alkyl group having 1 to 6 carbon atoms (preferably 1 to 3) are substituted with the above-mentioned aryl group.

[0090] Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

[0091] In the general formula (5), R 1 , R 2 , R 3 and R 4 The alkylaryl group as the hydrocarbon group represented by the formula (I) is not particularly limited, but from the viewpoint of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., examples thereof include alkylaryl groups in which hydrogen atoms (e.g., 1 to 3, preferably 1 hydrogen atom) of the aryl group are substituted with linear or branched alkyl groups having 1 to 6 carbon atoms (preferably 1 to 2).

[0092] Specific examples of the alkylaryl group include a tolyl group and a xylyl group.

[0093] In the general formula (5), R 1 , R 2 , R 3 and R 4 The alkylaralkyl group as the hydrocarbon group represented by the formula (I) is not particularly limited, and examples thereof include alkylaralkyl groups in which a hydrogen atom (e.g., 1 to 3, preferably 1 hydrogen atom) on the aromatic ring of the aralkyl group is substituted with a linear or branched alkyl group having 1 to 6 carbon atoms (preferably 1 to 2) from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), and the like.

[0094] In the general formula (5), R 1 , R 2 , R 3 and R 4 Examples of the substituent of the hydrocarbon group represented by the formula include an alkoxy group, a halogen atom, etc. The number of the substituents is not particularly limited, and is, for example, preferably 0 to 6, more preferably 0 to 3, and further preferably 0 to 1.

[0095] The alkoxy group as the substituent of the above-mentioned hydrocarbon group is not particularly limited, and may be a linear or branched (preferably linear) alkoxy group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 to 5 carbon atoms, which may be substituted with a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.). The number of the substituents is not particularly limited, and for example, 0 to 6 is preferable, 0 to 3 is more preferable, and 0 to 1 is even more preferable.

[0096] Examples of such an optionally substituted alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a perfluoromethoxy group, and a perfluoroethoxy group.

[0097] The halogen atom as a substituent of the above-mentioned hydrocarbon group is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0098] In addition, R 1 , R 2 , R 3 and R 4 is preferably the site at which a carbon atom bonds to the central phosphorus atom.

[0099] However, from the viewpoint of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., R 1 , R 2 , R 3 and R4 At least one (one, two, three or four) of the is an alkyl group.

[0100] In addition, from the viewpoint of the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., R 1 , R 2 , R 3 and R 4 As the alkyl group, an alkyl group is preferable. 1 , R 2 , R 3 and R 4 At least one (one, two, three or four) of the above is an alkyl group having 1 to 20 carbon atoms, preferably 3 to 15, more preferably 4 to 12, and even more preferably 5 to 10. In particular, by increasing the number of carbon atoms in the alkyl group of the phosphonium salt, it is possible to particularly improve the selectivity of the compound represented by general formula (1), the yield of the compound represented by general formula (1), and the like, and also to particularly reduce the amount of impurities produced.

[0101] In the general formula (5), the counter anion represented by Y is not particularly limited and various anions can be used. For example, a halide ion (fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) etc.), tetrafluoroborate ion (BF4 - ), hydrogen sulfate ion (HSO4 - ), acetate ion (CHCOO - ), hexafluorophosphate ion (PF6 - ) etc.

[0102] Specific examples of the compound represented by the general formula (5) that satisfies the above conditions include

[0103] [ka]

[0104] [ka]

[0105] etc.

[0106] These phosphonium salts may be known or commercially available products. The above phosphonium salts may be used alone or in combination of two or more.

[0107] In the reaction of the present disclosure, the amount of the phosphonium salt used is not particularly limited, but is preferably 0.01 to 3.0 mol, more preferably 0.05 to 2.0 mol, and even more preferably 0.10 to 1.0 mol, relative to 1 mol of the compound represented by general formula (2) from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), the yield of the compound represented by general formula (1), etc. When a plurality of phosphonium salts are used, it is preferable to adjust the total amount thereof to be within the above range.

[0108] (1-6) Reaction temperature In the reaction of the present disclosure, the reaction temperature can be set under mild conditions, and from the viewpoints of easily improving the conversion rate of the reaction, the yield and selectivity of the compound represented by general formula (1), easily reducing by-products, and easily shortening the reaction time, it is usually preferably 0 to 130° C., more preferably 30 to 120° C., and even more preferably 60 to 110° C. In addition, when the reaction temperature is set to 60° C. or higher, it is possible to significantly shorten the reaction time and to allow the reaction to proceed particularly efficiently.

[0109] (1-7)Reaction time The reaction time (maintenance time at the maximum temperature) of the reaction of the present disclosure can be set to a level at which the reaction can proceed sufficiently, and is preferably 1 minute to 48 hours, more preferably 5 minutes to 24 hours, from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), the yield of the compound represented by general formula (1), etc. When the reaction of the present disclosure is carried out in a gas phase, particularly in a gas phase flow continuous system, the contact time (W / F) of the raw material compound (compound represented by general formula (2)) to the catalyst (metal fluoride) [W: weight (g) of the catalyst (metal fluoride), F: flow rate (cc / sec) of the raw material compound (compound represented by general formula (2))] is preferably 0.1 to 100, more preferably 1 to 75, and even more preferably 5 to 50.

[0110] (1-8) Reaction pressure The reaction pressure of the reaction of the present disclosure is preferably -2.0 to 2.0 MPa, more preferably -1.0 to 1.0 MPa, and even more preferably -0.5 to 0.5 MPa, from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), the yield of the compound represented by general formula (1), etc. In the present disclosure, the pressure is a gauge pressure unless otherwise specified.

[0111] In the reaction of the present disclosure, the reactor in which the compound represented by the general formula (2) and the metal fluoride are reacted is not particularly limited in shape and structure as long as it can withstand the above-mentioned temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multi-tube reactor. Examples of the material of the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloys.

[0112] (1-9) Reaction examples The atmosphere in which the reaction of the present disclosure is carried out is preferably an inert gas atmosphere in order to suppress deterioration of the compound represented by general formula (2), the metal fluoride, and, if necessary, the phosphonium salt.

[0113] Examples of the inert gas include nitrogen, helium, argon, etc. Among these inert gases, nitrogen is preferred from the viewpoint of reducing costs.

[0114] After completion of the reaction, purification treatment can be carried out according to a conventional method, if necessary, to obtain the compound represented by the general formula (1).

[0115] (1-10) Target compound (general formula (1)) The target compound thus produced has the general formula (1):

[0116] [ka]

[0117] [In the formula, X 1 are the same or different and represent a hydrogen atom or a halogen atom, provided that the group -CX 1 In 3, 3 X's 1 At least one of the groups is a fluorine atom. X 2 are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 2 At least one of these is a fluorine atom. n represents an integer of 1 to 5. It is a compound represented by the formula:

[0118] In the general formula (1), X 1 , X 2 and n is as defined above.

[0119] That is, the target compound produced in the present disclosure, which is represented by the general formula (1), is specifically:

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] etc.

[0125] 2. Composition In the manner described above, the compound represented by the general formula (1) can be obtained. ) As a compound represented by the general formula (1A):

[0126] [ka]

[0127] [In the formula, X 2 are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 2 At least one of these is a fluorine atom. n represents an integer of 1 to 5. and a compound represented by the formula: General formula (1B):

[0128] [ka]

[0129] [In the formula, X 1a are the same or different and represent a hydrogen atom or a halogen atom, provided that the group -CX 1a In 3, 3 X's 1a One or two of these are fluorine atoms, and the remaining two or one are hydrogen atoms or halogen atoms other than fluorine atoms. X 2 are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 2 At least one of these is a fluorine atom. n represents an integer of 1 to 5. The compound may be obtained in the form of a composition containing both the compound represented by the formula:

[0130] In general formula (1A), X 1 , X 2 and n can be as defined above. The same also applies to the preferred specific examples.

[0131] Therefore, examples of the compound represented by the general formula (1A) include

[0132] [ka]

[0133] [ka]

[0134] etc.

[0135] In addition, in the general formula (1B), X 2 and n can be as defined above. The same also applies to the preferred specific examples.

[0136] In the general formula (1B), X 1a The halogen atom represented by the formula (1B) may be any of those mentioned above. 1a In 3, 3 X's 1a One or two of these are fluorine atoms, and the remaining two or one are hydrogen atoms or halogen atoms other than fluorine atoms.

[0137] Therefore, examples of the compound represented by the general formula (1B) include

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] etc.

[0142] In the composition of the present disclosure, the content of the compound represented by general formula (1A) can be 73.00 to 99.98 mol %, particularly 85.30 to 99.97 mol %, and further 86.60 to 99.93 mol %, relative to the total amount of the composition of the present disclosure related to the second aspect being 100 mol %.

[0143] In the composition of the present disclosure, the content of the compound represented by general formula (1B) can be 0.01 to 15.00 mol %, particularly 0.02 to 13.00 mol %, and further 0.05 to 12.00 mol %, relative to the total amount of the composition of the present disclosure being 100 mol %.

[0144] In the composition of the present disclosure, the total content of the compound represented by general formula (1A) and the compound represented by general formula (1B) can be 98.00 to 99.99 mol%, particularly 98.30 to 99.99 mol%, and further 98.60 to 99.98 mol%, relative to the total amount of the composition of the present disclosure being 100 mol%.

[0145] The compositions of the present disclosure may further comprise a compound represented by the general formula (3):

[0146] [ka]

[0147] [where, X 2 and n is the same as above.] A compound represented by the formula: General formula (4):

[0148] [ka]

[0149] [where, X 1 and n is the same as above. X 2a are the same or different and represent a hydrogen atom or a halogen atom, provided that n X's 2b At least one of them is a fluorine atom and at least one of them is a hydrogen atom. The composition may also include at least one additional compound selected from the group consisting of compounds represented by the formula:

[0150] This composition is a compound represented by the general formula (2) as a substrate, in which X 4 When n, the number of substitutions, is large, for example, 3, 4, or 5, preferably 4 or 5, this is likely to be produced.

[0151] In the general formula (3), X 2 and n can be as defined above. The same also applies to the preferred specific examples.

[0152] Therefore, examples of the compound represented by the general formula (3) include

[0153] [ka]

[0154] etc.

[0155] In the general formula (4), X 1 and n can be as defined above. The same also applies to the preferred specific examples.

[0156] In addition, in the general formula (4), X 2a The halogen atom represented by the formula (4) may be any of those mentioned above. 2aAt least one of them is a fluorine atom and at least one of them is a hydrogen atom. In this respect, the compound represented by general formula (4) is a compound different from the compounds represented by general formula (1A) and general formula (1B).

[0157] Therefore, examples of the compound represented by the general formula (4) include

[0158] [ka]

[0159] [ka]

[0160] [ka]

[0161] [ka]

[0162] etc.

[0163] In the composition of the present disclosure, the content of the compound represented by general formula (3) can be 0.001 to 2.00 mol %, particularly 0.005 to 1.70 mol %, or even 0.01 to 1.40 mol %, relative to the total amount of the composition of the present disclosure being 100 mol %.

[0164] In the composition of the present disclosure, the content of the compound represented by general formula (4) can be 0 to 0.50 mol %, particularly 0.005 to 0.40 mol %, or even 0.01 to 0.30 mol %, relative to the total amount of the composition of the present disclosure being 100 mol %.

[0165] In the composition of the present disclosure, the content of at least one additional compound selected from the group consisting of the compound represented by general formula (3) and the compound represented by general formula (4) is 0.01 to 2.00 mol %, particularly 0.01 to 1.70 mol %, based on the total amount of the composition of the present disclosure being 100 mol %. % by mole, and further, 0.02 to 1.40 mol %.

[0166] The composition according to the second aspect of the present disclosure can be effectively used in various applications such as an etching gas, a cleaning gas, and a deposition gas.

[0167] Although the embodiment of the present disclosure has been described above, various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0168] The following examples will clarify the features of the present disclosure, but the present disclosure is not limited to these examples.

[0169] In the examples and comparative examples, the substrate is

[0170] [ka]

[0171] The following compounds were used: pentafluorobenzotrichloride where n is 5, 2,4,6-trifluorobenzotrichloride where n is 3, 2,4-difluorobenzotrichloride where n is 2, and benzotrichloride where n is 0.

[0172] As the solvent, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), sulfolane, N,N-dimethylacetamide (DMAC), or 1,3-dimethyl-2-imidazolidinone (DMI) was used.

[0173] Examples 1 to 12 and Comparative Examples 1 to 3 A substrate (1 g, 0.005 mol), potassium fluoride (1.05 g, 0.018 mol), and 4.5 mL of a solvent shown in Tables 1 to 3 were added to a glass container, the container was closed, and the container was heated to 50 to 100° C. to carry out the reaction in a liquid phase batch system for 24 hours. When the reaction temperature was 50° C., the reaction time required was about 24 hours, but when the reaction temperature was 75° C. or 100° C., the reaction was completed in about 1 hour.

[0174] After the reaction was completed, mass analysis was performed by gas chromatography and GCMS (gas chromatography mass spectrometry), and structural analysis was performed by NMR (nuclear magnetic resonance).

[0175] From the results of mass spectrometry and structural analysis, pentafluorotrifluoride was confirmed as the target product when pentafluorobenzotrichloride in which n is 5 was used as the substrate, 2,4,6-trifluorobenzotrifluoride was confirmed when 2,4,6-trifluorobenzotrichloride in which n is 3 was used as the substrate, and 2,4-difluorobenzotrifluoride was confirmed when 2,4-difluorobenzotrichloride in which n is 2 was used as the substrate. However, when benzotrichloride in which n is 0 was used as the substrate, the reaction hardly proceeded even when the temperature was raised.

[0176] The results are shown in Tables 1 to 3.

[0177] In addition, in Tables 1 to 3, "trifluoro" means a compound in which all chlorine atoms in the trichloromethyl group of the substrate are fluorinated to form trifluoromethyl groups, "difluoro" means a compound in which two chlorine atoms in the trichloromethyl group of the substrate are fluorinated to form chlorodifluoromethyl groups, and "monofluoro" means a compound in which one chlorine atom in the trichloromethyl group of the substrate is fluorinated to form a dichloromonofluoromethyl group.

[0178] [Table 1]

[0179]

Table 2

[0180]

Table 3

Claims

1. General formula (1): 【Chemistry 1】 [In the formula, X １ are the same or different and each represents a hydrogen atom or a halogen atom, provided that the group -CX １ ３ In, three X １ At least one of these is a fluorine atom. X ２ are the same or different and each represents a hydrogen atom or a halogen atom. ２ At least one of these is a fluorine atom. n represents an integer of 1 to 5. A method for producing a compound represented by the following formula: General formula (2): 【Chemistry 2】 [In the formula, n is the same as defined above. X ３ are the same or different and each represents a hydrogen atom or a halogen atom other than a fluorine atom. ３ ３ In, three X ３ At least one of these is a halogen atom other than a fluorine atom. X ４ are the same or different and each represents a hydrogen atom or a halogen atom. ４ At least one of these is a fluorine atom. A compound represented by the formula: and reacting with a metal fluoride to form at least one group -CX ３ ３ One or more X's in ３ to produce a compound represented by the general formula (1) A manufacturing method comprising:

2. The X １ The method according to claim 1 , wherein each of the is a fluorine atom.

3. The process according to claim 1 or 2, wherein the reaction is carried out in a solvent.

4. The method according to claim 3 , wherein the solvent is an aprotic polar solvent.

5. The method according to any one of claims 1 to 4, wherein the metal fluoride is an alkali metal and / or alkaline earth metal fluoride.

6. The process according to any one of claims 1 to 5, wherein the reaction is carried out in the presence of a phosphonium salt.

7. The method according to any one of claims 1 to 6, wherein the reaction temperature in the reaction is 0 to 130°C.

8. General formula (1A): 【Chemistry 3】 [In the formula, X ２ are the same or different and each represents a hydrogen atom or a halogen atom. ２ At least one of these is a fluorine atom. n represents an integer of 1 to 5. A compound represented by the formula: General formula (1B): 【Chemistry 4】 [In the formula, X １ａ are the same or different and each represents a hydrogen atom or a halogen atom, provided that the group -CX １ａ ３ In, three X １ａ One or two of these are fluorine atoms, and the remaining two or one are hydrogen atoms or halogen atoms other than fluorine atoms. X ２ are the same or different and each represents a hydrogen atom or a halogen atom. ２ At least one of these is a fluorine atom. n represents an integer of 1 to 5. A composition comprising a compound represented by the formula:

9. Furthermore, the general formula (3): 【Chemistry 5】 [In the formula, X ２ and n is the same as above. A compound represented by the formula: General formula (4): 【Chemistry 6】 [In the formula, X １ and n is the same as above. X ２ａ are the same or different and each represents a hydrogen atom or a halogen atom. ２ａ At least one of them is a fluorine atom and at least one of them is a hydrogen atom. At least one additional compound selected from the group consisting of compounds represented by The composition of claim 8 comprising:

10. The composition according to claim 8 or 9, wherein the content of the compound represented by the general formula (1B) is 0.01 to 15.00 mol %, based on 100 mol % of the total amount of the composition.

11. The composition according to claim 9 or 10, wherein the content of the additional compound is 0.01 to 2.00 mol % relative to 100 mol % of the total amount of the composition.

12. The X １ The composition according to any one of claims 9 to 11, wherein each of is a fluorine atom.

13. The composition according to any one of claims 8 to 12, which is used as an etching gas, a cleaning gas, or a deposit gas.

Images