JP7381912B2 - Method for producing fluorine-containing aromatic compound - Google Patents

Description

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

As a method for producing a fluorine-containing aromatic compound represented by perfluorotoluene, which is expected to be used as a next-generation etching gas, for example, 1.2% by mass of tetrakis(diethylamino)phosphonium salt is used as a catalyst. It is known to fluorinate a halogenated aromatic compound with ~1.4 equivalents of an alkali metal or alkaline earth metal fluoride (see Patent Document 1).

Russian Patent Publication No. 2157800

An object of the present disclosure is to provide a novel method that can efficiently produce fluorine-containing aromatic compounds.

The present disclosure includes the following configurations.

Item 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 from 1 to 6. n1 represents an integer from 1 to 6. However, when n≧n1 and n is an integer from 2 to 6, n1 represents an integer from 2 to 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 manufacturing method comprising the 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 above general formula (1). .

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

Item 3. The manufacturing method according to claim 1 or 2, wherein the n is an integer of 3 to 6.

Item 4. Item 4. The manufacturing 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 containing difluorobenzotrifluoride and at least one halogenated fluorobenzotrifluoride selected from the group consisting of chlorofluorobenzotrifluoride, bromofluorobenzotrifluoride, and iodofluorobenzotrifluoride.

Item 6. When the total amount of the composition is 100 mol%, 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%. The composition according to item 5, which is mol %.

Section 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.

Section 8. Pentafluorobenzotrifluoride, chlorotetrafluorobenzotrifluoride, bromotetrafluorobenzotrifluoride, iodotetrafluorobenzotrifluoride, dichlorotrifluorobenzotrifluoride, dibromotrifluorobenzotrifluoride, diiodotrifluorobenzotrifluoride, At least one member selected from the group consisting of trichlorodifluorobenzotrifluoride, tribromodifluorobenzotrifluoride, triiododifluorobenzotrifluoride, tetrachlorofluorobenzotrifluoride, tetrabromofluorobenzotrifluoride, and tetraiodofluorobenzotrifluoride and a halogenated fluorobenzotrifluoride.

Item 9. When the total amount of the composition is 100 mol%, the content of the pentafluorobenzotrifluoride is 60.0 to 99.9 mol%, and the content of the halogenated fluorobenzotrifluoride is 0.1 to 40. The composition according to item 8, wherein the composition 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, a novel method that can efficiently produce a fluorine-containing aromatic compound can be provided.

In this specification, "contain" is a concept that includes all of "comprise," "consist essentially of," and "consist of."

Furthermore, in this specification, when a numerical range is expressed as "A to B", it means greater than or equal to A and less than or equal to B.

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

Patent Document 1 discloses that 1 to 5% by mass of tetrakis(diethylamino)phosphonium salt is used as a catalyst, and 1.2 to 1.4 equivalents of an alkali metal or alkaline earth metal fluoride (particularly potassium fluoride) is used. , it has been described that fluorination of halogenated aromatic compounds is carried out, but among these, tetrakis(diethylamino)phosphonium salt is not commercially available and is not a practical method due to high synthesis cost, so fluorine-containing There is a need for new methods by which aromatic compounds can be produced.

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

1. Method for producing fluorine-containing aromatic compound (Part 1)
The manufacturing method according to the first aspect of the present disclosure includes:
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 from 1 to 6. n1 represents an integer from 1 to 6. However, when n≧n1 and n is an integer from 2 to 6, n1 represents an integer from 2 to 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
The method includes a step of reacting with a metal fluoride and, when n is an integer of 2 or more, fluorinating two or more X ¹ to produce a compound represented by the above general formula (1).

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

[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 from 1 to 6. ]
It is a compound represented by

In general formula (2), the hydrocarbon group represented by R ¹ is not particularly limited, and includes, for example, an alkyl group, an aryl group, and a group formed by any combination of these groups (for example, an aralkyl group, an alkylaryl group, etc.). group, alkylaralkyl group), and the like.

In general formula (2), the alkyl group as a 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 a linear or branched chain) is not particularly limited, and the number of carbon atoms in the alkyl group (in the case of a linear or branched chain) is not particularly limited, and the number of carbon atoms in the alkyl group is not particularly limited. From the viewpoint of the yield of the represented compound, etc., the number is preferably from 1 to 20, more preferably from 3 to 15, and even more preferably from 5 to 10. The number of carbon atoms in the alkyl group (if cyclic) is not particularly limited, and depends on the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), and the yield of the compound represented by general formula (1). From the viewpoint of the like, for example, 3 to 8 is preferable, and 4 to 7 is 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, 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 a 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 selectivity of the compound represented by the general formula (1), etc. From the viewpoint of yield etc. of the compound represented by, those having 6 to 20 carbon atoms are preferred, those having 6 to 12 carbon atoms are more preferred, and those having 6 to 10 carbon atoms are even more preferred. The aryl group may be monocyclic or polycyclic (eg, bicyclic, tricyclic, etc.), but is preferably monocyclic.

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

In general formula (2), the aralkyl group as a hydrocarbon group represented by R ¹ is not particularly limited, but the conversion rate of reaction, selectivity of the compound represented by general formula (1), general formula (1) From the viewpoint of the yield of the compound represented by Examples thereof include an aralkyl group in which one hydrogen atom) is substituted with the above aryl group.

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

In the general formula (2), the alkylaryl group as a 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 selectivity of the compound represented by the general formula (1 ) From the viewpoint of the yield of the compound represented by Examples include alkylaryl groups substituted with (preferably 1 to 2) alkyl groups.

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

In the general formula (2), the alkylaralkyl group as a 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 selectivity of the compound represented by the general formula (1 ) From the viewpoint of the yield of the compound represented by Examples include alkylaralkyl groups substituted with 1 to 6 (preferably 1 to 2) alkyl groups.

In general formula (2), examples of the substituent for 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, and even more preferably 0 to 1.

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

Examples of such optionally substituted alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, per Examples include fluoromethoxy group and perfluoroethoxy group.

The halogen atom as a substituent for the above-mentioned hydrocarbon group is not particularly limited and includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

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.

The perfluoroalkyl group can be linear, branched, or cyclic. Among these, linear perfluoroalkyl groups are preferred from the viewpoints of reaction conversion rate, selectivity of the compound represented by general formula (1), yield of the compound represented by general formula (1), and the like.

The number of carbon atoms in this perfluoroalkyl group is not particularly limited, but it depends on the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), and the yield of the compound represented by the general formula (1). From the viewpoint of rate etc., the number is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.

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

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

In general formula (2), n, which is the number of ^{substitutions} for From the viewpoint of yield, etc., the number is preferably 1 to 6, and may also be 2 to 6, 3 to 6, 4 to 6, 5 to 6, etc.

In addition, when n, which is the number of substitutions for X, is 3 to 6, the compound represented by general formula (2) has general formula (2A):

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

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

etc.

As the compound represented by the above general formula (2), publicly known or commercially available products can be used. Moreover, the compound represented by the above general formula (2) can be used alone or in combination of two or more types.

(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 fluorinated by a metal fluoride in the presence of a specific phosphonium salt. By this reaction, a compound substituted with a fluorine atom and represented by the above general formula (1) is produced.

In this case, if there are multiple X ¹ atoms that are halogen atoms other than fluorine, that is, if n in general formula (2) is an integer of 2 or more, a compound in which two or more (especially all) of them are fluorinated. are selectively synthesized.

On the other hand, in the compound represented by the above general formula (2), R ¹ remains without reacting 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 according to the first aspect of the present disclosure can be carried out using either a batch method in which raw materials are charged into a reactor all at once, or a flow method in which raw materials are continuously supplied into the reactor and products are extracted from the reactor. This method can also be adopted. Since the reaction of the present disclosure is not a very fast reaction, it is preferable to employ a batch method.

(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, for example, has the 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. ]
Examples include phosphonium salts represented by:

In general formula (3), the hydrocarbon groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ include those described above. The types and number of substituents are also the same. Note that R ³ , R ⁴ , R ⁵ and R ⁶ are preferably sites to which a carbon atom is bonded to the phosphorus atom in the center.

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

In addition, 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 15 carbon atoms. 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. can be 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, such as halide ions (fluoride ions (F ^- ), chloride ions (Cl ^- ), bromide ion (Br ^- ), iodide ion (I ^- ), etc.), tetrafluoroborate ion (BF ₄ ^- ), hydrogen sulfate ion (HSO ₄ ^- ), acetate ion (CH ₃ COO ^- ), hexa Examples include fluorophosphate ion (PF ₆ ⁻ ).

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

etc.

As these phosphonium salts, known or commercially available products can be used. Moreover, the above-mentioned phosphonium salts can be used alone or in combination of two or more kinds.

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 the general formula (1), the selectivity of the compound represented by the general formula (1), etc. From the viewpoint of the yield of the compound represented by formula (2), the amount is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, and 1 to 5 mol, per 1 mol of the compound represented by general formula (2). 2.5 mol is more preferred. In addition, when using multiple phosphonium salts, it is preferable to adjust the total amount so that it falls 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), but the conversion rate of the reaction, the general formula From the viewpoint of the selectivity of the compound represented by (1) and the yield of the compound represented by general formula (1), fluorides of alkali metals or alkaline earth metals are preferable, and fluorides of alkali metals are more preferable. Preferable Therefore, examples of metals constituting the metal fluoride 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. Examples include 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.

As these metal fluorides, publicly known or commercially available products can be used. Further, the above metal fluorides can be used alone or in combination of two or more.

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 the general formula (1), the selectivity of the compound represented by the general formula (1), ) is preferably 0.01 to 30 mol, more preferably 0.1 to 20 mol, 1 to 1 mol of the compound represented by general formula (2). ˜15 mol is more preferred. In addition, when using multiple metal fluorides, it is preferable to adjust the total amount so that it falls within the above range.

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

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

The amount of solvent to be used is not particularly limited as long as it is a solvent amount, and an excess amount can be used. From the viewpoint of the yield of the compound represented by general formula (2), the amount is preferably 80 to 10,000 parts by mass, more preferably 100 to 1,000 parts by mass, and 150 to 800 parts by mass. is even more preferable.

(1-6) Reaction temperature In the reaction of the first aspect of the present disclosure, the reaction temperature can be set to mild conditions, and the conversion rate of the reaction, the yield of the compound represented by general formula (1), From the viewpoint of easily improving selectivity and reducing by-products, the temperature is usually 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 (maintenance time at the highest temperature) of the reaction according to the first aspect of the present disclosure can be set to such an extent that the reaction sufficiently proceeds, and the conversion rate of the reaction and the general formula (1 ) From the viewpoint of the selectivity of the compound represented by formula (1), the yield of the compound represented by general formula (1), etc., the time is preferably 1 minute to 48 hours, and 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 determined by the conversion rate of the reaction, the selectivity of the compound represented by the general formula (1), and the selectivity of the compound represented by the general formula (1). From the viewpoint of yield etc., -2 to 2 MPa is preferable, -1 to 1 MPa is more preferable, and -0.5 to 0.5 MPa is even more preferable. Note that in this disclosure, unless otherwise specified, pressure is referred to as gauge pressure.

In the reaction of the first aspect of the present disclosure, the reactor for reacting the compound represented by general formula (2) with the metal fluoride may have any shape and structure as long as it can withstand the above temperature and pressure. Not particularly limited. 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) Examples of reactions Regarding the atmosphere during the reaction in the first aspect of the present disclosure, from the viewpoint of suppressing deterioration of the compound represented by 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 preferred from the viewpoint of reducing costs.

In the production method of the first aspect of the present disclosure, the amount of water in the system is determined by the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), and the yield of the compound represented by general formula (1). From the viewpoint of rate etc., the amount is preferably 700 ppm by mass or less, more preferably 0.1 to 650 ppm by mass, even more preferably 1 to 600 ppm by mass, and particularly preferably 10 to 500 ppm by mass. The amount of water in the system is the amount of water contained in the reaction system, assuming that the total amount of the reagents (compound represented by general formula (2), phosphonium salt, metal fluoride, solvent, etc.) used in the reaction is 100% by mass. Means the total amount of water. Furthermore, water can be added to the reaction system in order to adjust the amount of water in the system. Note that in the present disclosure, the amount of water in the system is measured using a Karl Fischer moisture meter.

After the reaction is completed, a compound represented by the general formula (1) can be obtained by performing a purification treatment according to a conventional method if 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 from 1 to 6. n1 represents an integer from 1 to 6. However, when n≧n1 and n is an integer from 2 to 6, n1 represents an integer from 2 to 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 n−n1, n≧n1 is necessarily satisfied. Further, when n is an integer of 2 or more, it is preferable that two or more X ¹ are fluorinated, so when n is an integer of 2 to 6, n1 represents an integer of 2 to 6.

That is, the compound represented by the 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 manufacturing method according to the second aspect of the present disclosure is based on 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 from 3 to 6. n1 represents an integer from 2 to 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
The method includes a step of reacting with a metal fluoride to fluorinate two or more X ¹ 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) is represented by 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 from 3 to 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-mentioned “(1-1) starting compound (general formula (2) )", the explanation of the hydrocarbon group and perfluoroalkyl group represented by R ¹ and the halogen atom other than the fluorine atom represented by X ¹ can be adopted. Preferred types and specific examples are also the same.

In the general formula (2A), n, which is the number of substitutions for 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 can also be 4 to 6, 5 to 6, etc.

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

etc.

(2-2) Reaction, phosphonium salt, metal fluoride, solvent, reaction temperature, reaction time, reaction pressure, and reaction examples The reaction in the second aspect of the present disclosure is as described in "(1-2) Reaction" above. can be adopted.

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

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

In the second aspect of the present disclosure, the explanation of "(2-2) solvent" above can be adopted as the solvent. Preferred types and specific examples are also the same.

In the second aspect of the present disclosure, the reaction temperature can be as described in "(1-6) Reaction temperature" above. The same applies to preferred ranges.

In the second aspect of the present disclosure, the reaction time can be as described in "(1-7) Reaction time" above. The same applies to preferred ranges.

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

In the second aspect of the present disclosure, the explanation of "(1-9) Reaction example" above can be adopted as the reaction example. Preferred types and specific examples are also the same.

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

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

The amount of solvent to be used is not particularly limited as long as it is a solvent amount, and an excess amount can be used. From the viewpoint of the yield of the compound represented by general formula (2A), the amount is preferably 80 to 10,000 parts by mass, more preferably 100 to 1,000 parts by mass, and 150 to 800 parts by mass. is even more preferable.

(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 from 3 to 6. n1 represents an integer from 2 to 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 n−n1, n≧n1 is necessarily satisfied.

That is, the compound represented by the 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 manufacturing method according to the third aspect of the present disclosure includes 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 from 1 to 6. n1 represents an integer from 1 to 6. However, when n≧n1 and n is an integer from 2 to 6, n1 represents an integer from 2 to 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):

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

(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 (general formula (2)) For the compound represented by 2), the above description of "(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 above description of "(1-4) metal fluoride" can be adopted as the metal fluoride. Preferred types and specific examples are also the same.

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

In the third aspect of the present disclosure, the reaction temperature can be as described in "(1-6) Reaction temperature" above. The same applies to preferred ranges.

In the third aspect of the present disclosure, the reaction time can be as described in "(1-7) Reaction time" above. The same applies to preferred ranges.

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

In the third aspect of the present disclosure, the explanation of "(1-9) Reaction example" above can be adopted as the reaction example. 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 be as described in "(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 having 3 or more carbon atoms.

This phosphonium salt, for example, has the 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. ]
Examples include phosphonium salts represented by:

In general formula (3A), the hydrocarbon groups represented by R ^3a , R ^4a , R ^5a and R ^6a include those described above. The types and number of substituents are also the same. Note that R ^3a , R ^4a , R ^5a and R ^6a are preferably sites to which a carbon atom is bonded to the phosphorus atom at the center.

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

In addition, from the viewpoint of the selectivity of the compound represented by general formula (1), the yield of the compound represented by general formula (1), etc., R ^3a , R ^4a , R ^5a and R ^6a are selected from 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 carbon atoms, more preferably 5 to 15 carbon atoms. is an alkyl group. 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. can be particularly improved, The amount of impurities produced can be particularly reduced.

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

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

etc.

As these phosphonium salts, known or commercially available products can be used. Moreover, the above-mentioned phosphonium salts can be used alone or in combination of two or more kinds.

In the reaction according to the third aspect of the present disclosure, the amount of the phosphonium salt to be used is not particularly limited, but the conversion rate of the reaction, the selectivity of the compound represented by general formula (1), the selectivity of the compound represented by general formula (1), From the viewpoint of the yield of the compound represented by general formula (2), the amount is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, and 1 to 2.5 mol. Mole is more preferred. In addition, when using multiple phosphonium salts, it is preferable to adjust the total amount so that it falls within the above range.

4. Composition (Part 1)
As described above, the compound represented by the general formula (1) can be obtained, and the compound represented by the general formula (1) includes difluorobenzotrifluoride and one of X ¹ in the 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 you can get it.

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

There are no particular restrictions on the halogenated fluorobenzotrifluoride, which is a compound in which only a portion of X ¹ in the general formula (2) is fluorinated, but 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 halogenated fluorobenzotrifluorides can be used alone or in combination of two or more.

When the total amount of the composition of the present disclosure according to the first aspect is 100 mol%, the content of difluorobenzotrifluoride is 60.0 to 99.9 mol%, 65.0 to 99.5 mol%, and 70 mol%. .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 do so.

Furthermore, when 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 do this.

The composition of the present disclosure according to the first aspect can be effectively used for various purposes such as a solvent for organic synthesis, an agricultural chemical intermediate, and a pharmaceutical intermediate.

5. Composition (Part 2)
As described above, the compound represented by the general formula (1) can be obtained, and the compound represented by the general formula (1) includes pentafluorobenzotrifluoride and X ¹ in the general formula (2). Only partially fluorinated compounds include 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 a 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, which is a compound in which only a portion of X ¹ in the general formula (2) is fluorinated. The halogenated fluorobenzotrifluoride can be used alone or in combination of two or more.

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

Furthermore, when 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 do this.

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

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

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

In each Example and Comparative Example, the moisture content was measured using a Karl Fischer moisture meter at the start of the reaction.

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

After the reaction was completed, mass spectrometry was performed using 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.

In addition, in Table 1, the phosphonium salts used are as follows.

In addition, in Table 1, the product 2,4-2F-BTF means 2,4-difluorobenzotrifluoride, and 2,4-Cl-F-BTF means 2-chloro-4-fluorobenzotrifluoride. Means trifluoride and/or 4-chloro-2-fluorobenzotrifluoride. In Table 1, the selectivity of 2,4-Cl-F-BTF means the total selectivity of 2-chloro-4-fluorobenzotrifluoride and 4-chloro-2-fluorobenzotrifluoride.

Examples 8-13
Examples 1 to 7 except that the substrates shown in Tables 2 to 4 (0.005 mol) and the phosphonium salts shown in Tables 2 to 4 (0.0014 mol) were used instead of 2,4-dichlorobenzotrifluoride. The reaction was carried out in the same manner.

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 to 4.

In addition, 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.

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

Furthermore, 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- 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, and 4F,1Cl-BTF means chlorotetrafluoride. 3F,2Cl-BTF means dichlorotrifluorobenzotrifluoride (including all isotopes), 2F,3Cl-BTF means trichlorodifluoride 1F,4Cl-BTF means tetrachlorofluorobenzotrifluoride (including all isotopes). In addition, in Tables 2 to 4, the selectivity of 2,3-Cl-F-BTF means the total selectivity of 2-chloro-3-fluorobenzotrifluoride and 3-chloro-2-fluorobenzotrifluoride. , the selectivity of 4F,1Cl-BTF means the total isotopic selectivity of chlorotetrafluorobenzotrifluoride, and the selectivity of 3F,2Cl-BTF means the total isotopic selectivity of dichlorotrifluorobenzotrifluoride. The selectivity of 2F,3Cl-BTF means the total selectivity of trichlorodifluorobenzotrifluoride, and the selectivity of 1F,4Cl-BTF means the total selectivity of tetrachlorofluorobenzotrifluoride. do.

Claims (4)

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 from 1 to 6. n1 represents an integer from 1 to 6. However, when n≧n1 and n is an integer from 2 to 6, n1 represents an integer from 2 to 6. ]
A method for producing a compound represented by
In a solvent containing an amide 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 manufacturing method comprising the 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 above general formula (1). . The manufacturing method according to claim 1, wherein the fluorination is performed in a system having a water content of 700 mass ppm or less. The manufacturing method according to claim 1 or 2, wherein the n is an integer of 3 to 6. The manufacturing method according to any one of claims 1 to 3, wherein the metal fluoride is an alkali metal or alkaline earth metal fluoride.