Method for producing fluorine-containing aromatic compound

Abstract

A method for producing a fluorine-containing aromatic compound, whereby a fluorine-containing aromatic compound such as perfluorotoluene can be efficiently produced by reacting a compound represented by general formula (2) with hydrogen fluoride, a base, and an acid other than hydrogen fluoride to fluorinate at least one or more X3 of-CX33 groups to produce a compound represented by general formula (1). (In the formula, n is the same as below. And X3 may be the same or different and each represents a hydrogen atom or a halogen atom. Wherein, in the-CX33 group, at least one of the three X3 atoms is a halogen atom other than a fluorine atom. And X4 may be the same or different and each represents a hydrogen atom or a halogen atom. ] # imgabs0 #

Description

Technical Field

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

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

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 00 / 047539 Summary of the invention

[0006] Technical problem to be solved by the invention

[0007] The object of the present invention is to provide a novel method for efficiently producing fluorinated aromatic compounds such as perfluorotoluene.

[0008] Technical means for solving technical problems

[0009] The present invention includes the following configurations.

[0010] Item 1. A method for producing a compound represented by general formula (1),

[0011]

[0012] [Wherein,

[0013] X 1 are the same or different and represent a hydrogen atom or a halogen atom. 1 3 bases, 3 Xs 1 At least one of them is a fluorine atom.

[0014] X 2 The same or different represents a hydrogen atom or a halogen atom.

[0015] n represents an integer from 1 to 5.]

[0016] The preparation method comprises reacting a compound represented by the general formula (2) with hydrogen fluoride, a base and an acid other than hydrogen fluoride to at least 3 One or more X in the 3 bases 3 A step of fluorinating to produce the compound represented by the above general formula (1).

[0017]

[0018] [Wherein,

[0019] nSame as above.

[0020] X 3 are the same or different and represent a hydrogen atom or a halogen atom. 3 3 bases, 3 Xs 3 At least one of them is a halogen atom other than a fluorine atom.

[0021] X 4 The same or different, represents a hydrogen atom or a halogen atom.]

[0022] Item 2. The manufacturing method according to Item 1, wherein the X 1 All are fluorine atoms.

[0023] Item 3. The manufacturing method according to Item 1 or 2, wherein the n X 4 At least one of them is a halogen atom.

[0024] 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, the compound represented by the general formula (2), and an acid other than hydrogen fluoride.

[0025] Item 5. The production method according to any one of Items 1 to 4, wherein the acid other than hydrogen fluoride has a pKa of -10 to 20.

[0026] Item 6. A production method as described in any one of Items 1 to 5, wherein the base is at least one selected from amines, ureas, amides, ethers, esters, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, alkali metal hydrides, alkaline earth metal hydrides, alkaline earth metal oxides, alkali metals, and ammonium hydroxide salts that can carry a polymer.

[0027] 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 amines.

[0028] Item 7. A composition comprising a compound represented by the general formula (1A) and a compound represented by the general formula (1B),

[0029] The content of the compound represented by the above general formula (1B) is 0.1 to 95.0 mol % based on the total amount of the composition being 100 mol %.

[0030]

[0031] [Wherein,

[0032] X 2The same or different represents a hydrogen atom or a halogen atom.

[0033] n represents an integer from 1 to 5.]

[0034]

[0035] [Wherein,

[0036] X 2 Same as n.

[0037] X 1a are the same or different and represent a hydrogen atom or a halogen atom. 1a 3 bases, 3 Xs 1a One or two of them are fluorine atoms, and the remaining two or one are hydrogen atoms or halogen atoms other than fluorine atoms.]

[0038] Item 8. The composition according to Item 7, which satisfies any one of the following conditions (1) and (2),

[0039] (1) The above n X 2 0 to 4 of them are halogen atoms, and the content of the compound represented by the above general formula (1B) is 40.0 to 95.0 mol%,

[0040] (2) The above n X 2 1 to 5 of them are halogen atoms, and the content of the compound represented by the above general formula (1B) is 0.1 to 15.0 mol %.

[0041] Item 9. The composition according to Item 7 or 8, which is used as an etching gas, a cleaning gas or a deposition gas.

[0042] Item 10. A fluorinating agent comprising hydrogen fluoride, a base, and an acid other than hydrogen fluoride.

[0043] Item 10-1. The fluorinating agent according to Item 10, wherein the acid other than hydrogen fluoride has a pKa of -10 to 20.

[0044] Item 10-2. A fluorinating agent as described in Item 10 or 10-1, wherein the base is at least one selected from 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 can support a polymer.

[0045] 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.

[0046] 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 the general formula (2).

[0047]

[0048] [Wherein,

[0049] X 3 are the same or different and represent a hydrogen atom or a halogen atom. 3 3 bases, 3 Xs 3 At least one of them is a halogen atom other than a fluorine atom.

[0050] X 4 The same or different represents a hydrogen atom or a halogen atom.

[0051] n represents an integer from 1 to 5.]

[0052] Item 12. A method for producing a compound represented by general formula (1),

[0053]

[0054] [Wherein,

[0055] X 1 are the same or different and represent a hydrogen atom or a halogen atom. 1 3 bases, 3 Xs 1 At least one of them is a fluorine atom.

[0056] X 2 The same or different represents a hydrogen atom or a halogen atom.

[0057] n represents an integer from 1 to 5.]

[0058] The preparation method comprises reacting a compound represented by the general formula (2) with hydrogen fluoride to at least 3 One or more X in the 3 bases 3 A step of fluorinating to produce the compound represented by the general formula (1).

[0059]

[0060] [Wherein,

[0061] nSame as above.

[0062] X 3 are the same or different and represent a hydrogen atom or a halogen atom. 3 3 bases, 3 Xs 3 At least one of them is a halogen atom other than a fluorine atom.

[0063] X 4The same or different, represents a hydrogen atom or a halogen atom.]

[0064] Effects of the Invention

[0065] According to the present invention, a new method capable of efficiently producing a fluorine-containing aromatic compound can be provided. DETAILED DESCRIPTION

[0066] In the present specification, “comprising” is a concept including any of “including”, “consisting essentially of” and “consisting only of”.

[0067] In addition, in this specification, when a numerical range is expressed as "A to B", it means not less than A and not more than B.

[0068] In the present invention, the "selectivity" means the ratio (mol %) of the total molar amount of the target compound contained in the gas flowing out from the reactor outlet to the total molar amount of the compounds other than the raw material compound in the flowing out gas.

[0069] In the present invention, the "conversion rate" means the ratio (mol %) of the total molar amount of compounds other than the raw material compound contained in the gas flowing out from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

[0070] In the present invention, the "yield" means the ratio (mol %) of the total molar amount of the target compound contained in the gas flowing out from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

[0071] 1. Method for producing fluorinated aromatic compounds

[0072] The production method of the present invention is a method for producing a compound represented by the general formula (1).

[0073]

[0074] [Wherein,

[0075] X 1 are the same or different and represent a hydrogen atom or a halogen atom. 1 3 bases, 3 Xs 1 At least one of them is a fluorine atom.

[0076] X 2 The same or different represents a hydrogen atom or a halogen atom.

[0077] n represents an integer from 1 to 5.]

[0078] The preparation method comprises reacting a compound represented by the general formula (2) with hydrogen fluoride, a base and an acid other than hydrogen fluoride to at least 3 One or more X in the 3 bases 3 A step of fluorinating to produce the compound represented by the above general formula (1).

[0079]

[0080] [Wherein,

[0081] nSame as above.

[0082] X 3 are the same or different and represent a hydrogen atom or a halogen atom. 3 3 bases, 3 Xs 3 At least one of them is a halogen atom other than a fluorine atom.

[0083] X 4 The same or different, represents a hydrogen atom or a halogen atom.]

[0084] The production method of the present invention is not limited to the above method. By reacting the compound represented by the above general formula (2) with hydrogen fluoride, at least -CX 3 One or more X in the 3 bases 3 Fluorination to generate the compound represented by the above general formula (1). That is, without using one or both of the base and the acid other than hydrogen fluoride, it is also possible to at least convert -CX 3 One or more X in the 3 bases 3 Fluorination is performed to produce the compound represented by the above general formula (1). However, from the viewpoint of reaction stability and operability, it is preferred to use hydrogen fluoride, a base, or an acid other than hydrogen fluoride.

[0085] (1-1) Starting compound (general formula (2))

[0086] In the production method of the present invention, the compound represented by the general formula (2) is a compound represented by the following general formula (2).

[0087]

[0088] [Wherein,

[0089] X 3 are the same or different and represent a hydrogen atom or a halogen atom. 3 3 bases, 3 Xs 3 At least one of them is a halogen atom other than a fluorine atom.

[0090] X 4 The same or different represents a hydrogen atom or a halogen atom.

[0091] n represents an integer from 1 to 5.]

[0092] In the general formula (2), as X 3 The halogen atom shown is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among them, a chlorine atom is preferred from the viewpoints of conversion rate, selectivity, yield, etc.

[0093] X 3 It can be a hydrogen atom or a halogen atom, but in X 3 When all of X are hydrogen atoms, the reaction hardly proceeds, and even if the temperature is raised, the compound represented by the general formula (1) as the target product can hardly be obtained. 3 In the case where all of them are fluorine atoms, since they have already been fluorinated, there is no need to adopt the production method of the present invention. 3 3 bases, 3 Xs 3 At least one of them is a halogen atom other than a fluorine atom.

[0094] In the general formula (2), as X 4 The halogen atom shown is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among them, a fluorine atom is preferred from the viewpoints of conversion rate, selectivity, yield, etc.

[0095] Among them, in n X 4 In the present invention, if the number of halogen atoms (especially fluorine atoms) increases, there is a tendency for the conversion rate of the reaction to decrease. Nevertheless, in the present invention, by using an acid other than hydrogen fluoride, the conversion rate can be increased. 4 The more halogen atoms (especially fluorine atoms) there are in the present invention, the better the effect obtained by the production method of the present invention. 4 In the embodiment of the present invention, at least one of the halogen atoms is preferably a halogen atom. For example, when n is 5, at least one of the halogen atoms is preferably a halogen atom. 4 In the above, from the viewpoints of conversion rate, selectivity, yield, etc., the number of halogen atoms (particularly fluorine atoms) is preferably 1 to 5, more preferably 2 to 5, further preferably 3 to 5, particularly preferably 4 to 5.

[0096] In the general formula (2), n is an integer of 1 to 5. From the viewpoint 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.

[0097] Among them, in X 4 When the number of substitutions n is 5, the compound represented by the general formula (2) is a compound represented by the general formula (2A).

[0098]

[0099] [Wherein, X 3 and X 4 Same as above.]

[0100] Among them, the compound represented by the general formula (2) used as a substrate in the present invention preferably does not contain a nitro group. When a compound having a nitro group is used as a substrate, -CX 3 The reactivity of the 3-base becomes extremely high, and a side reaction occurs, resulting in a tendency for the selectivity of the target product to decrease.

[0101] Specific examples of the compound represented by the general formula (2) that satisfies the above conditions include:

[0102]

[0103]

[0104] wait.

[0105] The compound represented by the general formula (2) may be a known or commercially available compound. The compound represented by the general formula (2) may be used alone or in combination of two or more.

[0106] (1-2) Reaction

[0107] In the reaction of the present invention, at least -CX 3 One or more X in the 3 bases 3 Fluorinated to form the compound represented by the above general formula (1). Among the compounds represented by the above general formula (2), at least -CX 3 All X in 3-basis 3 Fluorinated, easily generate X 1 All of them are compounds represented by the above general formula (1) containing fluorine atoms.

[0108] At this time, in X 4 When X is a hydrogen atom or a fluorine atom, it remains unchanged even through the reaction of the present invention. 4 When X is a hydrogen atom or a fluorine atom, 2 Also a hydrogen atom or a fluorine atom.

[0109] On the other hand, in X 4 When X is a halogen atom other than a fluorine atom, it is easily fluorinated by the reaction of the present invention. 4 When X is a halogen atom other than a fluorine atom, 2 Easily converted into fluorine atoms.

[0110] According to the above, in the reaction of the present invention, in the compound represented by the above general formula (2), X 4 When a halogen atom other than a fluorine atom is contained, one or more X4 Halogen atoms other than the fluorine atom shown in the above formula are also fluorinated, and the compound shown in the above formula (1) is easily generated. 4 When a halogen atom other than a fluorine atom is included, all X 4 Fluorinated, easily generate X 2 All of them are compounds represented by the above general formula (1) containing fluorine atoms.

[0111] On the other hand, in the compound represented by the above general formula (2), X 4 When hydrogen atoms or fluorine atoms are contained, the hydrogen atoms or fluorine atoms remain without being changed by the reaction of the present invention.

[0112] As a result, a compound represented by the general formula (1) can be obtained.

[0113] (1-3) Hydrogen fluoride

[0114] The hydrogen fluoride used in the production method of the present invention 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, corrosiveness, etc. Among them, when using liquid hydrogen fluoride or an aqueous solution (hydrofluoric acid), the hydrogen fluoride may also be used as a solvent.

[0115] As hydrogen fluoride, a known or commercially available product can be used.

[0116] The amount of hydrogen fluoride used in the production method of the present invention is not particularly limited, but 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 the general formula (2), from the viewpoints of conversion rate, selectivity, yield, etc.

[0117] (1-4) Alkali

[0118] 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.

[0119] Examples of amines include aliphatic amines (aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines), alicyclic amines (aliphatic secondary amines, aliphatic tertiary amines), aromatic amines (aromatic primary amines, aromatic secondary amines, aromatic tertiary amines), heterocyclic amines, polymer-supported amines (polyallylamine, polyvinylpyridine, etc.), and the like.

[0120] Examples of the aliphatic primary amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, and ethylenediamine.

[0121] Examples of the aliphatic secondary amine include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di-n-pentylamine, di-n-hexylamine, and dicyclohexylamine.

[0122] Examples of the aliphatic tertiary amine include trimethylamine, triethylamine, diisopropylethylamine, and N,N,N′,N′-tetramethylethylenediamine.

[0123] Examples of the alicyclic secondary amine include piperidine, piperazine, pyrrolidine, and morpholine.

[0124] Examples of the alicyclic tertiary amine include N-methylpiperazine, N-methylpyrrolidine, 5-diazabicyclo[4.3.0]non-5-ene, and 1,4-diazabicyclo[2.2.2]octane.

[0125] Examples of the aromatic amine include aniline, methylaniline, dimethylaniline, N,N-dimethylaniline, halogenated aniline, and nitroaniline.

[0126] Examples of the heterocyclic amine include pyridine, pyrimidine, piperazine, quinoline, and imidazole.

[0127] 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'-dimethylpropyleneurea, N,N'-diethylpropyleneurea, N,N'-di-n-propylpropyleneurea, and N,N'-di-n-butylpropyleneurea.

[0128] Examples of the amide include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidone.

[0129] 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.

[0130] 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.

[0131] Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide.

[0132] Examples of the alkaline earth metal hydroxide include magnesium hydroxide, calcium hydroxide, and barium hydroxide.

[0133] 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.

[0134] Examples of the alkali metal hydride include sodium hydride, potassium hydride, lithium hydride and the like.

[0135] Examples of the alkaline earth metal hydride include calcium hydride and the like.

[0136] Examples of the alkaline earth metal oxide include magnesium oxide and calcium oxide.

[0137] Examples of the alkali metal include sodium, potassium, and lithium.

[0138] Examples of the ammonium hydroxide salt that can support a polymer include ammonia, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, n-octyltriethylammonium hydroxide, benzyltrimethylammonium hydroxide, and amberlite resin.

[0139] These bases can use known or commercially available products. In addition, the base 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 further preferred. Among them, when using a liquid base or an aqueous solution, the base can also be used as a solvent.

[0140] The amount of the base used in the production method of the present invention is not particularly limited, but is preferably 1 to 100 mol, more preferably 10 to 50 mol, and even more preferably 15 to 25 mol per mol of the compound represented by the general formula (2), from the viewpoints of conversion rate, selectivity, yield, etc.

[0141] (1-5) Acids other than hydrogen fluoride

[0142] The acid other than hydrogen fluoride that can be used in the production method of the present invention is not particularly limited, but the pKa is preferably -10 to 20, more preferably -7.5 to 15, and even more preferably -5 to 10 from the viewpoint of conversion, selectivity, yield, and the like.

[0143] As such an acid other than hydrofluoric acid, for example, organic acids such as sulfonic acid compounds (methanesulfonic acid, p-toluenesulfonic acid, etc.) and carboxylic acid compounds (trifluoroacetic acid, etc.) can be used, and inorganic acids such as phosphoric acid can also be used. Among them, organic acids are preferred, and sulfonic acid compounds are more preferred from the viewpoints of conversion rate, selectivity, yield, etc.

[0144] Acids other than these hydrogen fluorides can use known or commercially available products. In addition, the acids other than the above hydrogen fluorides can be used alone or in combination of two or more. Where an acid other than liquid hydrogen fluoride or an aqueous solution is used, the acid other than the hydrogen fluoride can also be used as a solvent.

[0145] In the reaction of the present invention, the amount of the acid other than hydrogen fluoride used is not particularly limited. From the viewpoints of conversion rate, selectivity, yield, etc., it is preferably 1 to 100 mol, more preferably 10 to 50 mol, and even more preferably 15 to 25 mol per 1 mol of the compound represented by the general formula (2). When a plurality of acids other than hydrogen fluoride are used, it is preferred that the total amount thereof be adjusted to fall within the above range.

[0146] (1-6) Reaction temperature

[0147] In the reaction of the present invention, the reaction temperature is not particularly limited, but is usually preferably 50 to 250°C, more preferably 100 to 200°C, and further preferably 125 to 175°C from the viewpoints of conversion, selectivity, yield, and the like.

[0148] (1-7) Reaction time

[0149] The reaction time (maintenance time at the highest temperature reached) of the reaction of the present invention can be set to a degree that the reaction proceeds fully, and from the viewpoints of conversion rate, selectivity, yield, etc., it is preferably 1 minute to 48 hours, and more preferably 5 minutes to 24 hours. Among them, when the reaction of the present invention is carried out in a gas phase, especially in a gas phase continuous flow mode, the contact time (W / F) [W: weight of catalyst (g), F: flow rate (cc / sec) of the raw material compound (octafluorobutene)] of the raw material compound (compound represented by general formula (2)) and the catalyst (acid other than hydrogen fluoride) is preferably 1 to 100, more preferably 5 to 75, and further preferably 10 to 50.

[0150] (1-8) Reaction pressure

[0151] The reaction pressure of the reaction of the present invention is not particularly limited, but 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 conversion, selectivity, yield, etc. In the present invention, pressure refers to gauge pressure unless otherwise specified.

[0152] In the reaction of the present invention, as the reactor that can be adopted, as long as it can withstand the above-mentioned temperature and pressure, the shape and structure are not particularly limited. As the reactor, for example, a vertical reactor, a horizontal reactor, a multi-tube reactor, etc. can be listed. As the material of the reactor, for example, glass, stainless steel, iron, nickel, iron-nickel alloy, etc. can be listed.

[0153] (1-9) Example of reaction

[0154] Such a reaction of the present invention can be carried out in any of a batch method in which raw materials are added to a reactor all at once, or a flow method in which raw materials are continuously supplied to a reactor and products are taken out from the reactor.

[0155] The above-mentioned reaction of the present invention may be carried out in a liquid phase or a gas phase, but it is preferably carried out in a liquid phase from the viewpoint of equipment cost, productivity, etc.

[0156] Furthermore, in the reaction of the present invention, the compound represented by the general formula (2), hydrogen fluoride, a base, and an acid other than hydrogen fluoride may be added simultaneously or sequentially. Furthermore, it is also possible to react some of the components in advance and then react the remaining components. Among them, from the viewpoint of operability, it is preferred to mix (react) hydrogen fluoride and a base in advance to produce a mixture of hydrogen fluoride and a base, and then react the above mixture, the compound represented by the general formula (2), and an acid other than hydrogen fluoride. Among them, regarding the mixture obtained by mixing hydrogen fluoride and a base, from the viewpoint of operability, a complex in which hydrogen fluoride and a base are combined and integrated is preferred. In addition, as described above, the reaction of the present invention can also be reacted by adding a compound represented by the general formula (2) and hydrogen fluoride.

[0157] Among them, in the case of hydrogen fluoride alone, due to its low boiling point (boiling point 20°C), it becomes a gas under normal operating conditions, and the high toxicity of hydrogen fluoride makes it difficult to operate, and it is difficult to use hydrogen fluoride alone on an industrial scale. On the other hand, by making a composite, the boiling point can be increased, and it becomes a liquid under normal operating conditions, so it is easy to operate, and it is also easy to operate on an industrial scale. In addition, when using the composite, as shown in the embodiment, it is also possible to reduce the amount of other impurities and the impurities that cannot be recycled, which is advantageous from the perspective of price.

[0158] Based on the above, hydrogen fluoride, base, and acid other than hydrogen fluoride that can be used in the production method of the present invention can be used as a fluorinating agent, especially a fluorinating agent for the compound represented by general formula (2). In such a fluorinating agent of the present invention, taking the total amount of the fluorinating agent of the present invention as 100 mol%, it is preferred that the content of hydrogen fluoride is set to 0.1 to 99 mol% (preferably 1 to 90 mol%), the content of the base is set to 0.1 to 99 mol% (preferably 1 to 90 mol%), and the content of the acid other than hydrogen fluoride is set to 0.1 to 99 mol% (preferably 1 to 90 mol%).

[0159] The atmosphere for carrying out the reaction of the present invention is preferably an inert gas atmosphere from the viewpoint of suppressing the degradation of the compound represented by the general formula (2), hydrogen fluoride, a base, and an acid other than hydrogen fluoride.

[0160] Examples of the inert gas include nitrogen, helium, and argon. Among these inert gases, nitrogen is preferred from the viewpoint of cost reduction.

[0161] After the reaction is completed, purification treatment may be performed according to a conventional method as necessary to obtain a compound represented by the general formula (1).

[0162] (1-10) Target compound (general formula (1))

[0163] Thus, the target compound is a compound represented by the general formula (1).

[0164]

[0165] [Wherein,

[0166] X 1 are the same or different and represent a hydrogen atom or a halogen atom. 1 3 bases, 3 Xs 1 At least one of them is a fluorine atom.

[0167] X 2 The same or different represents a hydrogen atom or a halogen atom.

[0168] n represents an integer from 1 to 5.]

[0169] In the general formula (1), as X 1 The halogen atom shown is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0170] The compound represented by the general formula (1) is a compound represented by the general formula (2) in which at least -CX 3 One or more X in the 3 bases 3 Fluorinated, so in -CX 1 3 bases, 3 Xs 1At least one of them is a fluorine atom.

[0171] In the general formula (1), X 2 The halogen atom represented by X is not particularly limited, and examples thereof include fluorine atom, chlorine atom, bromine atom, iodine atom, and the like. 4 When X is a hydrogen atom or a fluorine atom, in the compound represented by the general formula (1), 2 On the other hand, in the compound represented by the general formula (2), X 4 When X is a halogen atom other than a fluorine atom, in the compound represented by the general formula (1), 2 It is a halogen atom other than a fluorine atom as it is, but it may be fluorinated to form X 2 into fluorine atoms.

[0172] In the 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, similarly to the general formula (2).

[0173] Based on the above, the compound represented by the general formula (1) produced as the target compound in the present invention can be specifically listed as follows:

[0174]

[0175]

[0176]

[0177] wait.

[0178] 2. Composition

[0179] The compound represented by the general formula (1) can be obtained as described above. However, the compound represented by the general formula (1) may be obtained as a composition containing both the compound represented by the general formula (1A) and the compound represented by the general formula (1B).

[0180]

[0181] [Wherein,

[0182] X 2 The same or different represents a hydrogen atom or a halogen atom.

[0183] n represents an integer from 1 to 5.]

[0184]

[0185] [Wherein,

[0186] X 1a are the same or different and represent a hydrogen atom or a halogen atom. 1a 3 bases, 3 Xs 1a One or two of them are fluorine atoms, and the remaining two or one are hydrogen atoms or halogen atoms other than fluorine atoms.

[0187] X 2 The same or different represents a hydrogen atom or a halogen atom.

[0188] n represents an integer from 1 to 5.]

[0189] In the general formulae (1A) and (1B), X 1 , X 2 The groups described above can be used for n. The same applies to the preferred specific examples.

[0190] Therefore, examples of the compound represented by the general formula (1A) include:

[0191]

[0192] wait. In addition, examples of the compound represented by the general formula (1B) include:

[0193]

[0194]

[0195] wait.

[0196] In the composition of the present invention, the content of the compound represented by general formula (1A) can be 1.0 to 99.9 mol %, particularly 5.0 to 99.5 mol %, and can also be 8.0 to 99.0 mol %, based on 100 mol % of the total amount of the composition of the present invention.

[0197] In the composition of the present invention, the content of the compound represented by general formula (1B) can be 0.1 to 95.0 mol %, particularly 0.5 to 94.0 mol %, and can also be 1.0 to 92.0 mol %, based on the total amount of the composition of the present invention being 100 mol %.

[0198] Among them, in n X 2 When 0 to 4 of them 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 can also be 8.0 to 20.0 mol%, based on the total amount of the composition of the present invention being 100 mol%.

[0199] In addition, in n X 2 When 0 to 4 of them 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 can also be 80.0 to 92.0 mol%, based on the total amount of the composition of the present invention being 100 mol%.

[0200] In addition, in n X 2 When 1 to 5 of them 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 can also be 82.0 to 99.0 mol%, based on the total amount of the composition of the present invention being 100 mol%.

[0201] In addition, in n X 2 When 0 to 4 of them 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 can also be 1.0 to 14.0 mol%, based on the total amount of the composition of the present invention being 100 mol%.

[0202] In the composition of the present invention, taking the total amount of the composition of the present invention as 100 mol%, the total content of the compound represented by the general formula (1A) and the compound represented by the general formula (1B) can be set to 90.0 to 100 mol%, particularly 93.0 to 99.9 mol%, and can also be set to 95.0 to 99.8 mol%.

[0203] Such a composition of the present invention can be effectively used for various applications such as etching gas, cleaning gas, and deposition gas.

[0204] As mentioned above, although embodiment of this invention is described, unless it deviates from the summary and scope of the claim, various changes can be made in form and detail.

[0205] Example

[0206] The following examples are provided to make the features of the present invention more clear, but the present invention is not limited to these examples.

[0207] In the examples and comparative examples, as a substrate,

[0208]

[0209] Pentafluorobenzotrichloride in which n is 5, 2,4-difluorobenzotrichloride in which n is 2, and benzotrichloride in which n is 0 were used.

[0210] In the following examples and comparative examples, as the complex of hydrogen fluoride and amine, 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)) 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.

[0211] Examples 1 to 15 and Comparative Examples 1 to 5

[0212] The substrates (1 g, 0.005 mol) shown in Tables 1 to 4, 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 to 4 (0.0005 mol, 10 mol% relative to the molar number of the substrate) were added to a SUS reactor, the reactor was covered, and the reaction was heated to the temperature shown in Tables 1 to 5, and the reaction was carried out for 24 hours. However, in Examples 16 to 17, no base or acid other than hydrogen fluoride was used.

[0213] After the reaction was completed, mass spectrometry analysis was performed using gas chromatography and GCMS (gas chromatography mass spectrometry), and structural analysis was performed using NMR (nuclear magnetic resonance).

[0214] According to the results of mass spectrometry and structural analysis, when pentafluorotrichlorotoluene with n=5 was used as the substrate, the target product was confirmed to be pentafluorotrifluoride; when 2,4-difluorotrichlorotoluene with n=2 was used as the substrate, the target product was confirmed to be 2,4-difluorotrifluorotoluene; when trichlorotoluene with n=0 was used as the substrate, the target product was confirmed to be trifluorotoluene.

[0215] The results are shown in Tables 1 to 5.

[0216] In Tables 1 to 5, "trifluoro" means a compound in which all chlorine atoms in the trichloromethyl group of the substrate are fluorinated to become a trifluoromethyl group, "difluoro" means a compound in which two chlorine atoms in the trichloromethyl group of the substrate are fluorinated to become a chlorodifluoromethyl group, and "monofluoro" means a compound in which one chlorine atom in the trichloromethyl group of the substrate is fluorinated to become a dichloromonofluoromethyl group.

[0217] [Table 1]

[0218]

[0219] [Table 2]

[0220]

[0221] [Table 3]

[0222]

[0223] [Table 4]

[0224]

[0225] [Table 5]

[0226]

Claims

1. A method for producing a compound represented by general formula (1), characterized in that: In formula (1), X 1 The same or different, represents a hydrogen atom or a halogen atom, wherein -CX 1 3 bases, 3 Xs 1 At least one of them is a fluorine atom, X 2 the same or different, representing a hydrogen atom or a halogen atom, n represents an integer from 1 to 5, The preparation method comprises reacting a compound represented by the general formula (2) with hydrogen fluoride, a base and an acid other than hydrogen fluoride to at least 3 One or more X in 3 bases 3 a step of fluorinating to produce the compound represented by the general formula (1); In formula (2), nSame as above, X 3 are the same or different, representing a hydrogen atom or a halogen atom, wherein -CX 3 3 bases, 3 Xs 3 At least one of them is a halogen atom other than a fluorine atom, X 4 The same or different represents a hydrogen atom or a halogen atom.

2. The manufacturing method according to claim 1, characterized in that The X 1 All are fluorine atoms.

3. The manufacturing method according to claim 1 or 2, characterized in that: The n X 4 At least one of them is a halogen atom.

4. The production method according to any one of claims 1 to 3, characterized in that The reaction is a step of mixing the hydrogen fluoride and the base to obtain a mixture, and then reacting the mixture, the compound represented by the general formula (2), and an acid other than hydrogen fluoride.

5. The production method according to any one of claims 1 to 4, characterized in that The pKa of the acid other than hydrogen fluoride is -10 to 20.

6. The production method according to any one of claims 1 to 5, characterized in that The base is at least one selected from 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 can support a polymer.

7. A composition, characterized in that Containing a compound represented by the general formula (1A) and a compound represented by the general formula (1B), The content of the compound represented by the general formula (1B) is 0.1 to 95.0 mol%, based on 100 mol% of the total amount of the composition. In formula (1A), X 2 the same or different, representing a hydrogen atom or a halogen atom, n represents an integer from 1 to 5, In formula (1B), X 2 Same as n, X 1a are the same or different, representing a hydrogen atom or a halogen atom, wherein -CX 1a 3 bases, 3 Xs 1a One or two of them are fluorine atoms, and the remaining two or one are hydrogen atoms or halogen atoms other than fluorine atoms.

8. The composition according to claim 7, characterized in that If any of the following conditions (1) and (2) are met, (1) The n X 2 0 to 4 of them are halogen atoms, and the content of the compound represented by the general formula (1B) is 40.0 to 95.0 mol%, (2) The n X 2 1 to 5 of them are halogen atoms, and the content of the compound represented by the general formula (1B) is 0.1 to 15.0 mol %.

9. The composition according to claim 7 or 8, characterized in that Used as etching gas, cleaning gas or deposition gas.

10. A fluorinating agent, characterized in that Contains hydrogen fluoride, alkali and acids other than hydrogen fluoride.

11. The fluorinating agent according to claim 10, characterized in that It is a fluorinating agent for the compound represented by the general formula (2), In formula (2), X 3 are the same or different, representing a hydrogen atom or a halogen atom, wherein -CX 3 3 bases, 3 Xs 3 At least one of them is a halogen atom other than a fluorine atom, X 4 the same or different, representing a hydrogen atom or a halogen atom, n represents an integer of 1-5.

12. A method for producing a compound represented by general formula (1), characterized in that: In formula (1), X 1 are the same or different, representing a hydrogen atom or a halogen atom, wherein -CX 1 3 bases, 3 Xs 1 At least one of them is a fluorine atom, X 2 the same or different, representing a hydrogen atom or a halogen atom, n represents an integer from 1 to 5, The preparation method comprises reacting a compound represented by the general formula (2) with hydrogen fluoride to at least 3 One or more X in 3 bases 3 a step of fluorinating to produce the compound represented by the general formula (1); In formula (2), nSame as above, X 3 are the same or different, representing a hydrogen atom or a halogen atom, wherein -CX 3 3 bases, 3 Xs 3 At least one of them is a halogen atom other than a fluorine atom, X 4 The same or different represents a hydrogen atom or a halogen atom.

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