WO2023063301A1

WO2023063301A1 - Method for producing fluorinated aromatic compound

Info

Publication number: WO2023063301A1
Application number: PCT/JP2022/037838
Authority: WO
Inventors: 友亮江藤; 新吾中村; 隆行松永
Original assignee: ダイキン工業株式会社
Priority date: 2021-10-13
Filing date: 2022-10-11
Publication date: 2023-04-20
Also published as: JP2024016116A; JP7381912B2; TW202334067A; JP2023058169A

Abstract

Provided is a method for producing a compound represented by general formula (1) [wherein R¹ represents a hydrogen atom, a hydroxyl group, a fluorine atom, a cyano group, a nitro group, a hydrocarbon group or a perfluoroalkyl group; X¹'s may be the same as or different from each other and independently represent a halogen atom other than a fluorine atom; and n represents an integer of 1 to 6 and n1 represents an integer of 1 to 6, wherein n ≥ n1 and n1 represents an integer of 2 to 6 when n represents an integer of 2 to 6], the method comprising a step for reacting a compound represented by general formula (2) [wherein R¹, X¹ and n are as mentioned above] with a metal fluoride in a solvent comprising a nitrogenated organic compound in the presence of a phosphonium salt having at least one alkyl group to produce the compound represented by general formula (1), in which, when n represents an integer of 2 or more, at least two X¹'s are fluorinated in the reaction. The production method is a novel method whereby a fluorinated aromatic compound can be produced with high efficiency.

Description

Method for producing fluorine-containing aromatic compound

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

As a method for producing a fluorine-containing aromatic compound typified by perfluorotoluene, which is expected as a next-generation etching gas, for example, 1 to 5% by mass of tetrakis(diethylamino)phosphonium salt is used as a catalyst. It is known to carry out the fluorination of halogenated aromatic compounds with ˜1.4 equivalents of an alkali metal or alkaline earth metal fluoride (see US Pat.

Russian Patent Publication No. 2157800

An object of the present disclosure is to provide a novel method capable of efficiently producing a fluorine-containing aromatic compound.

The present disclosure includes the following configurations.

Section 1. General formula (1):

[In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a fluorine atom, a cyano group, a nitro group, a hydrocarbon group or a perfluoroalkyl group. X ¹ is the same or different and represents a halogen atom other than a fluorine atom. n represents an integer of 1-6. n1 represents an integer of 1-6. However, when n≧n1 and n is an integer of 2-6, n1 represents an integer of 2-6. ]
A method for producing a compound represented by
in a solvent containing a nitrogen-containing organic compound,
In the presence of a phosphonium salt having one or more alkyl groups,
General formula (2):

[In the formula, R ¹ , X ¹ and n are the same as above. ]
A compound represented by
A production method comprising a step of reacting with a metal fluoride and fluorinating two or more X ¹ when n is an integer of 2 or more to produce a compound represented by the general formula (1). .

Section 2. Item 2. The production method according to Item 1, wherein the fluorination is performed in a system having a water content of 700 ppm by mass or less.

Section 3. The production method according to claim 1 or 2, wherein said n is an integer of 3-6.

Item 4. Item 4. The production method according to any one of Items 1 to 3, wherein the metal fluoride is an alkali metal or alkaline earth metal fluoride.

Item 5. A composition comprising difluorobenzotrifluoride and at least one halogenated fluorobenzotrifluoride selected from the group consisting of chlorofluorobenzotrifluoride, bromofluorobenzotrifluoride and iodofluorobenzotrifluoride.

Item 6. The content of the difluorobenzotrifluoride is 60.0 to 99.9 mol% and the content of the halogenated fluorobenzotrifluoride is 0.1 to 40.0 mol% based on the total amount of the composition being 100 mol%. 6. The composition according to Item 5, which is mol %.

Item 7. Item 7. The composition according to Item 5 or 6, which is used as a solvent for organic synthesis, an agricultural chemical intermediate, or a pharmaceutical intermediate.

Item 8. pentafluorobenzotrifluoride, chlorotetrafluorobenzotrifluoride, bromotetrafluorobenzotrifluoride, iodotetrafluorobenzotrifluoride, dichlorotrifluorobenzotrifluoride, dibromotrifluorobenzotrifluoride, diiodotrifluorobenzotrifluoride, at least one selected from the group consisting of trichlorodifluorobenzotrifluoride, tribromodifluorobenzotrifluoride, triiododifluorobenzotrifluoride, tetrachlorofluorobenzotrifluoride, tetrabromofluorobenzotrifluoride, and tetraiodofluorobenzotrifluoride and a halogenated fluorobenzotrifluoride.

Item 9. The content of the pentafluorobenzotrifluoride is 60.0 to 99.9 mol% and the content of the halogenated fluorobenzotrifluoride is 0.1 to 40.9 mol% based on the total amount of the composition being 100 mol%. Item 9. The composition according to Item 8, which is 0 mol%.

Item 10. Item 10. The composition according to item 8 or 9, which is used as an etching gas or a cleaning gas.

According to the present disclosure, it is possible to provide a novel method capable of efficiently producing fluorine-containing aromatic compounds.

As used herein, "contain" is a concept that includes all of "comprise", "consist essentially of", and "consist of".

Also, in this specification, when a numerical range is indicated by "A to B", it means from A to B.

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

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

In the present disclosure, "yield" means the ratio (mol%) of the total molar amount of the target compound contained in the outflow gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

In Patent Document 1, using 1 to 5% by mass of tetrakis(diethylamino)phosphonium salt as a catalyst, 1.2 to 1.4 equivalents of alkali metal or alkaline earth metal fluoride (especially potassium fluoride) , describes the fluorination of halogenated aromatic compounds. There is a need for new methods by which aromatic compounds can be produced.

According to the present disclosure, in the method of reacting a specific halogenated aromatic compound with a metal fluoride in the presence of a phosphonium salt having one or more alkyl groups, desired reaction conditions (using a specific solvent or , adjusting the amount of water in the system to a specific range, adopting a specific substrate, or using a specific phosphonium salt), all halogen atoms other than fluorine in the halogenated aromatic compound are replaced by fluorine Fluorine-containing aromatic compounds can be efficiently produced by conversion, and in particular, fluorine-containing aromatic compounds can be produced with high conversion, high selectivity, and high yield.

1. Method for producing fluorine-containing aromatic compound (part 1)
A manufacturing method according to a first aspect of the present disclosure includes:
General formula (1):

[In the formula, R ¹ , X ¹ and n are the same as above. ]
A compound represented by
A step of reacting with a metal fluoride and fluorinating two or more X ¹ when n is an integer of 2 or more to produce a compound represented by the general formula (1).

(1-1) starting compound (general formula (2))
In the production method of the first aspect of the present disclosure, the compound represented by general formula (2) is represented by general formula (2):

[In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a fluorine atom, a cyano group, a nitro group, a hydrocarbon group or a perfluoroalkyl group. X ¹ is the same or different and represents a halogen atom other than a fluorine atom. n represents an integer of 1-6. ]
It is a compound represented by

In general formula (2), the hydrocarbon group represented by R ¹ is not particularly limited, and examples thereof include an alkyl group, an aryl group and the like, and groups formed by any combination thereof (eg, an aralkyl group, an alkylaryl group, alkylaralkyl group) and the like.

In general formula (2), the alkyl group as the hydrocarbon group represented by R ¹ may be linear, branched or cyclic (preferably linear or branched, more preferably linear ) are included. The number of carbon atoms in the alkyl group (in the case of linear or branched chain) is not particularly limited, and the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), the general formula (1) From the viewpoint of the yield of the represented compound, for example, 1 to 20 is preferable, 3 to 15 is more preferable, and 5 to 10 is even more preferable. The number of carbon atoms in the alkyl group (in the case of cyclic) is not particularly limited, and the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1) etc., for example, 3 to 8 are preferable, and 4 to 7 are more preferable.

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

In the general formula (2), the aryl group as the hydrocarbon group represented by R ¹ is not particularly limited, but the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the general formula (1) From the viewpoint of yield and the like of the compound represented by, those having 6 to 20 carbon atoms are preferable, those having 6 to 12 carbon atoms are more preferable, and those having 6 to 10 carbon atoms are even more preferable. The aryl group can be either monocyclic or polycyclic (eg, bicyclic, tricyclic, etc.), but is preferably monocyclic.

Specific examples of the aryl group include phenyl, naphthyl, biphenyl, pentalenyl, indenyl, anthranyl, tetracenyl, pentacenyl, pyrenyl, perylenyl, fluorenyl, and phenanthryl groups. be done.

In the general formula (2), the aralkyl group as the hydrocarbon group represented by R ¹ is not particularly limited, but the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the From the viewpoint of the yield of the compound represented by, for example, hydrogen atoms (eg, 1 to 3, preferably 1 and an aralkyl group in which one hydrogen atom) is substituted by the above aryl group.

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

In the general formula (2), the alkylaryl group as the hydrocarbon group represented by R ¹ is not particularly limited, but the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the general formula (1 ), for example, the hydrogen atoms (for example, 1 to 3, preferably 1 hydrogen atom) of the aryl group are linear or branched and have 1 to 6 carbon atoms. (preferably 1 to 2) alkylaryl groups substituted with alkyl groups, and the like.

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

In the general formula (2), the alkylaralkyl group as the hydrocarbon group represented by R ¹ is not particularly limited, but the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the general formula (1 ), for example, hydrogen atoms on the aromatic ring of the aralkyl group (eg, 1 to 3, preferably 1 hydrogen atom) are linear or branched carbon Examples thereof include alkylaralkyl groups substituted with alkyl groups of number 1 to 6 (preferably 1 to 2).

In general formula (2), examples of the substituent of the hydrocarbon group represented by R ¹ include an alkoxy group and a halogen atom. The number of substituents is not particularly limited, and is preferably 0 to 6, more preferably 0 to 3, even more preferably 0 to 1.

The alkoxy group as a substituent of the hydrocarbon group is not particularly limited, and may be linear or branched optionally substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) or the like. A (preferably linear) alkoxy group having 1 to 8, preferably 1 to 5, more preferably 1 to 3 carbon atoms can be mentioned. The number of substituents is not particularly limited, and is preferably 0 to 6, more preferably 0 to 3, even more preferably 0 to 1.

Examples of such optionally substituted alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, per A fluoromethoxy group, a perfluoroethoxy group, and the like can be mentioned.

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

In general formula (2), the perfluoroalkyl group represented by R ¹ means an alkyl group in which all hydrogen atoms are substituted with fluorine atoms.

Any of linear, branched and cyclic perfluoroalkyl groups can be adopted. Among them, a straight-chain perfluoroalkyl group is preferable from the viewpoint of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), and the like.

The number of carbon atoms in the perfluoroalkyl group is not particularly limited, but it is 1 to 5 are preferred, 1 to 4 are more preferred, and 1 to 3 are even more preferred from the viewpoint of ratio and the like.

Specific examples of such perfluoroalkyl groups include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and the like.

In the general formula (2), the halogen atom other than the fluorine atom represented by X ¹ is not particularly limited, and includes a chlorine atom, a bromine atom, an iodine atom and the like.

In the general formula (2), the substitution number n of X ¹ is not particularly limited, the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the compound represented by the general formula (1) 1 to 6 is preferable, and 2 to 6, 3 to 6, 4 to 6, 5 to 6, etc. can also be used.

When n, the number of substitutions of X, is 3 to 6, the compound represented by general formula (2) is represented by general formula (2A):

[In the formula, R ¹ and X ¹ are the same as above. n represents an integer of 3-6. ]
It is a compound represented by

Specifically, the compound represented by general formula (2) that satisfies the above conditions is

etc.

A known or commercially available product can be used as the compound represented by the above general formula (2). Moreover, the compounds represented by the general formula (2) can be used alone, or two or more of them can be used in combination.

(1-2) Reaction In the reaction of the present disclosure, in the compound represented by the above general formula (2), X ¹ , which is a halogen atom other than fluorine, is converted to fluorine by a metal fluoride in the presence of a specific phosphonium salt. By chemical conversion, the compound represented by the above general formula (1) is produced by substituting with a fluorine atom.

At this time, when there are a plurality of X ¹ which are halogen atoms other than fluorine, that is, when n in the general formula (2) is an integer of 2 or more, two or more (especially all) of them are fluorinated compounds are selectively synthesized.

On the other hand, in the compound represented by the general formula (2), R ¹ remains unreacted even after fluorination with a metal fluoride in the presence of a specific phosphonium salt.

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

The reaction of the first aspect of the present disclosure is either a batch type in which the raw materials are charged into the reactor at once, or a flow type in which the product is withdrawn from the reactor while continuously supplying the raw materials into the reactor. method can also be adopted. Since the reaction of the present disclosure is not a very fast reaction, it is preferred to adopt a batch mode.

(1-3) Phosphonium salt The phosphonium salt used in the production method of the first aspect of the present disclosure is a phosphonium salt having one or more alkyl groups.

This phosphonium salt has, for example, general formula (3):

[In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and represent a hydrocarbon group. However, at least one of R ³ , R ⁴ , R ⁵ and R ⁶ is an alkyl group. Y represents a counter anion. ]
Phosphonium salts represented by

In general formula (3), the hydrocarbon groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ include those mentioned above. The same applies to the type and number of substituents. R ³ , R ⁴ , R ⁵ and R ⁶ are preferably sites where carbon atoms are bonded to the central phosphorus atom.

However, from the viewpoint of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., R ³ , R ⁴ , R ⁵ and R ⁶ at least one (1, 2, 3 or 4) of is an alkyl group.

From the viewpoint of the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., R ³ , R ⁴ , R ⁵ and R ⁶ are alkyl groups is preferred. Among them, at least one (1, 2, 3 or 4) of R ³ , R ⁴ , R ⁵ and R ⁶ has 1 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 4 to 12, more preferably 5 to 10 alkyl groups are preferred. In particular, by increasing the number of carbon atoms in the alkyl group of the phosphonium salt, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc. are particularly improved, It is also possible to particularly reduce the amount of impurities produced.

In the general formula ( ³ ), the counter anion represented by Y is not particularly limited, and various anions can be employed. ⁻ ), bromide ion (Br ⁻ ), iodide ion (I ⁻ ), etc.), tetrafluoroborate ion (BF ₄ ⁻ ), hydrogen sulfate ion (HSO ₄ ⁻ ), acetate ion (CH ₃ COO ⁻ ), hexa Fluorophosphate ion (PF ₆ ⁻ ) and the like are included.

Specifically, as a compound represented by general formula (3) that satisfies the above conditions,

etc.

For these phosphonium salts, known or commercially available products can be used. Moreover, the above phosphonium salts can be used alone, or two or more of them can be used in combination.

In the reaction in the production method of the first aspect of the present disclosure, the amount of the phosphonium salt used is not particularly limited, but the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), the general formula (1) From the viewpoint of the yield of the compound represented by the general formula (2), relative to 1 mol of the compound represented by the general formula (2), preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, 1 to 2.5 mol is more preferred. When using a plurality of phosphonium salts, it is preferable to adjust the total amount within the above range.

(1-4) Metal Fluoride The metal fluoride is not particularly limited as long as it can fluorinate halogen atoms other than fluorine in the compound represented by the general formula (2). From the viewpoint of the selectivity of the compound represented by (1), the yield of the compound represented by the general formula (1), etc., alkali metal or alkaline earth metal fluorides are preferable, and alkali metal fluorides are more preferable. Therefore, examples of metals constituting metal fluorides include alkali metals such as lithium, sodium, potassium and cesium; alkaline earth metals such as magnesium, calcium and barium. These metals can be used alone or in combination of two or more.

Examples of metal fluorides that meet these conditions include alkali metal fluorides such as lithium fluoride, sodium fluoride, potassium fluoride, and cesium fluoride; magnesium fluoride, calcium fluoride, and barium fluoride. and alkaline earth metal fluorides such as Among them, lithium fluoride, sodium fluoride, fluoride Alkali metal fluorides such as potassium and cesium fluoride are preferred, and potassium fluoride is more preferred.

For these metal fluorides, known or commercially available products can be used. Moreover, said metal fluoride can also be used individually and can also be used in combination of 2 or more types.

In the reaction in the production method of the first aspect of the present disclosure, the amount of metal fluoride used is not particularly limited, but the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), the general formula (1 ), relative to 1 mol of the compound represented by the general formula (2), is preferably 0.01 to 30 mol, more preferably 0.1 to 20 mol, 1 ~15 moles is more preferred. When using a plurality of metal fluorides, it is preferable to adjust the total amount within the above range.

(1-5) Solvent The solvent used in the production method in the production method of the first aspect of the present disclosure is particularly capable of dissolving the compound represented by the general formula (2), phosphonium salt, metal fluoride, etc., and , the conversion of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., a solvent containing a nitrogen-containing organic compound, preferably nitrogen Use containing polar solvents. Examples of such solvents include amide compounds (N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric triamide, etc.), amine compounds (triethylamine, 1-methylpyrrolidine, etc.), pyridine compounds (pyridine, methylpyridine, etc.), quinoline compounds (quinoline, methylquinoline, etc.), and the like. Among them, amide compounds, pyridine compounds and the like are preferable from the viewpoint of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), and the like. , N-dimethylformamide, N,N-diethylformamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4, More preferred are 5,6-tetrahydropyrimidinone, hexamethylphosphoric acid triamide, pyridine, methylpyridine and the like, N,N-dimethylformamide, N,N-diethylformamide, N,N-diisopropylformamide, N-methyl-2 -pyrrolidone, pyridine and the like are more preferred, and N,N-dimethylformamide, N-methyl-2-pyrrolidone, pyridine and the like are particularly preferred.

For these solvents, known or commercially available products can be used. Moreover, these solvents can be used alone or in combination of two or more.

The amount of solvent used is not particularly limited as long as it is the amount of solvent, and it can be an excess amount. From the viewpoint of the yield of the compound represented by the general formula (2), it is preferably 80 to 10000 parts by mass, more preferably 100 to 1000 parts by mass, and 150 to 800 parts by mass. is more preferred.

(1-6) Reaction temperature In the reaction of the first aspect of the present disclosure, the reaction temperature can be a mild condition, the conversion rate of the reaction, the yield of the compound represented by the general formula (1), From the viewpoints of easy improvement of selectivity and the like and easy reduction of by-products, the temperature is generally preferably 0 to 400°C, more preferably 25 to 300°C, and even more preferably 50 to 200°C.

(1-7) Reaction time The reaction time of the reaction of the first aspect of the present disclosure (maintenance time at the highest temperature) can be set to the extent that the reaction progresses sufficiently, and the conversion rate of the reaction, the general formula (1 ), the yield of the compound represented by general formula (1), etc., the time is preferably 1 minute to 48 hours, more preferably 5 minutes to 24 hours.

(1-8) Reaction pressure The reaction pressure of the reaction of the first aspect of the present disclosure is the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the compound represented by the general formula (1) -2 to 2 MPa, more preferably -1 to 1 MPa, and even more preferably -0.5 to 0.5 MPa from the viewpoint of the yield of . In addition, in the present disclosure, pressure is assumed to be gauge pressure unless otherwise specified.

In the reaction of the first aspect of the present disclosure, the reactor for reacting the compound represented by the general formula (2) with the metal fluoride has the shape and structure as long as it can withstand the above temperature and pressure. It is not particularly limited. Examples of reactors include vertical reactors, horizontal reactors, multitubular reactors, and the like. Examples of materials for the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloys.

(1-9) Exemplification of Reaction Regarding the atmosphere when performing the reaction in the first aspect of the present disclosure, from the viewpoint of suppressing the deterioration of the compound represented by the general formula (2), the phosphonium salt and the metal fluoride, An inert gas atmosphere is preferred.

Examples of the inert gas include nitrogen, helium, argon, and the like. Among these inert gases, nitrogen is preferable from the viewpoint of cost reduction.

In the production method of the first aspect of the present disclosure, the amount of water in the system depends on the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1). From the viewpoint of rate, etc., it is preferably 700 mass ppm or less, more preferably 0.1 to 650 mass ppm, still more preferably 1 to 600 mass ppm, and particularly preferably 10 to 500 mass ppm. The amount of water in the system is contained in the reaction system, with the total amount of the reagents used in the reaction (the compound represented by the general formula (2), phosphonium salt, metal fluoride, solvent, etc.) being 100% by mass. means the total amount of water. Also, water can be added to the reaction system to adjust the amount of water in the system. In the present disclosure, the water content in the system is measured with a Karl Fischer moisture meter.

After completion of the reaction, the compound represented by the general formula (1) can be obtained by performing a purification treatment according to a conventional method as necessary.

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

[In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a fluorine atom, a cyano group, a nitro group, a hydrocarbon group or a perfluoroalkyl group. X ¹ is the same or different and represents a halogen atom other than a fluorine atom. n represents an integer of 1-6. n1 represents an integer of 1-6. However, when n≧n1 and n is an integer of 2-6, n1 represents an integer of 2-6. ]
It is a compound represented by

In general formula (1), R ¹ , X ¹ and n are as described above. However, since the number of X ¹ in general formula (1) is nn1, n≧n1 is necessarily satisfied. Also, when n is an integer of 2 or more, it is preferable that two or more X ¹ are fluorinated.

Specifically, the compound represented by general formula (1), which is the target compound produced in the present disclosure, is specifically

etc.

2. Method for producing fluorine-containing aromatic compound (Part 2)
The production method according to the second aspect of the present disclosure comprises general formula (1A):

[In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a fluorine atom, a cyano group, a nitro group, a hydrocarbon group or a perfluoroalkyl group. X ¹ is the same or different and represents a halogen atom other than a fluorine atom. n represents an integer of 3-6. n1 represents an integer of 2-6. However, n≧n1. ]
A method for producing a compound represented by
In the presence of a phosphonium salt having one or more alkyl groups,
General formula (2A):

[In the formula, R ¹ , X ¹ and n are the same as above. ]
A compound represented by
A step of reacting with a metal fluoride to fluorinate two or more ^X1 's to produce a compound represented by the general formula (1A).

(2-1) starting compound (general formula (2A))
In the second aspect of the present disclosure, the compound represented by general formula (2A) has general formula (2A):

[In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a fluorine atom, a cyano group, a nitro group, a hydrocarbon group or a perfluoroalkyl group. X ¹ is the same or different and represents a halogen atom other than a fluorine atom. n represents an integer of 3-6. ]
It is a compound represented by

In general formula (2A), the hydrocarbon group and perfluoroalkyl group represented by R ¹ and the halogen atom other than the fluorine atom represented by X ¹ include the above "(1-1) starting compound (general formula (2) )” can be adopted for the hydrocarbon group and perfluoroalkyl group represented by R ¹ and the halogen atom other than the fluorine atom represented by X ¹ . Preferred types and specific examples are also the same.

In the general formula (2A), n, which is the number of substitutions of X ¹ , is the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1A), the yield of the compound represented by the general formula (1A), etc. from the point of view, it is 3 to 6, and may be 4 to 6, 5 to 6, and the like.

Specifically, as a compound represented by general formula (2A) that satisfies the above conditions,

etc.

(2-2) Reaction, Phosphonium Salt, Metal Fluoride, Solvent, Reaction Temperature, Reaction Time, Reaction Pressure and Exemplification of Reaction can be adopted.

In the second aspect of the present disclosure, the phosphonium salt can adopt the description of "(1-3) phosphonium salt" above. Preferred types and specific examples are also the same.

In the second aspect of the present disclosure, the metal fluoride can adopt the description of "(1-4) metal fluoride" above. Preferred types and specific examples are also the same.

In the second aspect of the present disclosure, the solvent can adopt the description of "(2-2) Solvent" above. Preferred types and specific examples are also the same.

In the second aspect of the present disclosure, the reaction temperature can adopt the description of "(1-6) Reaction temperature" above. A preferable range is also the same.

In the second aspect of the present disclosure, the reaction time can adopt the description of "(1-7) reaction time" above. A preferable range is also the same.

In the second aspect of the present disclosure, the reaction pressure can adopt the description of "(1-8) Reaction pressure" above. Preferred types and specific examples are also the same.

In the second aspect of the present disclosure, examples of reactions can adopt the description of "(1-9) Examples of reactions" above. Preferred types and specific examples are also the same.

(2-3) Solvent The solvent used in the production method in the second aspect of the present disclosure is not particularly limited, but in particular, the compound represented by the general formula (2A), phosphonium salt, metal fluoride, etc. are dissolved. In addition, a polar organic solvent is preferable from the viewpoint of excellent conversion of the reaction, selectivity of the compound represented by the general formula (1A), yield of the compound represented by the general formula (1A), and the like. Further, the compound represented by the general formula (2A), a phosphonium salt, a metal fluoride, etc. are dissolved, and the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1A), the general formula (1A) A solvent containing a nitrogen-containing organic compound, preferably a nitrogen-containing polar solvent, is more preferable from the viewpoint of excellent yield of the compound represented by. Examples of such solvents include amide compounds (N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric triamide, etc.), amine compounds (triethylamine, 1-methylpyrrolidine, etc.), pyridine compounds (pyridine, methylpyridine, etc.), quinoline compounds (quinoline, methylquinoline, etc.), and the like. Among them, amide compounds, pyridine compounds and the like are preferable from the viewpoint of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1A), the yield of the compound represented by the general formula (1A), and the like. , N-dimethylformamide, N,N-diethylformamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4, More preferred are 5,6-tetrahydropyrimidinone, hexamethylphosphoric acid triamide, pyridine, methylpyridine and the like, N,N-dimethylformamide, N,N-diethylformamide, N,N-diisopropylformamide, N-methyl-2 -pyrrolidone, pyridine and the like are more preferred, and N,N-dimethylformamide, N-methyl-2-pyrrolidone, pyridine and the like are particularly preferred.

The amount of solvent used is not particularly limited as long as it is the amount of solvent, and can be an excess amount. From the viewpoint of the yield of the compound represented by the general formula (2A), it is preferably 80 to 10000 parts by mass, more preferably 100 to 1000 parts by mass, and 150 to 800 parts by mass. is more preferred.

(2-4) Target compound (general formula (1A))
The target compound thus produced has the general formula (1A):

[In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a fluorine atom, a cyano group, a nitro group, a hydrocarbon group or a perfluoroalkyl group. X ¹ is the same or different and represents a halogen atom other than a fluorine atom. n represents an integer of 3-6. n1 represents an integer of 2-6. However, n≧n1. ]
It is a compound represented by

In general formula (1A), R ¹ , X ¹ and n1 are as described above. However, since the number of X ¹ in general formula (1) is nn1, n≧n1 is necessarily satisfied.

Specifically, the compound represented by general formula (1A), which is the target compound produced in the present disclosure, is specifically

etc.

3. Method for producing fluorine-containing aromatic compound (Part 3)
The production method according to the third aspect of the present disclosure comprises general formula (1):

[In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a fluorine atom, a cyano group, a nitro group, a hydrocarbon group or a perfluoroalkyl group. X ¹ is the same or different and represents a halogen atom other than a fluorine atom. n represents an integer of 1-6. n1 represents an integer of 1-6. However, when n≧n1 and n is an integer of 2-6, n1 represents an integer of 2-6. ]
A method for producing a compound represented by
In the presence of a phosphonium salt having one or more alkyl groups having 3 or more carbon atoms,
General formula (2):

(3-1) Starting compound (general formula (2)), reaction, metal fluoride, solvent, reaction temperature, reaction time, reaction pressure and target compound In the third aspect of the present disclosure, the starting compound of the general formula ( For the compound represented by 2), the description of the above “(1-1) starting compound (general formula (2))” can be adopted. Preferred types and specific examples are also the same.

For the reaction in the third aspect of the present disclosure, the explanation of "(1-2) reaction" above can be adopted.

In the third aspect of the present disclosure, the metal fluoride can adopt the description of "(1-4) metal fluoride" above. Preferred types and specific examples are also the same.

In the third aspect of the present disclosure, the solvent can adopt the description of "(2-3) solvent" above. Preferred types and specific examples are also the same.

In the third aspect of the present disclosure, the reaction temperature can adopt the description of "(1-6) Reaction temperature" above. A preferable range is also the same.

In the third aspect of the present disclosure, the reaction time can adopt the description of "(1-7) reaction time" above. A preferable range is also the same.

In the third aspect of the present disclosure, the reaction pressure can adopt the description of "(1-8) Reaction pressure" above. Preferred types and specific examples are also the same.

In the third aspect of the present disclosure, examples of reactions can adopt the description of "(1-9) Examples of reactions" above. Preferred types and specific examples are also the same.

In the third aspect of the present disclosure, the compound represented by general formula (1), which is the target compound, can adopt the description of "(1-10) target compound (general formula (1))" above. Preferred types and specific examples are also the same.

(3-2) Phosphonium salt The phosphonium salt used in the third aspect of the present disclosure is a phosphonium salt having one or more alkyl groups with 3 or more carbon atoms.

This phosphonium salt has, for example, general formula (3A):

[In the formula, R ^3a , R ^4a , R ^5a and R ^6a are the same or different and represent a hydrocarbon group. However, at least one of R ^3a , R ^4a , R ^5a and R ^6a is an alkyl group having 3 or more carbon atoms. Y represents a counter anion. ]
Phosphonium salts represented by

In general formula (3A), the hydrocarbon groups represented by R ^3a , R ^4a , R ^5a and R ^6a include those mentioned above. The same applies to the type and number of substituents. It should be noted that R ^3a , R ^4a , R ^5a and R ^6a are preferably sites where carbon atoms are bonded to the central phosphorus atom.

However, from the viewpoint of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., R ^3a , R ^4a , R ^5a and R ^6a At least one of (1, 2, 3 or 4) is an alkyl group having 3 or more carbon atoms.

Further, from the viewpoint of the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc., R ^3a , R ^4a , R ^5a and R ^6a are alkyl groups is preferred. Among them, at least one (1, 2, 3 or 4) of R ^3a , R ^4a , R ^5a and R ^6a has 3 or more carbon atoms, preferably 4 to 20, more preferably 5 to 15 is an alkyl group of In particular, by increasing the number of carbon atoms in the alkyl group of the phosphonium salt, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), etc. are particularly improved, The production of impurities can be particularly reduced.

As the counter anion represented by Y in the general formula (3A), those described above can be employed.

Specifically, the compound represented by general formula (3A) that satisfies the above conditions is

etc.

In the reaction in the third aspect of the present disclosure, the amount of the phosphonium salt used is not particularly limited, but the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the general formula (1) From the viewpoint of the yield of the compound represented by the general formula (2), it is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, 1 to 2.5 Molar is more preferred. When using a plurality of phosphonium salts, it is preferable to adjust the total amount within the above range.

4. Composition (Part 1)
As described above, the compound represented by general formula (1) can be obtained. Difluorobenzotrifluoride and one of X ¹ in general formula (2) in the form of a composition containing at least one halogenated fluorobenzotrifluoride selected from the group consisting of chlorofluorobenzotrifluoride, bromofluorobenzotrifluoride and iodofluorobenzotrifluoride as a partially fluorinated compound sometimes obtained.

Difluorobenzotrifluoride as the compound represented by the general formula (1) is not particularly limited, but 2,3-difluorobenzotrifluoride, 2,4-difluorobenzotrifluoride, 2,6-difluorobenzotrifluoride etc. These difluorobenzotrifluorides can be used alone or in combination of two or more.

Halogenated fluorobenzotrifluoride as a compound in which only part of X ¹ in general formula (2) is fluorinated is not particularly limited, but 2-chloro-3-fluorobenzotrifluoride, 2-chloro-4 -fluorobenzotrifluoride, 2-chloro-6-fluorobenzotrifluoride, 3-chloro-2-fluorobenzotrifluoride, 4-chloro-2-fluorobenzotrifluoride, 6-chloro-2-fluorobenzotrifluoride, 2-bromo-3-fluorobenzotrifluoride, 2-bromo-4-fluorobenzotrifluoride, 2-bromo-6-fluorobenzotrifluoride, 3-bromo-2-fluorobenzotrifluoride, 4-bromo-2- fluorobenzotrifluoride, 6-bromo-2-fluorobenzotrifluoride, 2-iodo-3-fluorobenzotrifluoride, 2-iodo-4-fluorobenzotrifluoride, 2-iodo-6-fluorobenzotrifluoride, 3 -iodo-2-fluorobenzotrifluoride, 4-iodo-2-fluorobenzotrifluoride, 6-iodo-2-fluorobenzotrifluoride and the like. These halogenated fluorobenzotrifluorides can be used alone or in combination of two or more.

Taking the total amount of the composition of the present disclosure according to the first aspect as 100 mol %, the content of difluorobenzotrifluoride is 60.0 to 99.9 mol %, 65.0 to 99.5 mol %, 70 .0 to 99.0 mol%, 75.0 to 98.5 mol%, 80.0 to 98.0 mol%, 85.0 to 97.5 mol%, 90.0 to 97.0 mol%, etc. It is also possible to

Further, the total amount of the composition of the present disclosure according to the first aspect is 100 mol%, the halogenated fluorobenzotrifluoride is 0.1 to 40.0 mol%, 0.5 to 35.0 mol%, 1.0 to 30.0 mol%, 1.5 to 25.0 mol%, 2.0 to 20.0 mol%, 2.5 to 15.0 mol%, 3.0 to 10.0 mol%, etc. It is also possible to

The composition of the present disclosure according to such a first aspect can be effectively used for various applications such as organic synthesis solvents, agricultural chemical intermediates, and pharmaceutical intermediates.

5. Composition (Part 2)
As described above, the compound represented by the general formula (1) can be obtained. Pentafluorobenzotrifluoride and X ¹ in the general formula (2) Partially fluorinated compounds such as chlorotetrafluorobenzotrifluoride, bromotetrafluorobenzotrifluoride, iodotetrafluorobenzotrifluoride, dichlorotrifluorobenzotrifluoride, dibromotrifluorobenzotrifluoride, diiodotrifluorobenzo selected from the group consisting of trifluoride, trichlorodifluorobenzotrifluoride, tribromodifluorobenzotrifluoride, triiododifluorobenzotrifluoride, tetrachlorofluorobenzotrifluoride, tetrabromofluorobenzotrifluoride, and tetraiodofluorobenzotrifluoride It may also be obtained in the form of a composition comprising at least one halogenated fluorobenzotrifluoride.

Pentafluorobenzotrifluoride as the compound represented by general formula (1) is not particularly limited, but includes 2,3,4,5,6-pentafluorobenzotrifluoride. Pentafluorobenzotrifluoride can be used alone or in combination of two or more.

Any isotope can be employed as the halogenated fluorobenzotrifluoride as the compound in which only a part of X ¹ in the general formula (2) is fluorinated. Halogenated fluorobenzotrifluorides can be used alone or in combination of two or more.

Taking the total amount of the composition of the present disclosure according to the second aspect as 100 mol%, the content of pentafluorobenzotrifluoride is 60.0 to 99.9 mol%, 65.0 to 99.5 mol%, 70.0 to 99.0 mol%, 75.0 to 98.5 mol%, 80.0 to 98.0 mol%, 85.0 to 97.5 mol%, 90.0 to 97.0 mol%, etc. It is also possible to

Further, the total amount of the composition of the present disclosure according to the second aspect is 100 mol%, the halogenated fluorobenzotrifluoride is 0.1 to 40.0 mol%, 0.5 to 35.0 mol%, 1.0 to 30.0 mol%, 1.5 to 25.0 mol%, 2.0 to 20.0 mol%, 2.5 to 15.0 mol%, 3.0 to 10.0 mol%, etc. It is also possible to

The composition of the present disclosure according to such a second aspect can be effectively used for various uses such as etching gas and cleaning gas.

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

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

In addition, in each example and comparative example, the water content was measured with a Karl Fischer moisture meter at the start of the reaction.

Examples 1-7 and Comparative Examples 1-3
In an autoclave, 2,4-dichlorobenzotrifluoride (1 g, 0.005 mol), potassium fluoride (0.8 g, 0.014 mol), solvent (N-methyl-2-pyrrolidone (NMP) or sulfolane) 4.5 mL , and a phosphonium salt (0.0014 mol) shown in Table 1 were added, covered, heated to 200° C., and the reaction was allowed to proceed for 24 hours.

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).

From the results of mass spectrometry and structural analysis, it was confirmed that 2,4-difluorobenzotrifluoride was produced as the target product.

The results are shown in Table 1.

The phosphonium salts used in Table 1 are as follows.

In Table 1, the product 2,4-2F-BTF means 2,4-difluorobenzotrifluoride, and 2,4-Cl-F-BTF means 2-chloro-4-fluorobenzo It means trifluoride and/or 4-chloro-2-fluorobenzotrifluoride. In Table 1, selectivity for 2,4-Cl-F-BTF means total selectivity for 2-chloro-4-fluorobenzotrifluoride and 4-chloro-2-fluorobenzotrifluoride.

Examples 8-13
Instead of 2,4-dichlorobenzotrifluoride, the substrates shown in Tables 2-4 (0.005 mol) and phosphonium salts shown in Tables 2-4 (0.0014 mol) were used, except that Examples 1-7 were used. A similar reaction was performed.

From the results of mass spectrometry and structural analysis, it was confirmed that difluorobenzotrifluoride or pentafluorobenzotrifluoride was produced as the target product.

The results are shown in Tables 2-4.

In Tables 2 to 4, the substrate 2,3-2Cl-BTF means 2,3-dichlorobenzotrifluoride, and 2,6-2Cl-BTF means 2,6-dichlorobenzotrifluoride. 5Cl-BTF means 2,3,4,5,6-pentachlorobenzotrifluoride.

In addition, in Tables 2 to 4, the phosphonium salts used are as follows.

Further, in Tables 2 to 4, the product 2,3-2F-BTF means 2,3-difluorobenzotrifluoride, and 2,3-Cl-F-BTF means 2-chloro-3- means fluorobenzotrifluoride and/or 3-chloro-2-fluorobenzotrifluoride, 2,6-2F-BTF means 2,6-difluorobenzotrifluoride, 2,6-Cl-F- BTF means 2-chloro-6-fluorobenzotrifluoride, 5F-BTF means 2,3,4,5,6-pentafluorobenzotrifluoride, 4F,1Cl-BTF means chlorotetra means fluorobenzotrifluoride (including all isotopes), 3F,2Cl-BTF means dichlorotrifluorobenzotrifluoride (including all isotopes), 2F,3Cl-BTF means trichlorodifluoro 1F,4Cl-BTF means tetrachlorofluorobenzotrifluoride (including all isotopes). In Tables 2 to 4, the selectivity for 2,3-Cl-F-BTF means the total selectivity for 2-chloro-3-fluorobenzotrifluoride and 3-chloro-2-fluorobenzotrifluoride. , 4F,1Cl-BTF refers to the total isotopic selectivity of chlorotetrafluorobenzotrifluoride, and the selectivity of 3F,2Cl-BTF is the total isotopic selectivity of dichlorotrifluorobenzotrifluoride. selectivity for 2F,3Cl-BTF means total selectivity for trichlorodifluorobenzotrifluoride, selectivity for 1F,4Cl-BTF means total selectivity for tetrachlorofluorobenzotrifluoride. do.

Claims

General formula (1):

[In the formula, R 1 represents a hydrogen atom, a hydroxyl group, a fluorine atom, a cyano group, a nitro group, a hydrocarbon group or a perfluoroalkyl group. X 1 is the same or different and represents a halogen atom other than a fluorine atom. n represents an integer of 1-6. n1 represents an integer of 1-6. However, when n≧n1 and n is an integer of 2-6, n1 represents an integer of 2-6. ]
A method for producing a compound represented by
in a solvent containing a nitrogen-containing organic compound,
In the presence of a phosphonium salt having one or more alkyl groups,
General formula (2):

[In the formula, R 1 , X 1 and n are the same as above. ]
A compound represented by
A production method comprising a step of reacting with a metal fluoride and fluorinating two or more X 1 when n is an integer of 2 or more to produce a compound represented by the general formula (1). .
2. The production method according to claim 1, wherein the fluorination is performed in a system having a water content of 700 ppm by mass or less.
The production method according to claim 1 or 2, wherein said n is an integer of 3-6.
The production method according to any one of claims 1 to 3, wherein the metal fluoride is an alkali metal or alkaline earth metal fluoride.
A composition comprising difluorobenzotrifluoride and at least one halogenated fluorobenzotrifluoride selected from the group consisting of chlorofluorobenzotrifluoride, bromofluorobenzotrifluoride and iodofluorobenzotrifluoride.
The content of the difluorobenzotrifluoride is 60.0 to 99.9 mol% and the content of the halogenated fluorobenzotrifluoride is 0.1 to 40.0 mol% based on the total amount of the composition being 100 mol%. 6. The composition of claim 5 in mol %.
7. The composition according to claim 5 or 6, which is used as a solvent for organic synthesis, an agricultural chemical intermediate or a pharmaceutical intermediate.
pentafluorobenzotrifluoride, chlorotetrafluorobenzotrifluoride, bromotetrafluorobenzotrifluoride, iodotetrafluorobenzotrifluoride, dichlorotrifluorobenzotrifluoride, dibromotrifluorobenzotrifluoride, diiodotrifluorobenzotrifluoride, at least one selected from the group consisting of trichlorodifluorobenzotrifluoride, tribromodifluorobenzotrifluoride, triiododifluorobenzotrifluoride, tetrachlorofluorobenzotrifluoride, tetrabromofluorobenzotrifluoride, and tetraiodofluorobenzotrifluoride and a halogenated fluorobenzotrifluoride.
The content of the pentafluorobenzotrifluoride is 60.0 to 99.9 mol% and the content of the halogenated fluorobenzotrifluoride is 0.1 to 40.9 mol% based on the total amount of the composition being 100 mol%. 9. The composition of claim 8, which is 0 mol %.
Item 10. The composition according to item 8 or 9, which is used as an etching gas or a cleaning gas.