Methods for manufacturing fluorinated aromatic compounds, and fluorinating agents.

Abstract

By making the general form (2): [In the formula, n is the same as above; X3 is the same or different, representing hydrogen atoms or halogen atoms; however, in the base-CX33, at least one of the three X3s is a halogen atom other than fluorine; X4 is the same or different, representing hydrogen atoms or halogen atoms] The compound shown reacts with hydrogen fluoride, a base and an acid other than hydrogen fluoride to fluorinate at least one of the X3s in the base-CX33, to produce the general formula (1): The compound shown can be used to efficiently manufacture fluorine-containing aromatic compounds such as perfluorotoluene.

Description

Technical Field

[0001] The present disclosure relates to a method for producing fluorine-containing aromatic compounds. Prior Art

[0002] As a method for producing perfluorotoluene, which is expected to be a next-generation etching gas, etc., it is known to fluorinate benzotrichloride using a fluorinating agent composed of hydrogen fluoride and urea, amide, ether, ester, phosphoric acid, etc. having a specific structure (for example, see Patent Document 1). [Prior Art Literature] [Patent Document]

[0003] [Patent Document 1] International Publication No. 00 / 047539 Summary of the Invention

[0004] [Problems to be solved by the invention]

[0005] The present invention aims to provide a novel method for efficiently producing fluorine-containing aromatic compounds such as perfluorotoluene. [Methods for solving the problem]

[0006] This disclosure includes the following structures.

[0007] Item 1. A method for producing a compound represented by general formula (1):

[0008]

[0009] [Where, X1 is the same or different and represents a hydrogen atom or a halogen atom; -CX 1 3, at least one of the three X 1 is a fluorine atom; X 2 are the same or different and represent a hydrogen atom or a halogen atom; n represents an integer from 1 to 5]; It has the following properties:

[0010]

[0011] [Where, n is the same as above; X3 are the same or different and represent a hydrogen atom or a halogen atom; -CX 3 3, at least one of the three X 3 is a halogen atom other than a fluorine atom; X4 are the same or different and represent a hydrogen atom or a halogen atom] A step of reacting with hydrogen fluoride, a base and an acid other than hydrogen fluoride to fluorinate at least one X 3 in the group -CX 3 3 to produce the compound represented by the above general formula (1).

[0012] Item 2. The production method according to Item 1, wherein the aforementioned X 1 are all fluorine atoms.

[0013] Item 3. The production method according to Item 1 or 2, wherein at least one of the n X 4 is a halogen atom.

[0014] Item 4. The production method according to any one of Items 1 to 3, wherein the reaction is a step of mixing the hydrogen fluoride and the base to obtain a mixture, and then reacting the mixture with the compound represented by the general formula (2) and an acid other than hydrogen fluoride.

[0015] Item 5. The production method according to any one of Items 1 to 4, wherein the pKa of the acid other than hydrogen fluoride is -10 to 20.

[0016] Item 6. The production method according to any one of Items 1 to 5, wherein the base is at least one selected from the group consisting of amines, ureas, amides, ethers, esters, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, alkali metal hydrides, alkaline earth metal hydrides, alkaline earth metal oxides, alkali metals, and ammonium hydroxide salts capable of supporting a polymer.

[0017] Item 6-1. The production method according to any one of Items 1 to 6, wherein the base comprises at least one amine selected from the group consisting of aliphatic amines, alicyclic amines, aromatic amines, heterocyclic amines, and polymer-supported ammonium.

[0018] Item 7. A composition comprising a compound represented by general formula (1A):

[0019]

[0020] [Where, X 2 are the same or different and represent a hydrogen atom or a halogen atom; n represents an integer from 1 to 5], and Compounds represented by general formula (1B):

[0021]

[0022] [Where, X 2 and n are the same as above; X 1a is the same or different and represents a hydrogen atom or a halogen atom; -CX 1a 3, one or two of the three X 1a are fluorine atoms, and the remaining two or one are hydrogen atoms or halogen atoms other than fluorine atoms]; Wherein, the total amount of the composition is set to 100 mol%, and the content of the compound represented by the aforementioned general formula (1B) is 0.1-95.0 mol%.

[0023] Item 8. The composition as described in Item 7, which satisfies any one of the following (1) and (2): (1) Among the n X 2, 0 to 4 are halogen atoms, and the content of the compound represented by the general formula (1B) is 40.0 to 95.0 mol%; (2) Among the n X 2 s, 1 to 5 are halogen atoms, and the content of the compound represented by the general formula (1B) is 0.1 to 15.0 mol %.

[0024] Item 9. The composition as described in Item 7 or 8, which is used as an etching gas, a cleaning gas or a deposition gas.

[0025] Item 10. A fluorinating agent comprising hydrogen fluoride, a base, and an acid other than hydrogen fluoride.

[0026] Item 10-1. The fluorinating agent according to Item 10, wherein the acid other than hydrogen fluoride has a pKa of -10 to 20.

[0027] Item 10-2. The fluorinating agent according to Item 10 or 10-1, wherein the base is at least one selected from the group consisting of amines, ureas, amides, ethers, esters, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, alkali metal hydrides, alkaline earth metal hydrides, alkaline earth metal oxides, alkali metals, and ammonium hydroxide salts capable of supporting a polymer.

[0028] Item 10-3. The fluorinating agent according to any one of Items 10 to 10-2, wherein the base comprises at least one amine selected from the group consisting of aliphatic amines, alicyclic amines, aromatic amines, heterocyclic amines, and polymer-supported ammonium.

[0029] Item 11. The fluorinating agent according to any one of Items 10 to 10-3, which is a fluorinating agent for a compound represented by general formula (2):

[0030]

[0031] [Where, X3 are the same or different and represent a hydrogen atom or a halogen atom; -CX 3 3, at least one of the three X 3 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; n represents an integer from 1 to 5].

[0032] Item 12. A method for producing a compound represented by general formula (1):

[0033]

[0034] [Where, X1 is the same or different and represents a hydrogen atom or a halogen atom; -CX 1 3, at least one of the three X 1 is a fluorine atom; X 2 are the same or different and represent a hydrogen atom or a halogen atom; n represents an integer from 1 to 5]; It has the following properties:

[0035]

[0036] [Where, n is the same as above; X3 are the same or different and represent a hydrogen atom or a halogen atom; -CX 3 3, at least one of the three X 3 is a halogen atom other than a fluorine atom; X4 are the same or different and represent a hydrogen atom or a halogen atom] A step of reacting with hydrogen fluoride to fluorinate at least one X 3 in the group -CX 3 3 to produce the compound represented by the above general formula (1). [Effects of the Invention]

[0037] According to the present disclosure, a novel method for efficiently producing fluorine-containing aromatic compounds can be provided. Implementation Method

[0038] In this specification, "containing" includes "including The concept of "comprise", "consist essentially of", and "consist of".

[0039] In this specification, when a numerical range is expressed as "A to B", it means greater than A and less than B.

[0040] In this disclosure, the term "selectivity" refers to the ratio (in mole %) of the total molar amount of the target compound contained in the outflowing gas from the reactor outlet relative to the total molar amount of compounds other than the raw material compounds in the outflowing gas.

[0041] In this disclosure, the term "conversion rate" refers to the ratio (in mole %) of the total molar amount of compounds other than the raw material compounds contained in the outflow gas from the reactor outlet relative to the molar amount of the raw material compounds supplied to the reactor.

[0042] In this disclosure, the term "yield" refers to the ratio (in mole %) of the total molar amount of the target compound contained in the gas flowing out of the reactor outlet relative to the molar amount of the raw material compound supplied to the reactor.

[0043] 1. Method for producing fluorine-containing aromatic compounds The manufacturing method disclosed herein is Method for producing the compound represented by general formula (1):

[0044]

[0045] [Where, X1 is the same or different and represents a hydrogen atom or a halogen atom; -CX 1 3, at least one of the three X 1 is a fluorine atom; X 2 are the same or different and represent a hydrogen atom or a halogen atom; n represents an integer from 1 to 5]; It has the following properties:

[0046]

[0047] [Where, n is the same as above; X3 are the same or different and represent a hydrogen atom or a halogen atom; -CX 3 3, at least one of the three X 3 is a halogen atom other than a fluorine atom; X4 are the same or different and represent a hydrogen atom or a halogen atom] A step of reacting with hydrogen fluoride, a base and an acid other than hydrogen fluoride to fluorinate at least one X 3 in the group -CX 3 3 to produce the compound represented by the above general formula (1).

[0048] The production method disclosed herein is not limited to the above method. By reacting the compound represented by the above general formula (2) with hydrogen fluoride, at least one or more X3 in the group -CX33 can be fluorinated to produce the compound represented by the above general formula (1). In other words, even without using either or both a base and an acid other than hydrogen fluoride, at least one or more X3 in the group -CX33 can be fluorinated to produce the compound represented by the above general formula (1). However, from the perspective of reaction stability and operability, the use of hydrogen fluoride, a base, and an acid other than hydrogen fluoride is preferred.

[0049] (1-1) Starting compound (general formula (2)) In the production method disclosed herein, the compound represented by general formula (2) is:

[0050]

[0051] [Where, X3 are the same or different and represent a hydrogen atom or a halogen atom; -CX 3 3, at least one of the three X 3 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; n represents an integer of 1 to 5].

[0052] In general formula (2), the halogen atom represented by X 3 is not particularly limited, and examples thereof include fluorine, chlorine, bromine, and iodine. Of these, chlorine is preferred from the viewpoints of conversion, selectivity, and yield.

[0053] Although X 3 may be a hydrogen atom or a halogen atom, when all X 3 are hydrogen atoms, the reaction hardly proceeds, and even if the temperature is increased, the target compound represented by general formula (1) can hardly be obtained. When all X 3 are fluorine atoms, they are already fluorinated and there is no need to adopt the production method disclosed herein. Therefore, in the group -CX 3 3, at least one of the three X 3 is a halogen atom other than a fluorine atom.

[0054] In general formula (2), the halogen atom represented by X4 is not particularly limited, and examples thereof include fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Among them, fluorine atom is preferred from the viewpoints of conversion rate, selectivity, yield, etc.

[0055] Furthermore, increasing the number of halogen atoms (particularly fluorine atoms) among the n X4 groups tends to reduce the reaction conversion rate. Nevertheless, in the present disclosure, the conversion rate can be increased by using an acid other than hydrogen fluoride. Therefore, the greater the number of halogen atoms (particularly fluorine atoms) among the n X4 groups, the greater the effect achieved by the production method of the present disclosure. Therefore, it is preferred that at least one of the n X4 groups be a halogen atom. For example, when n is 5, the number of halogen atoms (particularly fluorine atoms) among the five X4 groups, from the perspectives of conversion rate, selectivity, and yield, is preferably 1 to 5, more preferably 2 to 5, even more preferably 3 to 5, and particularly preferably 4 to 5.

[0056] In 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.

[0057] In addition, when the number of substitutions n of X 4 is 5, the compound represented by general formula (2) is the compound represented by general formula (2A):

[0058]

[0059] [wherein, X 3 and X 4 are the same as above].

[0060] Furthermore, the compound represented by general formula (2) used as a substrate in this disclosure preferably does not contain a nitro group. If a compound having a nitro group is used as a substrate, the reactivity of the -CX 3 3 group is extremely high, and side reactions may occur, which may reduce the selectivity of the target product.

[0061] As the compound represented by the general formula (2) that satisfies the above conditions, specifically, there can be exemplified:

[0062]

[0063]

[0064] wait.

[0065] The compound represented by the general formula (2) can be a known or commercially available compound. The compound represented by the general formula (2) can be used alone or in combination of two or more.

[0066] (1-2) Reaction In the reaction disclosed herein, in the compound represented by the general formula (2), at least one or more X3 in the group -CX33 is fluorinated to produce the compound represented by the general formula (1). It is particularly easy to produce the compound represented by the general formula (1) in which at least all X3 in the group -CX33 are fluorinated and all X1 are fluorine atoms.

[0067] In this case, when X4 is a hydrogen atom or a fluorine atom, it remains unchanged even after the reaction disclosed herein. In other words, when X4 is a hydrogen atom or a fluorine atom, X2 is also a hydrogen atom or a fluorine atom.

[0068] On the other hand, when X4 is a halogen atom other than a fluorine atom, it is easily fluorinated by the reaction disclosed herein. That is, when X4 is a halogen atom other than a fluorine atom, X2 is easily converted into a fluorine atom.

[0069] As described above, in the reaction disclosed herein, when X4 in the compound represented by the general formula (2) contains a halogen atom other than a fluorine atom, one or more halogen atoms other than a fluorine atom represented by X4 are also fluorinated, thereby easily generating the compound represented by the general formula (1). Furthermore, when X4 in the compound represented by the general formula (2) contains a halogen atom other than a fluorine atom, it is easy to generate the compound represented by the general formula (1) in which all X4 are fluorinated and all X2 are fluorine atoms.

[0070] On the other hand, in the compound represented by the general formula (2), when X 4 contains a hydrogen atom or a fluorine atom, the hydrogen atom or the fluorine atom is likely to remain unchanged even through the reaction disclosed herein.

[0071] As a result, the compound represented by general formula (1) can be obtained.

[0072] (1-3) Hydrogen fluoride The hydrogen fluoride used in the production method disclosed herein can be gaseous, liquid, or an aqueous solution (hydrogen fluoride acid). Gaseous hydrogen fluoride is preferred from the perspectives of productivity and corrosiveness. Furthermore, when using liquid hydrogen fluoride or an aqueous solution (hydrogen fluoride acid), the hydrogen fluoride can also be used as a solvent.

[0073] As hydrogen fluoride, a known or commercially available product can be used.

[0074] The amount of hydrogen fluoride used in the production method disclosed herein is not particularly limited. However, from the viewpoints of conversion rate, selectivity, yield, etc., the amount is preferably 1 to 100 mol, more preferably 10 to 50 mol, and even more preferably 15 to 25 mol, relative to 1 mol of the compound represented by general formula (2).

[0075] (1-4) alkali The base is not particularly limited and examples thereof include amines, ureas, amides, ethers, esters, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, alkali metal hydrides, alkaline earth metal hydrides, alkaline earth metal oxides, alkali metals, and ammonium hydroxide salts capable of supporting a polymer.

[0076] Examples of amines include aliphatic amines (aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines), alicyclic amines (aliphatic secondary amines, alicyclic tertiary amines), aromatic amines (aromatic primary amines, aromatic secondary amines, aromatic tertiary amines), heterocyclic amines, and polymer-supported ammonium (polyallylamine, polyvinylpyridine, etc.).

[0077] Examples of the aliphatic primary amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, tertiary butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, and ethylenediamine.

[0078] Examples of the aliphatic secondary amine include dimethylamine, diethylamine, di(n-propyl)amine, diisopropylamine, di(n-butyl)amine, diisobutylamine, di(secondary butyl)amine, di(tertiary butyl)amine, di(n-pentyl)amine, di(n-hexyl)amine, and dicyclohexylamine.

[0079] Examples of the aliphatic tertiary amine include trimethylamine, triethylamine, diisopropylethylamine, and N,N,N',N'-tetramethylethylenediamine.

[0080] Examples of the alicyclic secondary amine include piperidine, , pyrrolidine, morpholine, etc.

[0081] Examples of the alicyclic tertiary amine include N-methylpiperidin , N-methylpyrrolidine, 5-diazabicyclo[4.3.0]nonane-5-ene, 1,4-diazabicyclo[2.2.2]octane, etc.

[0082] Examples of the aromatic amine include aniline, methylaniline, dimethylaniline, N,N-dimethylaniline, haloaniline, and nitroaniline.

[0083] Examples of heterocyclic amines include pyridine, pyrimidine, piperidine, , quinoline, imidazole, etc.

[0084] Examples of urea include 1,1,3,3-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-di(n-propyl)-2-imidazolidinone, 1,3-di(n-butyl)-2-imidazolidinone, N,N'-dimethylpropylurea, N,N'-diethylpropylurea, N,N'-di(n-propyl)propylurea, and N,N'-di(n-butyl)propylurea.

[0085] Examples of the amide include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidone.

[0086] Examples of the ether include di(n-butyl) ether, di(n-hexyl ether), anisole, phenethyl ether, n-butylphenyl ether, pentylphenyl ether, 2-methoxytoluene, 4-methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.

[0087] Examples of the ester include n-butyl acetate, n-amyl acetate, isoamyl acetate, cyclohexyl acetate, benzyl acetate, n-butyl propionate, isoamyl propionate, methyl benzoate, dimethyl phthalate, and γ-butyrolactone.

[0088] Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide.

[0089] Examples of the alkaline earth metal hydroxide include magnesium hydroxide, calcium hydroxide, and barium hydroxide.

[0090] Examples of the alkali metal alkoxide include sodium methoxide, sodium ethoxide, sodium n-butoxide, potassium methoxide, potassium ethoxide, potassium n-butoxide, lithium methoxide, and lithium ethoxide.

[0091] Examples of the alkali metal hydride include sodium hydride, potassium hydride, and lithium hydride.

[0092] Examples of the alkaline earth metal hydride include calcium hydride and the like.

[0093] Examples of the alkaline earth metal oxide include magnesium oxide and calcium oxide.

[0094] Examples of the alkali metal include sodium, potassium, and lithium.

[0095] Examples of ammonium hydroxide salts that can support polymers include ammonia, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra(n-butyl)ammonium hydroxide, (n-octyl)triethylammonium hydroxide, benzyltrimethylammonium hydroxide, and AMBERLITE resin.

[0096] These bases can be known or commercially available. Furthermore, the bases may be used alone or in combination of two or more. From the perspectives of conversion, selectivity, and yield, amines are preferred, with aliphatic amines and heterocyclic amines being more preferred, and aliphatic tertiary amines and heterocyclic amines being even more preferred. Furthermore, when using a liquid base or aqueous solution, the base may also be used as a solvent.

[0097] The amount of the base used in the production method disclosed herein is not particularly limited. However, from the perspectives of conversion rate, selectivity, yield, etc., the amount is preferably 1 to 100 mol, more preferably 10 to 50 mol, and even more preferably 15 to 25 mol relative to 1 mol of the compound represented by general formula (2).

[0098] (1-5) Acids other than hydrogen fluoride There are no particular limitations on the acids other than hydrogen fluoride that can be used in the production method disclosed herein. However, from the perspectives of conversion rate, selectivity, yield, etc., a pKa of -10 to 20 is preferred, -7.5 to 15 is more preferred, and -5 to 10 is even more preferred.

[0099] Acids other than hydrofluoric acid include organic acids such as sulfonic acid compounds (methanesulfonic acid, p-toluenesulfonic acid, etc.) and carboxylic acid compounds (trifluoroacetic acid, etc.), as well as inorganic acids such as phosphoric acid. Of these, organic acids are preferred from the perspectives of conversion, selectivity, and yield, and sulfonic acid compounds are even more preferred.

[0100] Acids other than hydrogen fluoride may be known or commercially available. These acids other than hydrogen fluoride may be used alone or in combination of two or more. Furthermore, when using a liquid or aqueous solution of an acid other than hydrogen fluoride, the acid may be used as a solvent.

[0101] In the reaction disclosed herein, the amount of acid other than hydrogen fluoride used is not particularly limited. However, from the perspectives of conversion rate, selectivity, yield, etc., the amount is preferably 1 to 100 moles, more preferably 10 to 50 moles, and even more preferably 15 to 25 moles per mole of the compound represented by general formula (2). Furthermore, when using multiple acids other than hydrogen fluoride, it is preferably adjusted so that the total amount falls within the above range.

[0102] (1-6) Reaction temperature In the reaction disclosed herein, the reaction temperature is not particularly limited, but from the viewpoints of conversion, selectivity, yield, etc., 50-250°C is generally preferred, 100-200°C is more preferred, and 125-175°C is even more preferred.

[0103] (1-7) Reaction time The reaction time (maintaining time at the highest temperature achieved) of the reaction disclosed herein can be set to a degree sufficient for the reaction to proceed fully. From the perspectives of conversion, selectivity, and yield, it is preferably 1 minute to 48 hours, and more preferably 5 minutes to 24 hours. Furthermore, when the reaction disclosed herein is conducted in a gas phase, particularly in a gas phase continuous flow process, the contact time (W / F) [W: weight of catalyst (g), F: flow rate (cc / sec) of the raw material compound (octafluorobutene)] of the catalyst (acid other than hydrogen fluoride) is preferably 1 to 100, more preferably 5 to 75, and even more preferably 10 to 50.

[0104] (1-8) Reaction pressure The reaction pressure of the disclosed reaction is not particularly limited, but is preferably -2.0 to 2.0 MPa from the viewpoints of conversion rate, selectivity, yield, etc. -1.0 to 1.0 MPa is more preferred, and -0.5 to 0.5 MPa is even more preferred. In addition, in this disclosure, unless otherwise specified, pressure is assumed to be gauge pressure.

[0105] In the reactions disclosed herein, the reactors that can be used are not particularly limited in shape or structure, as long as they can withstand the aforementioned temperatures and pressures. Examples of the reactor include vertical reactors, horizontal reactors, and multi-tube reactors. Examples of the reactor material include glass, stainless steel, iron, nickel, and iron-nickel alloys.

[0106] (1-9) Example of reaction The reaction disclosed herein can be carried out in either a batch method in which the raw materials are fed into the reactor all at once, or a flow method in which the raw materials are continuously supplied to the reactor while the product is taken out of the reactor.

[0107] Furthermore, the reaction disclosed above can be carried out in liquid phase or gas phase. However, from the perspectives of equipment cost and productivity, liquid phase is preferred.

[0108] Furthermore, in the reaction disclosed herein, the compound represented by general formula (2), hydrogen fluoride, a base, and an acid other than hydrogen fluoride may be added simultaneously or gradually. Furthermore, a portion of the components may be reacted in advance, and then the remaining components may be reacted. From the perspective of operability, it is preferred to first mix (react) hydrogen fluoride and a base to produce a mixture of hydrogen fluoride and a base, and then react the mixture with the compound represented by general formula (2) and an acid other than hydrogen fluoride. Furthermore, from the perspective of operability, the mixture obtained by mixing hydrogen fluoride and a base is preferably a complex in which hydrogen fluoride and a base are bonded together. Furthermore, as described above, the reaction disclosed herein may also be carried out by adding the compound represented by general formula (2) and hydrogen fluoride.

[0109] However, hydrogen fluoride, when used alone, has a low boiling point (20°C), becoming a gas under normal processing conditions. Furthermore, its high toxicity makes it difficult to handle, making it difficult to use on an industrial scale. On the other hand, by forming a composite, the boiling point is raised, allowing it to become a liquid under normal processing conditions, making it easier to handle and facilitate industrial-scale operation. Furthermore, as demonstrated in the examples, the use of a composite also facilitates the reduction of other impurities and the reduction of non-recyclable impurities, resulting in a cost advantage.

[0110] As described above, hydrogen fluoride, bases, and acids other than hydrogen fluoride that can be used in the production method disclosed herein can be used as fluorinating agents, particularly fluorinating agents for compounds represented by general formula (2). In the fluorinating agent disclosed herein, the total amount of the fluorinating agent disclosed herein is set to 100 mol%, and the content of hydrogen fluoride is preferably set to 0.1-99 mol% (preferably 1-90 mol%), the content of the base is preferably set to 0.1-99 mol% (preferably 1-90 mol%), and the content of the acid other than hydrogen fluoride is preferably set to 0.1-99 mol% (preferably 1-90 mol%).

[0111] Regarding the gas environment during the reaction of the present disclosure, an inert gas environment is preferred from the viewpoint of suppressing the degradation of the compound represented by general formula (2), hydrogen fluoride, base, and acid other than hydrogen fluoride.

[0112] Examples of the inert gas include nitrogen, helium, and argon. Among these inert gases, nitrogen is preferred from the perspective of reducing costs.

[0113] After the reaction is completed, purification can be performed according to conventional methods as needed to obtain the compound represented by general formula (1).

[0114] (1-10) Target compound (general formula (1)) The target compound generated in this manner is a compound represented by the general formula (1):

[0115]

[0116] [Where, X1 is the same or different and represents a hydrogen atom or a halogen atom; -CX 1 3, at least one of the three X 1 is a fluorine atom; X 2 are the same or different and represent a hydrogen atom or a halogen atom; n represents an integer from 1 to 5].

[0117] In the general formula (1), the halogen atom represented by X 1 is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0118] Since the compound represented by general formula (1) is a compound represented by general formula (2) in which at least one or more X 3 in the group -CX 3 3 is fluorinated, at least one of the three X 1 in the group -CX 1 3 is a fluorine atom.

[0119] In general formula (1), the halogen atom represented by X2 is not particularly limited, and examples thereof include fluorine, chlorine, bromine, and iodine. Furthermore, in the case where X4 in the compound represented by general formula (2) is a hydrogen atom or a fluorine atom, X2 in the compound represented by general formula (1) remains a hydrogen atom or a fluorine atom. On the other hand, in the case where X4 in the compound represented by general formula (2) is a halogen atom other than a fluorine atom, X2 in the compound represented by general formula (1) may remain a halogen atom other than a fluorine atom, or may be fluorinated so that X2 becomes a fluorine atom.

[0120] In general formula (1), n ​​is the same as in general formula (2), and is an integer of 1 to 5, 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.

[0121] From the above, the target compound generated in the present disclosure is the compound represented by the general formula (1). Specifically, it can be exemplified as:

[0122]

[0123]

[0124]

[0125]

[0126] wait.

[0127] 2. Composition As described above, the compound represented by the general formula (1) can be obtained. However, the compound represented by the general formula (1) also includes the compound represented by the general formula (1A):

[0128]

[0129] [Where, X 2 are the same or different and represent a hydrogen atom or a halogen atom; n represents an integer from 1 to 5], The compound represented by general formula (1B):

[0130]

[0131] [Where, X 1a is the same or different and represents a hydrogen atom or a halogen atom; -CX 1a 3, one or two of the three X 1a 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; n represents an integer from 1 to 5] The form of the composition of the two.

[0132] In general formulae (1A) and (1B), X1, X2, and n can be those described above. Preferred specific examples are also the same.

[0133] Therefore, as the compound represented by general formula (1A), for example:

[0134]

[0135]

[0136] wait.

[0137] Furthermore, as the compound represented by general formula (1B), for example:

[0138]

[0139]

[0140]

[0141] wait.

[0142] In the composition disclosed herein, the content of the compound represented by general formula (1A) can be set to 1.0-99.9 mol%, particularly 5.0-99.5 mol%, and further 8.0-99.0 mol%, based on the total amount of the composition disclosed herein being 100 mol%.

[0143] In the composition disclosed herein, the content of the compound represented by general formula (1B) can be set to 0.1-95.0 mol%, particularly 0.5-94.0 mol%, and further 1.0-92.0 mol%, based on the total amount of the composition disclosed herein being 100 mol%.

[0144] Furthermore, when 0 to 4 of the n X 2 atoms are halogen atoms, the content of the compound represented by general formula (1A) can be 1.0 to 60.0 mol%, particularly 5.0 to 40.0 mol%, and further 8.0 to 20.0 mol%, based on the total amount of the composition of the present disclosure being 100 mol%.

[0145] Furthermore, when 0 to 4 of the n X 2 atoms are halogen atoms, the content of the compound represented by general formula (1B) can be 40.0 to 95.0 mol%, particularly 60.0 to 94.0 mol%, and further 80.0 to 92.0 mol%, based on the total amount of the composition of the present disclosure being 100 mol%.

[0146] Furthermore, when 1 to 5 of the n X 2 atoms are halogen atoms, the content of the compound represented by general formula (1A) can be 80.0 to 99.9 mol%, particularly 81.0 to 99.5 mol%, and further 82.0 to 99.0 mol%, based on the total amount of the composition of the present disclosure being 100 mol%.

[0147] When 0 to 4 of the n X 2 atoms are halogen atoms, the content of the compound represented by general formula (1B) can be 0.1 to 15.0 mol %, particularly 0.5 to 14.5 mol %, and further 1.0 to 14.0 mol %, based on the total amount of the composition of the present disclosure being 100 mol %.

[0148] In the composition disclosed herein, when the total amount of the composition disclosed herein is set to 100 mol%, the total content of the compound represented by general formula (1A) and the compound represented by general formula (1B) can be set to 90.0-100 mol%, particularly 93.0-99.9 mol%, and further 95.0-99.8 mol%.

[0149] The composition disclosed herein can be effectively used in various applications such as etching gas, cleaning gas, and deposition gas.

[0150] Although the embodiments of the present disclosure are described above, various modifications of the embodiment and details are possible without departing from the spirit and scope of the claims. [Example]

[0151] The following examples are provided to clarify the features of the present disclosure, but the present disclosure is not limited to these examples.

[0152] In the Examples and Comparative Examples, the following compounds were used as substrates:

[0153] ,

[0154] Pentafluorobenzotrichloride with n being 5, 2,4-difluorobenzotrichloride with n being 2, and benzotrichloride with n being 0 were used.

[0155] In the following examples and comparative examples, hydrogen fluoride-amine complexes were prepared using a hydrogen fluoride-triethylamine complex (hydrogen fluoride:triethylamine = 1:3 (molar ratio)) and a hydrogen fluoride-pyridine complex (hydrogen fluoride:triethylamine = 1:9 (molar ratio)). The hydrogen fluoride-triethylamine complex was prepared by injecting hydrogen fluoride into triethylamine, and the hydrogen fluoride-pyridine complex was prepared by injecting hydrogen fluoride into pyridine.

[0156] Examples 1 to 15 and Comparative Examples 1 to 5 To a SUS reactor, the substrates listed in Tables 1-4 (1 g, 0.005 mol), a hydrogen fluoride-triethylamine complex (10 g, 0.06 mol), a hydrogen fluoride-pyridine complex (5 g, 0.02 mol), or anhydrous hydrogen fluoride (10 g, 0.5 mol), and the acids listed in Tables 1-4 (0.0005 mol, 10 mol% relative to the molar number of the substrate) were added. The reactor was closed, heated to the temperature listed in Tables 1-5, and reacted for 24 hours. However, in Examples 16-17, no base or acid other than hydrogen fluoride was used.

[0157] After the reaction, mass analysis was performed using gas chromatography and GCMS (gas chromatography mass spectrometry), and structural analysis was performed using NMR (nuclear magnetic resonance).

[0158] The results of mass spectrometry and structural analysis showed that the target pentafluorotrifluoride was confirmed when pentafluorobenzotrichloride (n=5) was used as the matrix. 2,4-difluorobenzotrichloride (n=2) was confirmed when 2,4-difluorobenzotrifluoride was used as the matrix. Benzotrifluoride was confirmed when benzotrichloride (n=0) was used as the matrix.

[0159] The results are shown in Tables 1 to 5.

[0160] In Tables 1 to 5, "trifluoro" refers to a compound in which all chlorine atoms in a trichloromethyl group of a substrate are fluorinated to form a trifluoromethyl group, "difluoro" refers to a compound in which two chlorine atoms in a trichloromethyl group of a substrate are fluorinated to form a chlorodifluoromethyl group, and "monofluoro" refers to a compound in which one chlorine atom in a trichloromethyl group of a substrate is fluorinated to form a dichloromonofluoromethyl group.

[0161]

[0162]

[0163]

[0164]

[0165]

Claims

1. A method for manufacturing a compound of general formula (1), comprising the steps of reacting a compound of general formula (2) with hydrogen fluoride, an amine and a sulfonic acid compound to fluorinate at least one halogen atom other than fluorine atom in X3 of at least one of the base-CX33, converting it into fluorine atom in X1, thereby generating the compound of general formula (1); General formula (1): [wherein, X1 is the same or different, representing a hydrogen atom or a halogen atom; however, in base-CX13, at least one of the three X1 is a fluorine atom; X2 is the same or different, representing a hydrogen atom or a fluorine atom; n represents an integer from 1 to 5]; General formula (2): [wherein, n is the same as above; X3 is the same or different, representing a hydrogen atom or a halogen atom; however, in base-CX33, at least one of the three X3 is a halogen atom other than fluorine atom; X4 is the same or different, representing a hydrogen atom or a fluorine atom].

2. The manufacturing method as described in claim 1, wherein all of the aforementioned X1 are fluorine atoms.

3. The manufacturing method of claim 1 or 2, wherein at least one of the aforementioned n X4 atoms is a fluorine atom.

4. The manufacturing method of claim 1 or 2, wherein the aforementioned reaction is a step of reacting the aforementioned mixture with the compound shown in the aforementioned general formula (2) and the aforementioned sulfonic acid compound after mixing the aforementioned hydrogen fluoride and the aforementioned amine to obtain a mixture.

5. The manufacturing method as claimed in claim 1 or 2, wherein the pKa of the aforementioned sulfonic acid compound is -10 to 20.

6. A fluorinating agent used to fluorinate at least one halogen atom other than fluorine atom in one or more X3s of the base-CX33 in a compound of general formula (2), [where X3s are the same or different and represent hydrogen atoms or halogen atoms; however, in the base-CX33, at least one of the three X3s is a halogen atom other than fluorine atom; X4s are the same or different and represent hydrogen atoms or fluorine atoms; n represents an integer from 1 to 5]; the fluorinating agent contains hydrogen fluoride, an amine and a sulfonic acid compound.