Process for producing a fluorine-containing aromatic compound

Abstract

To provide a novel method for making it possible to efficiently produce a fluorine-containing aromatic compound such as perfluorotoluene.SOLUTION: A method for producing a fluorine-containing aromatic compound comprises reacting a compound represented by general formula (2) (where n represents an integer from 1 to 5; X3 are the same or different and each represent a hydrogen atom or a halogen atom, provided that, in the group -CX33, at least one of the three X3 is a halogen atom other than a fluorine atom; and X4 are the same or different and each represent a hydrogen atom or a halogen atom) with hydrogen fluoride, a base, and an acid other than hydrogen fluoride so as to generate a compound in which at least one or more X3 in the group -CX33 are fluorinated.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

[0005] The present disclosure includes the following configurations.

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

[0007]

Chemical formula

[0008] [In the formula, X 1 independently represents a hydrogen atom or a halogen atom. However, in the group -CX 1 3, the three X 1At least one of them is a fluorine atom. X 2 is the same as or different from, and represents a hydrogen atom or a halogen atom. n represents an integer from 1 to 5. A method for producing a compound represented by General formula (2):

[0009]

Chemical formula

[0010] [In the formula, n is the same as above. X 3 is the same as or different from, and represents a hydrogen atom or a halogen atom. However, in the group -CX 3 3, at least one of the three X 3 is a halogen atom other than a fluorine atom. X 4 is the same as or different from, and represents a hydrogen atom or a halogen atom. Reacting the compound represented by hydrogen fluoride, a base, and an acid other than hydrogen fluoride, and fluorinating at least one or more X 3 in the group -CX 3 3 to produce the compound represented by the above general formula (1). A manufacturing method comprising the above step.

[0011] Item 2. The manufacturing method according to Item 1, wherein all of the said X 1 are fluorine atoms.

[0012] Item 3. The manufacturing method according to Item 1 or 2, wherein at least one of the n X 4 is a halogen atom.

[0013] Item 4. The manufacturing method according to any one of Items 1 to 3, wherein the reaction is a step of reacting the mixture obtained by mixing the hydrogen fluoride and the base with the compound represented by the general formula (2) and the acid other than hydrogen fluoride.

[0014] 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.

[0015] 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 which may be supported on a polymer.

[0016] Item 6-1. The production method according to any one of Items 1 to 6, wherein the base contains at least one amine selected from the group consisting of aliphatic amines, alicyclic amines, aromatic amines, heterocyclic amines, and polymer-supported amines.

[0017] Item 7. General formula (1A):

[0018]

Chemical formula

[0019] [In the formula, X 2 is the same or different and represents a hydrogen atom or a halogen atom. n represents an integer of 1 to 5.] and a compound represented by General formula (1B):

[0020]

Chemical formula

[0021] [In the formula, 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. However, in the group -CX 1a 3, the three Xs1a One or two of them are fluorine atoms, and the remaining two or one are hydrogen atoms or halogen atoms other than fluorine atoms. and contains a compound represented by A composition in which the content of the compound represented by the general formula (1B) is 0.1 to 95.0 mol% based on the total amount of the composition being 100 mol%.

[0022] Item 8. (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%, and (2) Among the n X 2 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% The composition according to item 7, which satisfies any one of the above.

[0023] Item 9. The composition according to item 7 or 8, which is used as an etching gas, a cleaning gas, or a deposit gas.

[0024] Item 10. A fluorinating agent containing hydrogen fluoride, a base, and an acid other than hydrogen fluoride.

[0025] Item 10-1. The fluorinating agent according to item 10, wherein the pKa of the acid other than hydrogen fluoride is -10 to 20.

[0026] 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 which may be supported by a polymer.

[0027] Item 10-3. The fluorinating agent according to any one of Items 10 to 10-2, wherein the base contains at least one amine selected from the group consisting of aliphatic amines, alicyclic amines, aromatic amines, heterocyclic amines, and polymer-supported amines.

[0028] Item 11. General formula (2):

[0029]

Chemical formula

[0030] [In the formula, X 3 are the same or different and each represents a hydrogen atom or a halogen atom. However, in the group -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 each represents a hydrogen atom or a halogen atom. n represents an integer of 1 to 5. ] The fluorinating agent according to any one of Items 10 to 10-3, which is a fluorinating agent for a compound represented by the formula.

[0031] Item 12. General formula (1):

[0032]

Chemical formula

[0033] [In the formula, X 1 are the same or different and each represents a hydrogen atom or a halogen atom. However, in the group -CX 1 3, at least one of the three X 1 is a fluorine atom. X 2 are the same or different and each represents a hydrogen atom or a halogen atom. n represents an integer of 1 to 5. ] A method for producing a compound represented by the formula, General formula (2):

[0034] [Chemical formula]

[0035] [In the formula, n is the same as described above. X 3 is the same or different and represents a hydrogen atom or a halogen atom. However, in the group -CX 3 3, at least one of the three X 3 is a halogen atom other than a fluorine atom. X 4 is the same or different and represents a hydrogen atom or a halogen atom.] A compound represented by is reacted with hydrogen fluoride to fluorinate at least one or more of X 3 in -CX 3 3 to produce a compound represented by the above general formula (1). A production method comprising [Advantages of the Invention]

[0036] According to the present disclosure, a novel method capable of efficiently producing a fluorine-containing aromatic compound can be provided. [Modes for Carrying Out the Invention]

[0037] In this specification, "containing" is a concept encompassing any of "comprise", "consist essentially of", and "consist of".

[0038] Also, in this specification, when a numerical range is indicated as "A to B", it means A or more and B or less.

[0039] In the present disclosure, the "selectivity" means the ratio (mol%) of the total molar amount of the target compound contained in the effluent gas to the total molar amount of compounds other than the raw material compound in the effluent gas from the reactor outlet.

[0040] In the present disclosure, the "conversion rate" means the ratio (mol%) of the total molar amount of compounds other than the raw material compound contained in the effluent gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

[0041] In the present disclosure, the "yield" means 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 compound supplied to the reactor.

[0042] 1. Method for producing fluorine-containing aromatic compound The production method of the present disclosure is General formula (1):

[0043] [Chemical formula]

[0044] [In the formula, X 1 are the same or different and each represents a hydrogen atom or a halogen atom. However, in the group -CX 1 3, at least one of the three X 1 is a fluorine atom. X 2 are the same or different and each represents a hydrogen atom or a halogen atom. n represents an integer from 1 to 5.] It is a method for producing a compound represented by General formula (2):

[0045] [Chemical formula]

[0046] [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. However, in the group -CX 3 3, at least one of the three X 3 is a halogen atom other than a fluorine atom. X 4 is the same or different and represents a hydrogen atom or a halogen atom.] and a compound represented by hydrogen fluoride, a base, and an acid other than hydrogen fluoride are reacted to fluorinate at least one X in the group -CX 3 3 to produce a compound represented by the above general formula (1). 3 The process comprises In the production method of the present disclosure, it is not limited to only the above method, and by reacting the compound represented by the above general formula (2) with hydrogen fluoride, at least the group -CX

[0047] one or more X in 3 can also be fluorinated to produce the compound represented by the above general formula (1). That is, even when one or both of the base and the acid other than hydrogen fluoride are not used, at least one or more X in the group -CX 3 3 can be fluorinated to produce the compound represented by the above general formula (1). However, from the viewpoints of reaction stability and handleability, it is preferable to use hydrogen fluoride, a base, and an acid other than hydrogen fluoride. 3 In the production method of the present disclosure, it is not limited to only the above method, and by reacting the compound represented by the above general formula (2) with hydrogen fluoride, at least the group -CX 3 3 can also be fluorinated to produce the compound represented by the above general formula (1). That is, even when one or both of the base and the acid other than hydrogen fluoride are not used, at least one or more X in the group -CX 3 3 can be fluorinated to produce the compound represented by the above general formula (1). However, from the viewpoints of reaction stability and handleability, it is preferable to use hydrogen fluoride, a base, and an acid other than hydrogen fluoride.

[0048] (1-1) Starting compound (general formula (2)) In the production method of the present disclosure, the compound represented by the general formula (2) is represented by the general formula (2):

[0049]

Chemical formula

[0050] [wherein, X 3 is the same or different and represents a hydrogen atom or a halogen atom. However, in the group -CX 3 3, at least one of the three X 3 is a halogen atom other than a fluorine atom.] X 4is the same or different and represents a hydrogen atom or a halogen atom. n represents an integer from 1 to 5. It is a compound represented by the formula:

[0051] In the general formula (2), X 3 The halogen atom represented by is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Among them, from the viewpoints of conversion rate, selectivity, yield, etc., a chlorine atom is preferable.

[0052] X 3 may be a hydrogen atom or a halogen atom, but when all of X 3 are hydrogen atoms, the reaction hardly proceeds, and even if the temperature is raised, hardly any compound represented by the general formula (1) which is the target product can be obtained. When all of X 3 are fluorine atoms, since it is already fluorinated and there is no need to adopt the production method of the present disclosure, in the group - CX 3 3, at least one of the three X 3 is a halogen atom other than a fluorine atom.

[0053] In the general formula (2), X 4 The halogen atom represented by is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Among them, from the viewpoints of conversion rate, selectivity, yield, etc., a fluorine atom is preferable.

[0054] In addition, as the number of halogen atoms (especially fluorine atoms) among n X 4 increases, the conversion rate of the reaction tends to decrease easily. In the present disclosure, nevertheless, by using an acid other than hydrogen fluoride, it is possible to increase the conversion rate. Therefore, the more the number of halogen atoms (especially fluorine atoms) among n X 4 is, the higher the effect of adopting the production method of the present disclosure. From this, it is preferable that at least one of n X 4 is a halogen atom. For example, when n is 5, among the five X 4Among them, the number of halogen atoms (especially fluorine atoms) is preferably 1 to 5, more preferably 2 to 5, still more preferably 3 to 5, and particularly preferably 4 to 5, from the viewpoints of conversion rate, selectivity, yield, etc.

[0055] 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 still more preferably an integer of 4 to 5.

[0056] Incidentally, when n, which is the number of substitutions of X 4 is 5, the compound represented by the general formula (2) is a compound represented by the general formula (2A):

[0057]

Chemical formula

[0058] [In the formula, X 3 and X 4 are the same as described above.] is a compound represented by this.

[0059] Incidentally, the compound represented by the general formula (2) used as a substrate in the present disclosure preferably does not contain a nitro group. When a compound having a nitro group is used as a substrate, the reactivity of the group -CX 3 3 is extremely high, and as a result, side reactions proceed, and the selectivity of the target product tends to decrease.

[0060] Specific examples of the compound represented by the general formula (2) that satisfies the above conditions include

[0061]

Chemical formula

[0062]

Chemical formula

[0063] etc.

[0064] As for the compound represented by the above general formula (2), known or commercially available products can be used. Further, the compound represented by the above general formula (2) can be used alone or in combination of two or more.

[0065] (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 in 3 3 is fluorinated to produce the compound represented by the above general formula (1). Among them, in the compound represented by the above general formula (2), at least the group -CX 3 all X in 3 3 is fluorinated, and the compound represented by the above general formula (1) in which X 1 is all fluorine atoms is likely to be produced.

[0066] At this time, when X 4 is a hydrogen atom or a fluorine atom, it remains unchanged by the reaction of the present disclosure. That is, when X 4 is a hydrogen atom or a fluorine atom, X 2 is also a hydrogen atom or a fluorine atom.

[0067] On the other hand, when X 4 is a halogen atom other than a fluorine atom, it is likely to be fluorinated by the reaction of the present disclosure. That is, when X 4 is a halogen atom other than a fluorine atom, X 2 is likely to become a fluorine atom.

[0068] From the above, in the reaction of the present disclosure, in the compound represented by the above general formula (2), when X 4 contains a halogen atom other than a fluorine atom, one or more halogen atoms other than the fluorine atom represented by X 4 are also fluorinated, and the compound represented by the above general formula (1) is likely to be produced. Among them, in the compound represented by the above general formula (2), X 4When it contains a halogen atom other than a fluorine atom, all X 4 is fluorinated, and X 2 are all fluorine atoms, and the compound represented by the general formula (1) is likely to be produced.

[0069] On the other hand, in the compound represented by the general formula (2) described above, when X 4 contains a hydrogen atom or a fluorine atom, the hydrogen atom or the fluorine atom remains unchanged even by the reaction of the present disclosure.

[0070] As a result, the compound represented by the general formula (1) is obtained.

[0071] (1-3) Hydrogen fluoride The hydrogen fluoride used in the production method of the present disclosure may be gaseous hydrogen fluoride, liquid hydrogen fluoride, or an aqueous solution (hydrofluoric acid). Among them, gaseous hydrogen fluoride is preferred from the viewpoints of productivity, corrosivity, etc. When using liquid hydrogen fluoride or an aqueous solution (hydrofluoric acid), it is also possible to use the hydrogen fluoride as a solvent.

[0072] Known or commercially available hydrogen fluoride can be used.

[0073] The amount of hydrogen fluoride used in the production method of the present disclosure is not particularly limited, but from the viewpoints of conversion rate, selectivity, yield, etc., 1 to 100 moles, preferably 10 to 50 moles, more preferably 15 to 25 moles, are preferred per 1 mole of the compound represented by the general formula (2).

[0074] (1-4) Base 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 that may be supported on polymers.

[0075] Examples of the amine include aliphatic amines (aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines), alicyclic amines (alicyclic secondary amines, alicyclic tertiary amines), aromatic amines (aromatic primary amines, aromatic secondary amines, aromatic tertiary amines), heterocyclic amines, polymer-supported amines (polyallylamine, polyvinylpyridine, etc.).

[0076] Examples of the aliphatic primary amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, ethylenediamine, etc.

[0077] Examples of the aliphatic secondary amine include dimethylamine, diethylamine, di(n-propyl)amine, diisopropylamine, di(n-butyl)amine, diisobutylamine, di(sec-butyl)amine, di(tert-butylamine), di(n-pentyl)amine, di(n-hexyl)amine, dicyclohexylamine, etc.

[0078] Examples of the aliphatic tertiary amine include trimethylamine, triethylamine, diisopropylethylamine, N,N,N’,N’-tetramethylethylenediamine, etc.

[0079] Examples of the alicyclic secondary amine include piperidine, piperazine, pyrrolidine, morpholine, etc.

[0080] Examples of the alicyclic tertiary amine include N-methylpiperazine, N-methylpyrrolidine, 5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, etc.

[0081] Examples of aromatic amines include aniline, methylaniline, dimethylaniline, N,N-dimethylaniline, haloaniline, nitroaniline, etc.

[0082] Examples of heterocyclic amines include pyridine, pyrimidine, piperazine, quinoline, imidazole, etc.

[0083] Examples of ureas 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'-dimethylpropyleneurea, N,N'-diethylpropyleneurea, N,N'-di(n-propyl)propyleneurea, N,N'-di(n-butyl)propyleneurea, etc.

[0084] Examples of amides include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, etc.

[0085] Examples of ethers include di(n-butyl) ether, di(n-hexyl) ether, anisole, phenetole, n-butyl phenyl ether, amyl phenyl 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, diethylene glycol dibutyl ether, etc.

[0086] Examples of esters include n-butyl acetate, n-pentyl acetate, isopentyl acetate, cyclohexyl acetate, benzyl acetate, n-butyl propionate, isopentyl propionate, methyl benzoate, dimethyl phthalate, γ-butyrolactone, etc.

[0087] Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and the like.

[0088] Examples of the alkaline earth metal hydroxide include magnesium hydroxide, calcium hydroxide, barium hydroxide, and the like.

[0089] Examples of the alkali metal alkoxide include sodium methoxide, sodium ethoxide, sodium n-butoxide, potassium methoxide, potassium ethoxide, potassium n-butoxide, lithium methoxide, lithium ethoxide, and the like.

[0090] Examples of the alkali metal hydride include sodium hydride, potassium hydride, lithium hydride, and the like.

[0091] Examples of the alkaline earth metal hydride include calcium hydride, and the like.

[0092] Examples of the alkaline earth metal oxide include magnesium oxide, calcium oxide, and the like.

[0093] Examples of the alkali metal include sodium, potassium, lithium, and the like.

[0094] Examples of the ammonium hydroxide salt which may carry a polymer include ammonia, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra(n-butyl)ammonium hydroxide, (n-octyl)triethylammonium hydroxide, benzyltrimethylammonium hydroxide, Amberlite resin, and the like.

[0095] These bases can be known or commercially available products. The bases can be used alone or in combination of two or more. Among them, from the viewpoints of conversion rate, selectivity, yield, etc., amines are preferred, aliphatic amines, heterocyclic amines, etc. are more preferred, and aliphatic tertiary amines, heterocyclic amines, etc. are even more preferred. When using a liquid base or an aqueous solution, it is also possible to use the base as a solvent.

[0096] The amount of the base used in the production method of the present disclosure is not particularly limited, but from the viewpoints of conversion rate, selectivity, yield, etc., 1 to 100 moles, preferably 10 to 50 moles, more preferably 15 to 25 moles, are preferred per 1 mole of the compound represented by the general formula (2).

[0097] (1 - 5) Acids other than hydrogen fluoride The acids other than hydrogen fluoride that can be used in the production method of the present disclosure are not particularly limited, but from the viewpoints of conversion rate, selectivity, yield, etc., it is preferable that the pKa is -10 to 20, more preferably -7.5 to 15, and even more preferably -5 to 10.

[0098] Examples of such acids other than hydrogen fluoride acid include, for example, organic acids such as sulfonic acid compounds (methanesulfonic acid, p-toluenesulfonic acid, etc.), carboxylic acid compounds (trifluoroacetic acid, etc.), and inorganic acids such as phosphoric acid can also be used. Among them, from the viewpoints of conversion rate, selectivity, yield, etc., organic acids are preferred, and sulfonic acid compounds are more preferred.

[0099] These acids other than hydrogen fluoride can be known or commercially available products. The above-mentioned acids other than hydrogen fluoride can be used alone or in combination of two or more. When using a liquid acid other than hydrogen fluoride or an aqueous solution, it is also possible to use the acid other than hydrogen fluoride as a solvent.

[0100] In the reaction of the present disclosure, the amount of the acid other than hydrogen fluoride is not particularly limited. However, from the viewpoints of conversion rate, selectivity, yield, etc., 1 to 100 moles, more preferably 10 to 50 moles, and even more preferably 15 to 25 moles are preferred per 1 mole of the compound represented by the general formula (2). When using a plurality of acids other than hydrogen fluoride, it is preferable to adjust the total amount to be within the above range.

[0101] (1-6) Reaction temperature In the reaction of the present disclosure, the reaction temperature is not particularly limited. However, from the viewpoints of conversion rate, selectivity, yield, etc., usually 50 to 250 °C is preferred, more preferably 100 to 200 °C, and even more preferably 125 to 175 °C.

[0102] (1-7) Reaction time The reaction time (maintenance time at the maximum temperature reached) of the reaction of the present disclosure can be set to such an extent that the reaction proceeds sufficiently. From the viewpoints of conversion rate, selectivity, yield, etc., 1 minute to 48 hours is preferred, and 5 minutes to 24 hours is more preferred. When the reaction of the present disclosure is carried out in the gas phase, particularly in a gas-phase continuous flow mode, the contact time (W / F) [W: weight of the catalyst (g), F: flow rate of the raw material compound (octafluorobutene) (cc / sec)] of the raw material compound (compound represented by the general formula (2)) with respect to the catalyst (acid other than hydrogen fluoride) is preferably 1 to 100, more preferably 5 to 75, and even more preferably 10 to 50.

[0103] (1-8) Reaction pressure The reaction pressure of the reaction of the present disclosure is not particularly limited. However, from the viewpoints of conversion rate, selectivity, yield, etc., -2.0 to 2.0 MPa is preferred, more preferably -1.0 to 1.0 MPa, and even more preferably -0.5 to 0.5 MPa. In the present disclosure, when there is no particular notation about the pressure, it is the gauge pressure.

[0104] In the reaction of the present disclosure, the reactor that can be employed is not particularly limited in terms of shape and structure as long as it can withstand the above temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multitubular reactor. Examples of the material of the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloy.

[0105] (1-9) Exemplification of the reaction The reaction of the present disclosure can be carried out in either a batch mode in which the raw materials are charged into the reactor all at once or a flow mode in which the raw materials are continuously supplied into the reactor while the product is withdrawn from the reactor.

[0106] Further, the reaction of the present disclosure described above can be carried out in the liquid phase or in the gas phase. Among them, from the viewpoints of equipment cost, productivity, etc., it is preferably carried out in the liquid phase.

[0107] In addition, in the reaction of the present disclosure, the compound represented by the general formula (2), hydrogen fluoride, a base, and an acid other than hydrogen fluoride can be added simultaneously or sequentially. Further, after reacting some of the components in advance, the remaining components can be reacted. Among them, from the viewpoint of handleability, it is preferable to react the mixture of hydrogen fluoride and a base prepared by mixing (reacting) hydrogen fluoride and a base in advance with the mixture, the compound represented by the general formula (2), and an acid other than hydrogen fluoride. Note that, from the viewpoint of handleability, the mixture obtained by mixing hydrogen fluoride and a base is preferably a complex in which hydrogen fluoride and a base are combined into one body. Also, as described above, in the reaction of the present disclosure, the reaction can also be advanced by adding the compound represented by the general formula (2) and hydrogen fluoride.

[0108] However, hydrogen fluoride alone becomes a gas under normal handling conditions due to its low boiling point (boiling point 20°C), and combined with its high toxicity, it is difficult to handle. Therefore, it is difficult to use hydrogen fluoride alone on an industrial scale. On the other hand, by forming a complex, the boiling point can be raised, and it can be made into a liquid under normal handling conditions, making it easy to handle and easy to handle on an industrial scale. Furthermore, as shown in the examples, using a complex is more likely to reduce the amount of other impurities and is more likely to reduce impurities that cannot be recycled, which is also advantageous in terms of cost.

[0109] From the above, hydrogen fluoride, a base, and an acid other than hydrogen fluoride that can be used in the production method of the present disclosure can be used as fluorinating agents, particularly as fluorinating agents for the compounds represented by the general formula (2). In the fluorinating agent of the present disclosure, taking the total amount of the fluorinating agent of the present disclosure as 100 mol%, the content of hydrogen fluoride is 0.1 to 99 mol% (preferably 1 to 90 mol%), the content of the base is 0.1 to 99 mol% (preferably 1 to 90 mol%), and the content of the acid other than hydrogen fluoride is 0.1 to 99 mol% (preferably 1 to 90 mol%) is preferred.

[0110] Regarding the atmosphere when carrying out the reaction of the present disclosure, an inert gas atmosphere is preferred from the viewpoint of suppressing the deterioration of the compound represented by the general formula (2), hydrogen fluoride, the base, and the acid other than hydrogen fluoride.

[0111] Examples of the inert gas include nitrogen, helium, argon, etc. Among these inert gases, nitrogen is preferred from the viewpoint of cost reduction.

[0112] After completion of the reaction, purification treatment can be carried out according to a conventional method as necessary to obtain the compound represented by the general formula (1).

[0113] (1 - 10) Target compound (general formula (1)) The target compound thus produced has the general formula (1):

[0114]

Chemical formula

[0115] [In the formula, X 1 is the same or different and represents a hydrogen atom or a halogen atom. However, in the group - CX 1 3, at least one of the three X 1 is a fluorine atom. X 2 is the same or different and represents a hydrogen atom or a halogen atom. n represents an integer of 1 to 5. ] It is a compound represented by the formula.

[0116] In the general formula (1), the halogen atom represented by X 1 is not particularly limited, and examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0117] The compound represented by the general formula (1) is at least one of the X in the group - CX 3 3 in the compound represented by the general formula (2) is fluorinated, so in the group - CX 3 3, at least one of the three X 1 3 is a fluorine atom. 1 is a fluorine atom.

[0118] Also, in the general formula (1), the halogen atom represented by X 2 is not particularly limited, and examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. In the compound represented by the general formula (2), when X 4 is a hydrogen atom or a fluorine atom, in the compound represented by the general formula (1), X 2 remains a hydrogen atom or a fluorine atom. On the other hand, in the compound represented by the general formula (2), when X 4 is a halogen atom other than a fluorine atom, in the compound represented by the general formula (1), X 2 may remain a halogen atom other than a fluorine atom, or may be fluorinated and X 2 may become a fluorine atom.

[0119] In general formula (1), n 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, in the same manner as in general formula (2).

[0120] From the above, the compound represented by general formula (1), which is the target compound produced in the present disclosure, specifically,

[0121]

Chemical formula

[0122]

Chemical formula

[0123]

Chemical formula

[0124]

Chemical formula

[0125] etc. can be mentioned.

[0126] 2. Composition As described above, the compound represented by general formula (1) can be obtained. As the compound represented by general formula (1), general formula (1A):

[0127]

Chemical formula

[0128] [In the formula, X 2 is the same or different and represents a hydrogen atom or a halogen atom. n represents an integer of 1 to 5.] and the compound represented by General formula (1B):

[0129] [Chemical formula]

[0130] [In the formula, X 1a are the same or different and each represents a hydrogen atom or a halogen atom. However, in the group - CX 1a 3, one or two of the three X 1a are fluorine atoms, and the remaining two or one are a hydrogen atom or a halogen atom other than a fluorine atom. X 2 are the same or different and each represents a hydrogen atom or a halogen atom. n represents an integer from 1 to 5.] It may also be obtained in the form of a composition containing both of them and a compound represented by

[0131] In general formulas (1A) and (1B), X 1 , X 2 and n can adopt the above-mentioned ones. The same applies to the preferred specific examples.

[0132] Therefore, as the compound represented by general formula (1A), for example,

[0133] [Chemical formula]

[0134] [Chemical formula]

[0135] etc. can be mentioned.

[0136] Also, as the compound represented by general formula (1B), for example,

[0137] [Chemical formula]

[0138]

Chem.

[0139]

Chem.

[0140] etc. can be mentioned.

[0141] In the composition of the present disclosure, the content of the compound represented by the general formula (1A) can be 1.0 to 99.9 mol%, particularly 5.0 to 99.5 mol%, and further 8.0 to 99.0 mol% based on 100 mol% of the total amount of the composition of the present disclosure.

[0142] In the composition of the present disclosure, the content of the compound represented by the general formula (1B) can be 0.1 to 95.0 mol%, particularly 0.5 to 94.0 mol%, and further 1.0 to 92.0 mol% based on 100 mol% of the total amount of the composition of the present disclosure.

[0143] In addition, when 0 to 4 of n X 2 are halogen atoms, the content of the compound represented by the 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 100 mol% of the total amount of the composition of the present disclosure.

[0144] In addition, when 0 to 4 of n X 2 are halogen atoms, the content of the compound represented by the 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 100 mol% of the total amount of the composition of the present disclosure.

[0145] In addition, when 0 to 4 of n X 2Among them, when 1 to 5 are halogen atoms, the content of the compound represented by the 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 100 mol% of the total amount of the composition of the present disclosure.

[0146] Also, among n X 2 when 0 to 4 are halogen atoms, the content of the compound represented by the 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 100 mol% of the total amount of the composition of the present disclosure.

[0147] In the composition of the present disclosure, the total content of the compound represented by the general formula (1A) and the compound represented by the general formula (1B) can be 90.0 to 100 mol%, particularly 93.0 to 99.9 mol%, and further 95.0 to 99.8 mol% based on 100 mol% of the total amount of the composition of the present disclosure.

[0148] Such a composition of the present disclosure can be effectively used for various applications such as etching gas, cleaning gas, and deposit gas.

[0149] As described above, the embodiments of the present disclosure have been described. However, various changes in form and details are possible without departing from the spirit and scope of the claims.

Examples

[0150] Examples are shown below to clarify the features of the present disclosure. The present disclosure is not limited to these examples.

[0151] In Examples and Comparative Examples, as the substrate,

[0152]

Chemical formula

[0153] Using pentafluorobenzotrichloride with n = 5, 2,4-difluorobenzotrichloride with n = 2, and benzotrichloride with n = 0.

[0154] In the following examples and comparative examples, as the complex of hydrogen fluoride and amine, hydrogen fluoride-triethylamine complex (hydrogen fluoride:triethylamine = 1:3 (molar ratio)) and hydrogen fluoride-pyridine complex (hydrogen fluoride:triethylamine = 1:9 (molar ratio)) were used. The hydrogen fluoride-triethylamine complex was produced by blowing hydrogen fluoride into triethylamine, and the hydrogen fluoride-pyridine complex was produced by blowing hydrogen fluoride into pyridine.

[0155] Examples 1 to 15 and Comparative Examples 1 to 5 Into a SUS reactor, the substrates shown in Tables 1 - 4 (1 g, 0.005 mol), hydrogen fluoride-triethylamine complex (10 g, 0.06 mol), hydrogen fluoride-pyridine complex (5 g, 0.02 mol) or anhydrous hydrogen fluoride (10 g, 0.5 mol), and the acids shown in Tables 1 - 4 (0.0005 mol, 10 mol% based on the number of moles of the substrate) were added. The lid of the reactor was closed, heated to the temperatures shown in Tables 1 - 5, and the reaction was allowed to proceed for 24 hours. However, in Examples 16 - 17, no acids other than the base and hydrogen fluoride were used.

[0156] After the reaction was completed, mass spectrometry was performed by gas chromatography and GCMS (gas chromatography-mass spectrometry), and structural analysis was performed using NMR (nuclear magnetic resonance).

[0157] From the results of mass spectrometry and structural analysis, as the target product, when pentafluorobenzotrichloride with n = 5 was used as the substrate, pentafluorotrifluoride could be confirmed; when 2,4-difluorobenzotrichloride with n = 2 was used as the substrate, 2,4-difluorobenzotrifluoride could be confirmed; and when benzotrichloride with n = 0 was used as the substrate, benzotrifluoride could be confirmed.

[0158] The results are shown in Tables 1 to 5.

[0159] Also, in Tables 1 to 5, "trifluoro" means a compound in which all chlorine atoms in the trichloromethyl group of the substrate are fluorinated to form a trifluoromethyl group, "difluoro" means a compound in which two chlorine atoms in the trichloromethyl group of the substrate are fluorinated to form a chlorodifluoromethyl group, and "monofluoro" means a compound in which one chlorine atom in the trichloromethyl group of the substrate is fluorinated to form a dichloromonofluoromethyl group.

[0160] [Table 1]

[0161] [Table 2]

[0162] [Table 3]

[0163] [Table 4]

[0164] [Table 5]

Claims

1. General formula (1): 【Chemical 1】 [In the formula, X １ is the same as or different from, and represents a hydrogen atom or a halogen atom. However, in the group -CX １ ３ at least one of the three X １ is a fluorine atom. X ２ is the same as or different from, and represents a hydrogen atom or a fluorine atom. n represents an integer from 1 to 5.] A method for producing a compound represented by General formula (2): [Chemical 2] [In the formula, n is the same as defined above. X ３ is the same as or different from, and represents a hydrogen atom or a halogen atom. However, in the group -CX ３ ３ among the three X ３ at least one is a halogen atom other than a fluorine atom. X ４ is the same as or different from, and represents a hydrogen atom or a fluorine atom. and a compound represented by Reacting hydrogen fluoride, an amine, and a sulfonic acid compound to fluorinate at least one of the halogen atoms other than fluorine atoms in the group -CX ３ ３ in and converting it to a fluorine atom in the X ３ in to produce a compound represented by the above general formula (1). A production method comprising the step of １ ​

2. Said X １ The production method according to claim 1, wherein all of them are fluorine atoms.

3. Said n Xs ４ The production method according to claim 1 or 2, wherein at least one of them is a fluorine atom.

4. The method according to claim 1 or 2, wherein the reaction is a step of reacting the mixture obtained by mixing the hydrogen fluoride and the amine with the compound represented by the general formula (2) and the sulfonic acid compound.

5. The method according to claim 1 or 2, wherein the pKa of the sulfonic acid compound is -10 to 20.

6. General formula (1A): 【Chemical Formula 3】 [In the formula, X ２ is the same as or different from and represents a hydrogen atom or a fluorine atom. n represents an integer from 1 to 5.] and a compound represented by General formula (1B): [Chemical Formula 4] [In the formula, X ２ and n is the same as described above. X １ａ is the same or different and represents a hydrogen atom or a halogen atom. However, in the group -CX １ａ ３ in which one or two of the three X １ａ are fluorine atoms, and the remaining two or one are a hydrogen atom or a halogen atom other than a fluorine atom.] and a compound represented by, containing with the total amount of the composition being 100 mol%, (1) Among the n X's ２ , 0 to 4 are fluorine atoms, and the content of the compound represented by the general formula (1A) is 15.4 to 20.0 mol%, and the content of the compound represented by the general formula (1B) is 80.0 to 84.3 mol%, and Among the n X's, 1 to 5 are fluorine atoms, and the content of the compound represented by the general formula (1A) is 80.0 to 99.9 mol%, and the content of the compound represented by the general formula (1B) is 0.1 to 15.0 mol%. ２ ​ A composition satisfying any of the above.

7. The composition according to claim 6, which is used as an etching gas, a cleaning gas, or a deposition gas.

8. General formula (2): 【Chemical Formula 5】 [In the formula, X ３ is the same as or different from, and represents a hydrogen atom or a halogen atom. However, in the group -CX ３ ３ in, at least one of the three X ３ is a halogen atom other than a fluorine atom. X ４ is the same or different and represents a hydrogen atom or a fluorine atom. n represents an integer from 1 to 5.] In the compound represented by, the group -CX ３ ３ One or more X in ３ A fluorinating agent used to fluorinate at least one of the halogen atoms other than fluorine atoms in, A fluorinating agent containing hydrogen fluoride, an amine, and a sulfonic acid compound.

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