CN118119583A

CN118119583A - Method for producing fluorine-containing aromatic compound

Info

Publication number: CN118119583A
Application number: CN202280068988.8A
Authority: CN
Inventors: 江藤友亮; 中村新吾; 松永隆行
Original assignee: Daikin Industries Ltd
Current assignee: Daikin Industries Ltd
Priority date: 2021-10-13
Filing date: 2022-10-11
Publication date: 2024-05-31
Also published as: JP7381912B2; JP2024016116A; JP2023058169A; WO2023063301A1; TW202334067A

Abstract

The invention provides a general formula (1) [ wherein 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, which are the same or different, represent halogen atoms other than fluorine atoms. n represents an integer of 1 to 6. n1 represents an integer of 1 to 6. Wherein, when n is not less than n1 and n is an integer of 2 to 6, n1 represents an integer of 2 to 6. A process for producing a compound represented by the general formula (2) [ wherein R ¹、X¹ and n are as defined above ] in the presence of a phosphonium salt having 1 or more alkyl groups in a solvent containing a nitrogen-containing organic compound. And (2) reacting the compound represented by the general formula (1) with a metal fluoride, and fluorinating 2 or more X ¹ when n is an integer of 2 or more. The production method is a novel method capable of producing a fluorine-containing aromatic compound with high efficiency.

Description

Method for producing fluorine-containing aromatic compound

Technical Field

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

Background

As a method for producing a fluorinated aromatic compound represented by perfluorotoluene, which is expected to be used as a new generation etching gas, for example, a method of fluorinating a halogenated aromatic compound with 1.2 to 1.4 equivalents of an alkali metal or alkaline earth metal fluoride using, for example, 1 to 5 mass% of a tetra (diethylamino) phosphonium salt as a catalyst is known (see patent document 1).

Prior art literature

Patent literature

Patent document 1: russian patent publication No. 2157800

Disclosure of Invention

Technical problem to be solved by the invention

The purpose of the present invention is to provide a novel method by which a fluorine-containing aromatic compound can be efficiently produced.

Technical means for solving the technical problems

The present invention includes the following means.

A process for producing a compound represented by the following general formula (1),

[ Wherein 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, which are the same or different, represent halogen atoms other than fluorine atoms. n represents an integer of 1 to 6. n1 represents an integer of 1 to 6. Wherein, when n is not less than n1 and n is an integer of 2 to 6, n1 represents an integer of 2 to 6. ]

The production method comprises a step of reacting a compound represented by the general formula (2) with a metal fluoride in the presence of a phosphonium salt having 1 or more alkyl groups in a solvent containing a nitrogen-containing organic compound, and fluorinating 2 or more X ¹ when n is an integer of 2 or more to produce the compound represented by the general formula (1).

[ Wherein R ¹、X¹ and n are as defined above. ]

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

The method according to item 3, wherein n is an integer of 3 to 6.

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.

The composition of item 5, which comprises a difluorobenzotrifluoride and a halofluorobenzotrifluoride, wherein the halofluorobenzotrifluoride is at least 1 selected from the group consisting of chlorotrifluorotoluene, bromofluorobenzotrifluoride and iodofluorobenzotrifluoride.

The composition according to item 5, wherein the total amount of the composition is 100 mol%, the difluorobenzotrifluoride content is 60.0 to 99.9 mol%, and the halobenzotrifluoride content is 0.1 to 40.0 mol%.

Item 7 the composition of item 5 or 6, which is used as a solvent for organic synthesis, a pesticidal intermediate or a pharmaceutical intermediate.

The composition of item 8, which comprises a pentafluoroetrifluorotoluene and a halofluorotrifluorotoluene, wherein the halofluorotrifluorotoluene is at least 1 selected from chlorotetrafluorotrifluorotoluene, bromotetrafluorobenzotrifluoride, iodotetrafluorobenzotrifluoride, dichlorotrifluorobenzotrifluoride, dibromotrifluorobenzotrifluoride, diiodotrifluorobenzotrifluoride, trichlorodifluorobenzotrifluoride, tribromodifluorobenzotrifluoride, triiododifluorobenzotrifluoride, tetrachlorofluorobenzotrifluoride, tetrabromofluorobenzotrifluoride and tetraiodofluorobenzotrifluoride.

The composition according to item 8, wherein the total amount of the composition is 100 mol%, the content of the pentafluoroetrifluorotoluene is 60.0 to 99.9 mol%, and the content of the halofluorobenzotrifluoride is 0.1 to 40.0 mol%.

Item 10. The composition of item 8 or 9 for use as an etching gas or a cleaning gas.

Effects of the invention

According to the present invention, a novel method is provided which enables efficient production of fluorine-containing aromatic compounds.

Detailed Description

In the present specification, "containing" is a concept including any one of meanings of "comprising", "consisting essentially of … … (consist essentially of)" and "consisting of only … … (consist of)".

In the present specification, "a to B" means a or more and B or less when the numerical range is expressed.

In the present invention, the term "selectivity" means a ratio (mol%) of the total molar amount of the target compounds contained in the effluent gas from the outlet of the reactor to the total molar amount of the compounds other than the raw material compounds in the effluent gas.

In the present invention, the "conversion" means a ratio (mol%) of the total molar amount of the compounds other than the raw material compounds contained in the effluent gas from the outlet of the reactor to the molar amount of the raw material compounds supplied to the reactor.

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

Patent document 1 discloses a novel method for producing a fluorinated aromatic compound, in which a fluorinated aromatic compound is fluorinated with 1.2 to 1.4 equivalents of an alkali metal or alkaline earth metal fluoride (in particular, potassium fluoride) using 1 to 5 mass% of a tetra (diethylamino) phosphonium salt as a catalyst, but the tetra (diethylamino) phosphonium salt is not commercially available and is not a practical method because it is costly to synthesize.

According to the present invention, a specific halogenated aromatic compound is reacted with a metal fluoride in the presence of a phosphonium salt having 1 or more alkyl groups, and in this method, all halogen atoms other than fluorine in the halogenated aromatic compound are fluorinated under a predetermined reaction condition (a specific solvent is used, the amount of water in the system is adjusted to a specific range, a specific substrate is used, or a specific phosphonium salt is used), whereby a fluorine-containing aromatic compound can be efficiently produced, and in particular, a fluorine-containing aromatic compound can be produced with a high conversion rate, a high selectivity, and a high yield.

1. Method for producing fluorine-containing aromatic compound (one of them)

The production method according to the first aspect of the present invention is a production method of a compound represented by the general formula (1),

The production method comprises a step of reacting a compound represented by the general formula (2) with a metal fluoride in the presence of a phosphonium salt having 1 or more alkyl groups in a solvent containing a nitrogen-containing organic compound, and fluorinating 2 or more X ¹ when n is an integer of 2 or more to produce the compound represented by the general formula (1),

[ Wherein R ¹、X¹ and n are as defined above. ].

(1-1) Starting Compound (general formula (2))

In the production method according to the first aspect of the present invention, the compound represented by the general formula (2) is a compound represented by the following general formula (2).

[ Wherein 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, which are the same or different, represent halogen atoms other than fluorine atoms. n represents an integer of 1 to 6. ]

In the 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 a group (for example, an aralkyl group, an alkylaryl group, an alkylarylalkyl group) formed by any combination thereof, and the like.

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

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

In the general formula (2), the aryl group as the hydrocarbon group represented by R ¹ is not particularly limited, but from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), and the like, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 12 is more preferable, and an aryl group having 6 to 10 is even more preferable. The aryl group may be of a single ring type or a multiple ring type (for example, 2-ring type, 3-ring type, etc.), and is preferably of a single ring type.

Specific examples of the aryl group include phenyl, naphthyl, biphenyl, pentylene, indenyl, anthracenyl, tetracenyl, pentacenyl, pyrenyl, perylenyl, fluorenyl, phenanthryl, and the like.

In the general formula (2), the aralkyl group as the hydrocarbon group represented by R ¹ is not particularly limited, but examples thereof include aralkyl groups in which a hydrogen atom (for example, 1 to 3, preferably 1 hydrogen atom) of an alkyl group having 1 to 6 (preferably 1 to 3) carbon atoms (straight chain or branched chain) is substituted with the above aryl group from the viewpoints of 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), and the like.

Specific examples of the aralkyl group include benzyl and phenethyl.

In the general formula (2), the alkylaryl group as the hydrocarbon group represented by R ¹ is not particularly limited, but from the viewpoints of 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), for example, alkylaryl groups in which the hydrogen atoms (for example, 1 to 3, preferably 1) of the above aryl groups are substituted with straight-chain or branched-chain alkyl groups having 1 to 6 (preferably 1 to 2) carbon atoms, and the like are exemplified.

Specific examples of the alkylaryl group include tolyl and xylyl.

In the general formula (2), the alkylaryl group as the hydrocarbon group represented by R ¹ is not particularly limited, but from the viewpoints of 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), for example, alkylaryl groups in which a hydrogen atom (for example, 1 to 3, preferably 1 hydrogen atom) on an aromatic ring of the above-mentioned arylalkyl group is substituted with a linear or branched alkyl group having 1 to 6 (preferably 1 to 2) carbon atoms, and the like are exemplified.

In the 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 the substituents is not particularly limited, but is, for example, preferably 0 to 6, more preferably 0 to 3, and still more preferably 0 to 1.

The alkoxy group as a substituent of the above-mentioned hydrocarbon group is not particularly limited, and examples thereof include straight-chain or branched (preferably straight-chain) alkoxy groups having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, which may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom or the like) or the like. The number of substituents is not particularly limited, and is, for example, preferably 0 to 6, more preferably 0 to 3, and still more preferably 0 to 1.

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

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

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

The perfluoroalkyl group may be any of linear, branched and cyclic perfluoroalkyl groups. Among them, linear perfluoroalkyl groups are preferable from the viewpoints of conversion of the reaction, selectivity of the compound represented by the general formula (1), yield of the compound represented by the general formula (1), and the like.

The number of carbon atoms of the perfluoroalkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3 from the viewpoints of conversion of the reaction, selectivity of the compound represented by the general formula (1), yield of the compound represented by the general formula (1), and the like.

Specific examples of such perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and heptafluoropropyl.

In the general formula (2), the halogen atom other than the fluorine atom shown by X ¹ is not particularly limited, and examples thereof include 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, but may be preferably 1 to 6, or may be 2 to 6, 3 to 6, 4 to 6, 5 to 6, or the like, from the viewpoints of conversion rate of reaction, selectivity of the compound represented by the general formula (1), yield of the compound represented by the general formula (1), and the like.

Wherein when the substitution number n of X is 3 to 6, the compound represented by the general formula (2) is a compound represented by the general formula (2A):

[ wherein R ¹ and X ¹ are as defined above. n represents an integer of 3 to 6. ].

Specific examples of the compound represented by the general formula (2) satisfying the above conditions include:

Etc.

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

(1-2) Reaction

In the reaction of the present invention, a halogen atom X ¹ other than fluorine in the compound represented by the above general formula (2) is substituted with a fluorine atom by fluorination with a metal fluoride in the presence of a specific phosphonium salt to produce the compound represented by the above general formula (1).

In this case, when a plurality of halogen atoms X ¹ other than fluorine, that is, when n in the general formula (2) is an integer of 2 or more, 2 or more (particularly, all) of the fluorinated compounds are selectively synthesized.

On the other hand, R ¹ in the compound represented by the above general formula (2) does not react by fluorination with a metal fluoride even in the presence of a specific phosphonium salt, but remains.

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

The reaction according to the first aspect of the present invention may be carried out in a batch type in which the raw materials are fed into the reactor at one time, or in a flow type in which the raw materials are continuously fed into the reactor and the product is taken out of the reactor. Since the reaction of the present invention is not as rapid, batch-type is preferred.

(1-3) Phosphonium salts

The phosphonium salt used in the production method according to the first aspect of the present invention is a phosphonium salt having 1 or more alkyl groups.

Examples of the phosphonium salt include phosphonium salts represented by the general formula (3).

[ Wherein R ³、R⁴、R⁵ and R ⁶ are the same or different and each represents a hydrocarbon group. Wherein at least 1 of R ³、R⁴、R⁵ and R ⁶ is alkyl. Y represents a balancing anion. ].

In the general formula (3), as the hydrocarbon group represented by R ³、R⁴、R⁵ and R ⁶, the above-mentioned groups can be exemplified. The same applies to the types and amounts of substituents. Among them, R ³、R⁴、R⁵ and R ⁶ are preferably a site where a carbon atom is bonded to a phosphorus atom in the central portion.

However, at least 1 (1, 2, 3, or 4) of R ³、R⁴、R⁵ and R ⁶ are alkyl groups from the viewpoints of conversion of the reaction, selectivity of the compound represented by the general formula (1), yield of the compound represented by the general formula (1), and the like.

In addition, from the viewpoints of 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, alkyl groups are preferable as R ³、R⁴、R⁵ and R ⁶. Of these, at least 1 (1, 2,3 or 4) of R ³、R⁴、R⁵ and R ⁶ is preferably an alkyl group having 1 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, still more preferably 5 to 10 carbon atoms. In particular, by increasing the number of carbon atoms of 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), and the like can be particularly improved, and the amount of impurities generated can be particularly reduced.

In the general formula (3), the counter anion represented by Y is not particularly limited, and various anions may be used, and examples thereof include halide ions (fluoride ion (F ^－), chloride ion (Cl ^－), bromide ion (Br ^－), iodide ion (I ^－), tetrafluoroborate ion (BF ₄ ^－), hydrogen sulfate ion (HSO ₄ ^－), acetate ion (CH ₃COO^－), hexafluorophosphate ion (PF ₆ ^－), and the like.

Specific examples of the compound represented by the general formula (3) satisfying the above conditions include:

Etc.

As these phosphonium salts, known products or commercially available products can be used. The above phosphonium salts may be used alone or in combination of 2 or more.

In the reaction in the production method of the first aspect of the present invention, the amount of the phosphonium salt used is not particularly limited, but is preferably 0.01 to 10 moles, more preferably 0.1 to 5 moles, still more preferably 1 to 2.5 moles, relative to 1 mole of the compound represented by the general formula (2) from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), and the like. Among them, in the case of using a plurality of phosphonium salts, it is preferable to adjust the total amount thereof to be within the above range.

(1-4) Metal fluorides

The metal fluoride is not particularly limited as long as it can fluorinate a halogen atom other than fluorine in the compound represented by the general formula (2), but is preferably an alkali metal or alkaline earth metal fluoride, more preferably an alkali metal fluoride, from the viewpoints of conversion rate of reaction, selectivity of the compound represented by the general formula (1), yield of the compound represented by the general formula (1), and the like.

Thus, examples of the metal constituting the metal fluoride include: alkali metals such as lithium, sodium, potassium, cesium, etc.; alkaline earth metals such as magnesium, calcium, and barium. These metals may be used alone or in combination of 2 or more.

As the metal fluoride satisfying such a condition, specific examples are: alkali metal fluorides such as lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, and the like; alkaline earth metal fluorides such as magnesium fluoride, calcium fluoride, and barium fluoride. Among them, from the viewpoints of conversion of the reaction, selectivity of the compound represented by the general formula (1), yield of the compound represented by the general formula (1), and the like, alkali metal fluorides such as lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride and the like are preferable, and potassium fluoride is more preferable.

These metal fluorides may be used as known products or commercially available products. The metal fluoride may be used alone, or 2 or more kinds may be used in combination.

In the reaction in the production method of the first aspect of the present invention, the amount of the metal fluoride to be used is not particularly limited, but is preferably 0.01 to 30 moles, more preferably 0.1 to 20 moles, still more preferably 1 to 15 moles, relative to 1 mole of the compound represented by the general formula (2) from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), and the like. Among them, in the case of using a plurality of metal fluorides, it is preferable to adjust the total amount thereof to be within the above range.

(1-5) Solvent

The solvent used in the production method according to the first embodiment of the present invention is preferably a solvent containing a nitrogen-containing organic compound, and more preferably a nitrogen-containing polar solvent, from the viewpoints of dissolving the compound represented by the general formula (2), a phosphonium salt, a metal fluoride, and the like, and excellent conversion of the reaction, selectivity of the compound represented by the general formula (1), yield of the compound represented by the general formula (1), and the like. Examples of such solvents include amide compounds (N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, and the like), amine compounds (triethylamine, 1-methylpyrrolidine, and the like), pyridine compounds (pyridine, picoline, and the like), quinoline compounds (quinoline, methylquinoline, and the like), and the like. Among them, from the viewpoints of conversion of the reaction, selectivity of the compound represented by the general formula (1), yield of the compound represented by the general formula (1), and the like, amide compounds, pyridine compounds, and the like are preferable, N-dimethylformamide, N-diethylformamide, N are more preferable, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, pyridine, picoline, and the like are further preferable, N-dimethylformamide, N-diethylformamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, pyridine, and the like are particularly preferable, N-dimethylformamide, N-methyl-2-pyrrolidone, pyridine, and the like are further preferable.

As such solvents, known ones or commercially available ones can be used. These solvents may be used alone or in combination of 2 or more.

The amount of the solvent to be used is not particularly limited as long as it is an excessive amount, but is preferably 80 to 10000 parts by mass, more preferably 100 to 1000 parts by mass, and even more preferably 150 to 800 parts by mass based on 100 parts by mass of the compound represented by the general formula (2) from the viewpoints of 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), and the like.

(1-6) Reaction temperature

In the reaction according to the first embodiment of the present invention, the reaction temperature may be set to a mild condition, and is usually preferably 0 to 400 ℃, more preferably 25 to 300 ℃, still more preferably 50 to 200 ℃ from the viewpoints of easiness in increasing the conversion rate of the reaction, yield, selectivity and the like of the compound represented by the general formula (1), and easiness in reducing by-products.

(1-7) Reaction time

The reaction time (the time for maintaining at the maximum temperature) of the reaction according to the first embodiment of the present invention may be set to a level at which the reaction proceeds sufficiently, and is preferably 1 minute to 48 hours, more preferably 5 minutes to 24 hours, from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), and the like.

(1-8) Reaction pressure

The reaction pressure of the reaction according to the first embodiment of the present invention is preferably-2 to 2MPa, more preferably-1 to 1MPa, and even more preferably-0.5 to 0.5MPa, from the viewpoints of 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), and the like. In the present invention, the gauge pressure is taken when the pressure is not specifically described.

In the reaction according to the first embodiment of the present invention, the shape and structure of the reactor for reacting the compound represented by the general formula (2) with the metal fluoride are not particularly limited as long as the reactor can withstand the above temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multitubular reactor. Examples of the material of the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloy.

(1-9) Illustrations of reactions

The atmosphere in which the reaction is performed in the first embodiment of the present invention is preferably under an inert gas atmosphere from the viewpoint of suppressing degradation of the compound represented by the general formula (2), the phosphonium salt and the metal fluoride.

The inert gas may be nitrogen, helium, argon, or the like. Among these inert gases, nitrogen is preferable from the viewpoint of cost control.

In the production method according to the first aspect of the present invention, the water content in the system is preferably 700 mass ppm or less, more preferably 0.1 to 650 mass ppm, still more preferably 1 to 600 mass ppm, particularly preferably 10 to 500 mass ppm, from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), and the like. The amount of water in the system is the total amount of water contained in the reaction system, when the total amount of the reagents (the compound represented by the general formula (2), the phosphonium salt, the metal fluoride, the solvent, etc.) used in the reaction is 100% by mass. In order to adjust the amount of water in the system, water may be added to the reaction system. In the present invention, the amount of water in the system is measured by a karl fischer moisture meter.

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

(1-10) Target Compound (general formula (1))

The target compound produced in this way is a compound represented by the general formula (1).

In formula (1), R ¹、X¹ and n are as described above. Wherein, because the number of X ¹ in the general formula (1) is n-n1, n is not less than n1. In addition, when n is an integer of 2 or more, preferably 2 or more of X ¹ are fluorinated, and thus when n is an integer of 2 to 6, n1 represents an integer of 2 to 6.

Specifically, specific examples of the compound represented by the general formula (1) as the target compound to be produced in the present invention include:

Etc.

2. Method for producing fluorine-containing aromatic compound (II)

The production method according to the second aspect of the present invention is a production method of a compound represented by general formula (1A),

[ Wherein 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, which are the same or different, represent halogen atoms other than fluorine atoms. n represents an integer of 3 to 6. n1 represents an integer of 2 to 6. Wherein n is greater than or equal to n1.]

The production method comprises a step of reacting a compound represented by the general formula (2A) with a metal fluoride in the presence of a phosphonium salt having 1 or more alkyl groups to fluorinate 2 or more X ¹ groups to produce a compound represented by the general formula (1A),

[ Wherein R ¹、X¹ and n are as defined above. ].

(2-1) Starting Compound (general formula (2A))

In a second embodiment of the present invention, the compound represented by the general formula (2A) is a compound represented by the general formula (2A):

[ wherein 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, which are the same or different, represent halogen atoms other than fluorine atoms. n represents an integer of 3 to 6. ].

In the general formula (2A), as the hydrocarbon group and perfluoroalkyl group represented by R ¹ and halogen atom other than fluorine atom represented by X ¹, the hydrocarbon group and perfluoroalkyl group represented by R ¹ and halogen atom other than fluorine atom represented by X ¹ in the above "(1-1) starting compound (general formula (2))" can be used. The same applies to the preferred types and specific examples.

In the general formula (2A), the number n of substitution of X ¹ may be 3 to 6, or may be 4 to 6, 5 to 6, or the like, from the viewpoints of 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.

Specific examples of the compound represented by the general formula (2A) satisfying the above conditions include:

etc. (2-2) reaction, phosphonium salt, metal fluoride, solvent, reaction temperature, reaction time, reaction pressure, and illustration of reaction

The reaction in the second embodiment of the present invention can be described as the "(1-2) reaction" described above.

In the second embodiment of the present invention, the phosphonium salt may be as described in the above "(1-3) phosphonium salt". The same applies to the preferred types and specific examples.

In the second embodiment of the present invention, the metal fluoride may be as described in the above "(1-4) description of the metal fluoride". The same applies to the preferred types and specific examples.

In the second embodiment of the present invention, the solvent may be as described in the above "(2-2) solvent". The same applies to the preferred types and specific examples.

In the second embodiment of the present invention, the reaction temperature may be as described above for "(1-6) reaction temperature". The same applies to the preferred ranges.

In the second mode of the present invention, the reaction time may be as described above for "(1-7) reaction time". The same applies to the preferred ranges.

In the second embodiment of the present invention, the reaction pressure may be as described above for "(1-8) reaction pressure". The same applies to the preferred types and specific examples.

In the second embodiment of the present invention, the reaction can be exemplified by the description of "(examples of 1 to 9)" above. The same applies to the preferred types and specific examples.

(2-3) Solvent

The solvent used in the production method according to the second embodiment of the present invention is not particularly limited, and in particular, a polar organic solvent is preferable from the viewpoints of dissolving the compound represented by the general formula (2A), a phosphonium salt, a metal fluoride, and the like, and 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. In addition, from the viewpoints of dissolving the compound represented by the general formula (2A), the phosphonium salt, the metal fluoride, etc., and excellent in 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., a solvent containing a nitrogen-containing organic compound is preferable, and a nitrogen-containing polar solvent is more preferable. Examples of such solvents include amide compounds (N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, and the like), amine compounds (triethylamine, 1-methylpyrrolidine, and the like), pyridine compounds (pyridine, picoline, and the like), quinoline compounds (quinoline, methylquinoline, and the like), and the like. Among them, from the viewpoints of 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, amide compounds, pyridine compounds, and the like are preferable, N-dimethylformamide, N-diethylformamide, N are more preferable, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, pyridine, picoline, and the like are further preferable, N-dimethylformamide, N-diethylformamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, pyridine, and the like are particularly preferable, N-dimethylformamide, N-methyl-2-pyrrolidone, pyridine, and the like are further preferable.

The amount of the solvent to be used is not particularly limited as long as it is an excessive amount, and is preferably 80 to 10000 parts by mass, more preferably 100 to 1000 parts by mass, and even more preferably 150 to 800 parts by mass based on 100 parts by mass of the compound represented by the general formula (2A) from the viewpoints of the conversion 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.

(2-4) Target Compound (general formula (1A))

The target compound produced in this way is a compound represented by the general formula (1A):

[ wherein 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, which are the same or different, represent halogen atoms other than fluorine atoms. n represents an integer of 3 to 6. n1 represents an integer of 2 to 6. Wherein n is greater than or equal to n1.].

In the general formula (1A), R ¹、X¹ and n1 are as described above. Wherein, because the number of X ¹ in the general formula (1) is n-n1, n is not less than n1.

Specifically, specific examples of the compound represented by the general formula (1A) as the target compound to be produced in the present invention include:

Etc.

3. Method for producing fluorine-containing aromatic compound (III)

The production method according to the third embodiment of the present invention is a production method of a compound represented by the general formula (1),

The production method comprises a step of reacting a compound represented by the general formula (2) with a metal fluoride in the presence of a phosphonium salt having 1 or more alkyl groups having 3 or more carbon atoms, and fluorinating 2 or more X ¹ when n is an integer of 2 or more to produce the compound represented by the general formula (1),

[ Wherein R ¹、X¹ and n are as defined above. ].

(3-1) Starting Compound (formula (2)), reaction, metal fluoride, solvent, reaction temperature, reaction time, reaction pressure and target Compound

In the third embodiment of the present invention, the compound represented by the general formula (2) as the starting compound may be described as "(1-1) starting compound (general formula (2)"). The same applies to the preferred types and specific examples.

The reaction in the third embodiment of the present invention can be described as the "(1-2) reaction" described above.

In the third embodiment of the present invention, the metal fluoride may be as described in the above "(1-4) description of the metal fluoride". The same applies to the preferred types and specific examples.

In the third embodiment of the present invention, the solvent may be as described in the above "(2-3) solvent". The same applies to the preferred types and specific examples.

In the third embodiment of the present invention, the reaction temperature may be as described above for "(1-6) reaction temperature". The same applies to the preferred ranges.

In the third embodiment of the present invention, the reaction time may be as described in the above "(1-7) reaction time". The same applies to the preferred ranges.

In the third embodiment of the present invention, the reaction pressure may be as described in the above "(1-8) reaction pressure". The same applies to the preferred types and specific examples.

In the third embodiment of the present invention, the reaction can be exemplified by the description of "(examples of 1 to 9)" above. The same applies to the preferred types and specific examples.

In the third embodiment of the present invention, the compound represented by the general formula (1) as the target compound may be described as "(1-10) the target compound (general formula (1))". The same applies to the preferred types and specific examples.

(3-2) Phosphonium salts

The phosphonium salt used in the third aspect of the present invention is a phosphonium salt having 1 or more alkyl group having 3 or more carbon atoms.

Examples of the phosphonium salt include phosphonium salts represented by the general formula (3A).

[ Wherein R ^3a、R^4a、R^5a and R ^6a are the same or different and each represents a hydrocarbon group. Wherein at least 1 of R ^3a、R^4a、R^5a and R ^6a is an alkyl group having 3 or more carbon atoms. Y represents a balancing anion. ]

In the general formula (3A), as the hydrocarbon group represented by R ^3a、R^4a、R^5a and R ^6a, the above-mentioned groups can be exemplified. The same applies to the types and amounts of substituents. Among them, R ^3a、R^4a、R^5a and R ^6a are preferably a site where a carbon atom is bonded to a phosphorus atom in the central portion.

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

In addition, from the viewpoints of 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, alkyl groups are preferable as R ^3a、R^4a、R^5a and R ^6a. Wherein at least 1 (1, 2, 3 or 4) of R ^3a、R^4a、R^5a and R ^6a is an alkyl group having 3 or more carbon atoms, preferably 4 to 20, more preferably 5 to 15. In particular, by increasing the number of carbon atoms of 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), and the like can be improved, and the amount of impurities generated can be reduced in particular.

In the general formula (3A), as the counter anion represented by Y, the above-mentioned ions can be used.

Specific examples of the compound represented by the general formula (3A) satisfying the above conditions include:

Etc. /(I)

In the reaction according to the third aspect of the present invention, the amount of the phosphonium salt used is not particularly limited, but is preferably 0.01 to 10 moles, more preferably 0.1 to 5 moles, still more preferably 1 to 2.5 moles, relative to 1 mole of the compound represented by the general formula (2), from the viewpoints of the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), the yield of the compound represented by the general formula (1), and the like. Among them, in the case of using a plurality of phosphonium salts, it is preferable to adjust the total amount thereof to be within the above range.

4. Composition 1

The compound represented by the general formula (1) can be obtained by the above-described procedure, but may be obtained as a composition containing a difluorobenzotrifluoride as the compound represented by the general formula (1) and at least 1 halobenzotrifluoride selected from chlorotrifluorotoluene, bromofluorobenzotrifluoride and iodofluorobenzotrifluoride as the compound in which X ¹ in the general formula (2) is only partially fluorinated.

The difluorobenzotrifluoride of the compound represented by the general formula (1) is not particularly limited, and examples thereof include 2, 3-difluorobenzotrifluoride, 2, 4-difluorobenzotrifluoride, and 2, 6-difluorobenzotrifluoride. These difluorobenzotrifluoride may be used alone or in combination of 2 or more.

The halofluorobenzotrifluoride of the compound in which X ¹ in the general formula (2) is only partially fluorinated is not particularly limited, and examples thereof include 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 halofluorobenzotrifluoride may be used alone or in combination of 2 or more.

The total amount of the composition of the present invention according to the first aspect is 100 mol%, and the content of difluorobenzotrifluoride is 60.0 to 99.9 mol%, or 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%, or the like.

The total amount of the composition of the present invention according to the first embodiment is 100 mol%, and the halofluorobenzotrifluoride may be 0.1 to 40.0 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%, or the like.

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

5. Composition (II)

The compound represented by the general formula (1) can be obtained by the above-described procedure, but may be obtained as a composition containing, as the compound represented by the general formula (1), pentafluorotrifluorotoluene and at least 1 halotrifluorotoluene selected from chlorotetrafluorotoluene, bromotetrafluorobenzotrifluoride, iodotetrafluorobenzotrifluoride, dichlorotrifluorobenzotrifluoride, dibromotrifluorobenzotrifluoride, diiodotrifluorobenzotrifluoride, trichlorodifluorobenzotrifluoride, tribromodifluorobenzotrifluoride, triiododifluorobenzotrifluoride, tetrachlorotrifluorobenzotrifluoride, tetrabromofluorobenzotrifluoride and tetraiodofluorobenzotrifluoride as the compound of the general formula (2) in which X ¹ is only partially fluorinated.

The pentafluorotrifluorotoluene of the compound represented by the general formula (1) is not particularly limited, and 2,3,4,5, 6-pentafluorotrifluorotoluene may be mentioned. The pentafluoroetrifluorotoluene may be used alone or in combination of 2 or more kinds.

As the halofluorobenzotrifluoride of the compound in which X ¹ in the general formula (2) is only partially fluorinated, any isotope may be used. The halofluorobenzotrifluoride may be used alone or in combination of 2 or more.

The total amount of the composition of the present invention according to the second aspect may be set to 100 mol%, the content of pentafluoroetrifluorotoluene may be set to 60.0 to 99.9 mol%, or 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%, or the like.

The total amount of the composition of the present invention according to the second aspect may be set to 100 mol%, 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%, or the like.

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

The embodiments of the present invention have been described above, but various modifications in form and detail may be made without departing from the gist and scope of the claimed scope.

Examples

The following examples illustrate the features of the present invention. However, the present invention is not limited to these examples.

In each of examples and comparative examples, the water content was measured by a karl fischer moisture meter at the start of the reaction.

Examples 1 to 7 and comparative examples 1 to 3

2, 4-Dichloro-benzotrifluoride (1 g,0.005 mol), potassium fluoride (0.8 g,0.014 mol), 4.5mL of a solvent (N-methyl-2-pyrrolidone (NMP) or sulfolane), and a phosphonium salt (0.0014 mol) shown in Table 1 were charged in an autoclave, capped and heated to 200℃for reaction for 24 hours.

After the completion of the reaction, mass analysis was performed by gas chromatography or GCMS (gas chromatography mass spectrometry), and structural analysis was performed by NMR (nuclear magnetic resonance).

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

The results are shown in Table 1.

Among them, the phosphonium salts used in table 1 were 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-fluorobenzotrifluoride and/or 4-chloro-2-fluorobenzotrifluoride. In Table 1, the selectivity of 2,4-Cl-F-BTF refers to the total selectivity of 2-chloro-4-fluorobenzotrifluoride and 4-chloro-2-fluorobenzotrifluoride.

TABLE 1

Examples 8 to 13

The reaction was carried out in the same manner as in examples 1 to 7 except that the substrate (0.005 mol) shown in tables 2 to 4 and the phosphonium salt (0.0014 mol) shown in tables 2 to 4 were used in place of 2, 4-dichlorobenzotrifluoride.

Based on the results of mass analysis and structural analysis, it was confirmed that difluorobenzotrifluoride or pentafluoroethyltoluene was produced as the target.

The results are shown in tables 2 to 4.

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

The phosphonium salts used in tables 2 to 4 are as follows.

In tables 2 to 4, the product 2,3-2F-BTF means 2, 3-difluorobenzotrifluoride; 2,3-Cl-F-BTF refers to 2-chloro-3-fluorobenzotrifluoride and/or 3-chloro-2-fluorobenzotrifluoride; 2,6-2F-BTF refers to 2, 6-difluoro-benzotrifluoride; 2,6-Cl-F-BTF refers to 2-chloro-6-fluorobenzotrifluoride; 5F-BTF refers to 2,3,4,5, 6-pentafluorotrifluorotoluene; 4F,1Cl-BTF refers to chlorotetrafluorobenzotrifluoride (both including isotopes); 3F,2Cl-BTF refers to dichlorotrifluoro benzotrifluoride (both including isotopes); 2F,3Cl-BTF refers to trichlorodifluorobenzotrifluoride (both including isotopes); 1F,4Cl-BTF refers to tetrachlorofluorobenzotrifluoride (both including isotopes). In tables 2 to 4, the selectivity of 2,3-Cl-F-BTF refers to the total selectivity of 2-chloro-3-fluorobenzotrifluoride and 3-chloro-2-fluorobenzotrifluoride; the selectivity of 4F,1Cl-BTF refers to the total selectivity of isotopes of chlorotetrafluorotrifluorotoluene; the selectivity of 3F,2Cl-BTF refers to the total selectivity of isotopes of dichlorotrifluoro-benzotrifluoride; the selectivity of 2F,3Cl-BTF refers to the total selectivity of trichlorodifluorobenzotrifluoride; the selectivity of 1F,4Cl-BTF refers to the total selectivity of the tetrachlorofluorobenzotrifluoride.

TABLE 2

TABLE 3

TABLE 4

Claims

1. A process for producing a compound represented by the following general formula (1),

In the general formula (1), 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 to 6, n1 represents an integer of 1 to 6, wherein when n.gtoreq.n1 is an integer of 2 to 6, n1 represents an integer of 2 to 6,

The manufacturing method is characterized in that,

Comprising a step of reacting a compound represented by the general formula (2) with a metal fluoride in a solvent containing a nitrogen-containing organic compound in the presence of a phosphonium salt having 1 or more alkyl groups, and fluorinating 2 or more X ¹ when n is an integer of 2 or more to produce the compound represented by the general formula (1),

In the general formula (2), R ¹、X¹ and n are as defined above.

2. The method of manufacturing according to claim 1, wherein,

The fluorination is performed in a system having a water content of 700 mass ppm or less.

3. The method of manufacturing according to claim 1 or 2, wherein,

And n is an integer of 3-6.

4. The method according to any one of claim 1 to 3,

The metal fluoride is fluoride of alkali metal or alkaline earth metal.

5. A composition comprising, as a main ingredient,

Contains difluoro-benzotrifluoride and halogenated fluoro-benzotrifluoride, wherein the halogenated fluoro-benzotrifluoride is at least 1 selected from chloro-benzotrifluoride, bromo-benzotrifluoride and iodo-benzotrifluoride.

6. The composition of claim 5,

The total amount of the composition is set to 100 mol%, the content of the difluoro benzotrifluoride is 60.0-99.9 mol%, and the content of the halo fluoro benzotrifluoride is 0.1-40.0 mol%.

7. The composition of claim 5 or 6,

The composition is useful as a solvent for organic synthesis, a pesticidal intermediate or a pharmaceutical intermediate.

8. A composition comprising, as a main ingredient,

Containing pentafluoroetrifluorotoluene and halofluorotrifluorotoluene, wherein the halofluorobenzotrifluoride is at least 1 selected from chlorotetrafluorobenzotrifluoride, bromotetrafluorobenzotrifluoride, iodotetrafluorobenzotrifluoride, dichlorotrifluorobenzotrifluoride, dibromotrifluorobenzotrifluoride, diiodotrifluorobenzotrifluoride, trichlorodifluorobenzotrifluoride, tribromodifluorobenzotrifluoride, triiododifluorobenzotrifluoride, tetrachlorobenzotrifluoride, tetrabromofluorobenzotrifluoride and tetraiodofluorobenzotrifluoride.

9. The composition of claim 8, wherein the composition comprises,

The total amount of the composition is set to 100 mol%, the content of the pentafluoroetrifluorotoluene is 60.0 to 99.9 mol%, and the content of the halogenated fluorobenzotrifluoride is 0.1 to 40.0 mol%.

10. A composition according to claim 8 or 9,

The composition is used as an etching gas or a cleaning gas.