TW202328034A - Method for producing perfluoroalkyl group-containing aromatic compound - Google Patents

Abstract

The present invention makes it possible to efficiently produce a perfluoroalkyl group-containing aromatic compound by reacting, in a solvent, a compound represented by general formula (3): R6Cu (3) [where R6 indicates a perfluoroalkyl group] and/or a complex, and a compound represented by general formula (2): (2) [where R1, R2, R3, R4, and R5 are the same as above, and X indicates a bromine atom or a chlorine atom]. The compound represented by general formula (3) and/or the complex thereof can be obtained by, for example, a step (I) for mixing, in a solvent, a compound represented by general formula (4): R6X2 (4) [where R6 is the same as above, and X2 indicates a bromine atom or an iodine atom], an inorganic material including copper, and a solvent so as to produce a compound represented by general formula (3) and/or a complex thereof.

Description

Process for producing aromatic compounds containing perfluoroalkyl groups

The present invention relates to a method for producing aromatic compounds containing perfluoroalkyl groups.

A method for producing perfluoroalkyl-containing aromatic compounds, represented by perfluorotoluene, which is expected as a next-generation etching gas, is known, for example, using a pyridine solvent, copper, CF ₃ I and iodobenzene (Refer to Non-Patent Document 1). [Prior art literature] [Non-patent literature]

[Non-Patent Document 1] Journal of Chemical Society Perkin Trans 1980 (3) pp 661-664.

[Problem to be Solved by the Invention]

An object of the present invention is to provide a method for efficiently producing a perfluoroalkyl-containing aromatic compound. [Means used to solve problems]

The present invention includes the following constitutions.

Item 1. A general formula (1):

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different, and represent a hydrogen atom or a fluorine atom. However, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ represents a fluorine atom. R ⁶ represents a perfluoroalkyl group. ] The production method of the compound represented, wherein, possess (II) in solvent, make general formula (3): [In the formula, R represents a ^{perfluoroalkyl} group. ] represented by the compound and/or its complex, and the general formula (2):

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above. X ¹ represents a bromine atom or a chlorine atom. ] The step (II) of reacting the compound represented by the above-mentioned general formula (1) to generate the compound represented by it.

Item 2. The production method as described in item 1, wherein, before the aforementioned step (II), (I) is provided in the solvent, so that the general formula (4): [In the formula, R is ^the same as above. X ² represents a bromine atom or an iodine atom. ] reacting the compound represented by copper with an inorganic material containing copper to generate the compound represented by the aforementioned general formula (3) and/or its complexes (I).

Item 3. The production method according to Item 1 or 2, wherein the carbon number of the aforementioned R ⁶ is 1-5.

Item 4. The production method according to any one of Items 1 to 3, wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are all fluorine atoms.

Item 5. The manufacturing method according to any one of Items 1 to 4, wherein the inorganic material containing copper is copper.

Item 6. The production method according to any one of Items 1 to 5, wherein the solvent is an organic compound containing nitrogen.

Item 7. The production method described in any one of Items 2 to 6, which further adds a ligand compound in the aforementioned step (I).

Item 8. The production method according to Item 7, wherein the coordination compound is a coordination compound in which the coordination atom is a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom.

Item 9. The production method according to any one of Items 1 to 8, wherein the reaction temperature in the aforementioned step (II) is 0 to 200°C.

Item 10. A composition comprising the general formula (1):

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different, and represent a hydrogen atom or a fluorine atom. However, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ represents a fluorine atom. R ⁶ represents a perfluoroalkyl group. ] represented by the compound, and the general formula (5):

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above. ] represented by the compound, and/or the general formula (6):

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above. ], and when the total amount of the composition is 100 mol%, the content of the compound represented by the aforementioned general formula (1) is 10.0-99.9 mol%.

Item 11. The composition as described in Item 10, wherein the total content of the compound represented by the aforementioned general formula (5) and the compound represented by the aforementioned general formula (6) is equal to or equal to 100 mol of the total amount of the composition. When ear%, it is 0.01-90.0 mole%.

Item 12. The composition as described in Item 10 or 11, which is used as a cleaning gas, an etching gas, or a synthesis intermediate. [Effect of Invention]

According to the present invention, a method for efficiently producing a perfluoroalkyl group-containing aromatic compound can be provided.

In this specification, "contains" includes any concept of "comprise", "consist essentially of" and "consist of".

In addition, in the present specification, when a numerical range is expressed as "A to B", it means that A or more and B or less.

In the present invention, the so-called "selectivity" refers to the ratio of the total molar amount of the target compound contained in the effluent gas flowing out from the reactor outlet to the total molar amount of the compounds other than the raw material compound in the effluent gas. Proportion (mole %).

In the present invention, the so-called "conversion rate" means the ratio of the total molar amount of compounds other than the raw material compound contained in the effluent gas flowing out from the reactor outlet to the molar amount of the raw material compound supplied to the reactor. Proportion (mole %).

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

1. Method for producing aromatic compounds containing perfluoroalkyl groups The manufacturing method of the present invention is General formula (1):

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different, and represent a hydrogen atom or a fluorine atom. However, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ represents a fluorine atom. R ⁶ represents a perfluoroalkyl group. ] The production method of the compound represented, wherein, possess (II) in solvent, make general formula (3): [In the formula, R represents a ^{perfluoroalkyl} group. ] represented by the compound and/or its complex, and the general formula (2):

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above. X ¹ represents a bromine atom or a chlorine atom. ] The step (II) of reacting the compound represented by the above-mentioned general formula (1) to generate the compound represented by it.

Also, in the present invention, the compound represented by the general formula (3) or its complex is not particularly limited, but for example, can be obtained by the following steps: (1) in a solvent, make the general formula (4) : [In the formula, R is ^the same as above. X ² represents a bromine atom or an iodine atom. ] reacting the compound represented by copper with an inorganic material containing copper to generate the compound represented by the aforementioned general formula (3) and/or its complexes (I).

As a method for producing perfluoroalkyl-containing aromatic compounds represented by perfluorotoluene, it has been known to use perchloroalkyl-containing aromatic compounds represented by perchlorotoluene as starting materials, Potassium chloride was used to fluorinate the starting material.

However, in the above-mentioned conventional method, since the reaction temperature is set at a high temperature of 400 to 500° C., it is sought to advance the reaction under mild conditions.

Also, Non-Patent Document 1 discloses, for example, a method of quantitatively producing perfluorotoluene by injecting a pyridine solvent, copper, CF ₃ I and iodobenzene in an autoclave at one time and reacting them. However, in this method, it is necessary to use a compound containing an iodine atom like iodobenzene as a substrate. According to Non-Patent Document 1, when bromobenzene is used as a substrate, impurities such as pentafluoroethylbenzene and benzene are produced to the same extent as the target product, and perfluorotoluene cannot be efficiently produced. Therefore, since the method of Non-Patent Document 1 lacks room for selecting a substrate, a method of obtaining an aromatic compound containing a perfluoroalkyl group by using a substrate containing other halogen atoms such as chlorine atoms and bromine atoms was sought.

According to the present invention, in a solvent, the copper compound containing a perfluoroalkyl group and/or its complex is reacted with an aromatic compound containing a chlorine atom or a bromine atom belonging to a substrate, whereby it can be efficiently produced under mild conditions. Aromatic compounds containing perfluoroalkyl groups are obtained. At this time, by not making the reaction temperature too high, high selectivity and yield can be obtained for the obtained perfluoroalkyl-containing aromatic compound. In addition, the copper compound containing a perfluoroalkyl group and/or its complex can be obtained by reacting an iodine compound containing a perfluoroalkyl group with an inorganic material containing copper in a solvent.

[1-1] Step (I) In the production method of the present invention, when step (I) is used, the compound represented by the general formula (4) is reacted with an inorganic material containing copper in a solvent. In this way, the general formula (3) can be formed in the system: [In the formula, R represents a ^{perfluoroalkyl} group. ] represents the compound and/or its complex.

Specifically, for example, in the case of using copper as the copper-containing inorganic material and not using a coordination compound described later, the following reaction formula is followed: [In the formula, R is ^the same as above. ], copper compounds containing perfluoroalkyl groups can be obtained.

(1-1-1) Compound represented by general formula (4) The compound represented by general formula (4) is general formula (4): [In the formula, R represents a ^{perfluoroalkyl} group. X ² represents a bromine atom or an iodine atom. ] represents the compound.

In the general formula (4), the perfluoroalkyl group represented by R ⁶ means an alkyl group in which all hydrogen atoms are replaced by fluorine atoms.

Any of linear, branched and cyclic perfluoroalkyl groups may be used. Among them, it is easier to form the compound represented by the general formula (3) and/or its complex through the step (I), and it is easy to improve the conversion rate of the step (II), and finally obtain the general formula (1) From the viewpoint of the yield, selectivity, etc. of the compounds shown, a linear perfluoroalkyl group is preferable.

The carbon number of this perfluoroalkyl group is not particularly limited, yet, form the compound represented by general formula (3) and/or its complex by step (I) more easily, and improve step (II) easily ), the yield of the compound represented by the general formula (1) finally obtained, the selectivity, etc., the 1-5 series are better, the 1-4 series are more preferable, and the 1-3 series are more preferred. good.

As such a perfluoroalkyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, etc. are mentioned specifically,.

In the general formula (4), X ² is a bromine atom or an iodine atom, and it is easier to form the compound represented by the general formula (3) and/or its complex by step (I), and it is easy to improve the step (II) ), the yield and selectivity of the compound represented by the general formula (1) finally obtained, the iodine atom is preferred.

As the compound represented by the general formula (4) satisfying the above conditions, specifically, CF ₃ I, CF ₃ Br, CF ₃ CF ₂ I, CF ₃ CF ₂ Br, CF ₃ CF ₂ CF ₂ I. CF ₃ CF ₂ CF ₂ Br, etc.

As the compound represented by the above general formula (4), known or commercially available compounds can be used. Moreover, the compound represented by the said general formula (4) may be used individually or in combination of 2 or more types.

(1-1-2) Inorganic materials containing copper The inorganic material containing copper is not particularly limited, but for example, in addition to copper, gold-plated metal, gun metal, brass, phosphor bronze, Muntz metal, aluminum bronze, beryllium copper, Copper alloys of foreign copper, white copper, cadmium copper, chromium copper, etc. Among them, it is easier to form the compound represented by the general formula (3) and/or its complex through the step (I), and it is easy to improve the conversion rate of the step (II), and finally obtain the general formula (1) From the standpoint of the yield and selectivity of the compounds shown, copper is preferred.

As the above-mentioned inorganic material containing copper, known or commercially available materials can be used. In addition, the above-mentioned inorganic materials containing copper may be used alone or in combination of two or more.

In the step (I) of the present invention, the usage amount of the inorganic material comprising copper is not particularly limited, however, it is easier to form the compound represented by the general formula (3) and/or its complex, and it is easy to improve the conversion rate of step (II), the yield and selectivity of the compound represented by the general formula (1) finally obtained, compared to the compound represented by the general formula (4) 1 mol of the compound is preferably 0.05-5.0 mol, more preferably 0.1-3.0 mol, and even more preferably 0.2-2.0 mol.

(1-1-3)Solvent The solvent that can be used in the step (I) is not particularly limited, however, especially from the viewpoint of dissolving the compound represented by the general formula (4), the inorganic material containing copper, etc., and it is easier to use the solvent in the step ( I) to form the compound represented by the general formula (3) and/or its complex, and easily improve the conversion rate of step (II), the yield of the compound represented by the general formula (1) finally obtained, select From the viewpoint of efficiency, etc., polar organic solvents are preferable, and polar solvents containing nitrogen are more preferable. As such a solvent, for example, amide compounds (N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N- -Diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, 1,3-dimethyl-3,4,5,6-tetrahydro pyrimidone, triamide hexamethylphosphate, etc.), amine compounds (triethylamine, 1-methylpyrrolidinium, etc.), pyridine compounds (pyridine, picoline, etc.), quinoline compounds (quinoline, methylquinoline, etc.) phylloline, etc.), etc. Among them, it is easier to form the compound represented by the general formula (3) and/or its complex through the step (I), and it is easy to improve the conversion rate of the step (II), and finally obtain the general formula (1) From the standpoint of the yield, selectivity, etc. of the compounds shown, and the ease of reducing by-products, amide compounds, pyridine compounds, etc. are preferred, amide compounds are more preferred, and N,N-dimethylformyl Amine, N,N-diethylformamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, 1, 3-Dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethyl triamide phosphate, etc. are even better, N,N-dimethylformamide, N,N-diethyl Formamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, etc. are particularly preferred, and N,N-dimethylformamide, N-methyl-2-pyrrolidone, etc. And even better.

As these solvents, known or commercially available ones can be used. In addition, these solvents may be used alone or in combination of two or more.

The amount of solvent used is not particularly limited if it is the amount of solvent, and it can be set as an excess amount. It is easier to form the compound represented by the general formula (3) or its complex by step (I), and it is easy to improve the step. (II) conversion rate, the yield and selectivity of the compound represented by the general formula (1) finally obtained, and from the viewpoint of easily reducing by-products, compared with the compound represented by the general formula (4), 100 parts by mass is preferably 80 to 10000 parts by mass, more preferably 100 to 1000 parts by mass, and still more preferably 150 to 800 parts by mass.

(1-1-4) Ligand compounds The reaction of the step (I) of the present invention can also be further carried out in the presence of a coordination compound. In particular, it is preferable to use a substance that can enhance the activity of the compound represented by the general formula (3) and/or its complex, that is, a coordination compound that can coordinate to copper.

In the reaction of step (I) of the present invention, as the coordination compound that can be used, for example, can enumerate the coordination compound that coordination atom is nitrogen atom, phosphorus atom, oxygen atom, sulfur atom etc., these coordination A dentate compound is a monodentate ligand having only one coordination atom at one site, and a multidentate complex having two or more sites.

Examples of monodentate ligands include triphenylphosphine, trimethoxyphosphine, triethylphosphine, triisopropylphosphine, tri(tert-butyl)phosphine, tri(n-butyl)phosphine , triisopropoxyphosphine, tricyclopentylphosphine, tricyclohexylphosphine, bis(tert-butyl)methylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, triethylamine, pyridine, etc. .

Examples of multidentate ligands include 2,2'-bipyridine, 4,4'-(tert-butyl)bipyridine, 4,4'-bis(trifluoromethyl)-2,2 '-bipyridine, 5,5'-bis(trifluoromethyl)-2,2'-bipyridine, 6,6'-bis(trifluoromethyl)-2,2'-bipyridine, 4,4 '-bis(methoxycarbonyl)-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine Pyridine, 4,4'-dimethoxy-2,2'-bipyridine, 4,4'-dicyano-2,2'-bipyridine, morpholine, 2,2'-bipyrimidine, 1, 4-diazabicyclo[2.2.2]octane, 2-(dimethylamino)ethanol, tetramethylethylenediamine, N,N-dimethylethylenediamine, N,N'-dimethyl Ethylenediamine, 2-aminomethylpyridine, 1,1'-bis(diphenylphosphino)ferrocene, diphenylphosphinomethane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,5-bis(diphenylphosphino)pentane, 1,2-bis(dicyclohexylphosphino)ethane, 1,3-(bis Cyclohexylphosphino)propane, 1,2-bis(di-tert-butylphosphino)ethane, 1,3-bis(di-tert-butylphosphino)propane, 1,2-bis(diphenyl phosphino)benzene, 1,5-cyclooctadiene, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), 2,2'-dimethyl-6 ,6'-bis(diphenylphosphino)biphenyl (BIPHEMP), 1,2-bis(diphenylphosphino)propane (PROPHOS), 2,3-O-isopropylidene-2,3- Dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP), 3,4-bis(diphenylphosphino)-1-benzylpyrrolidine (DEGUPHOS), 1,2-bis[ (2-methoxyphenyl)phenylphosphino]ethane (DIPAMP), substituted-1,2-bisphosphoranebenzene (DuPHOS), 5,6-bis(diphenylphosphino)-2-nor Camphene (NORPHOS), N,N'-bis(diphenylphosphino)-N,N'-bis(1-phenylethyl)ethylenediamine (PNNP), 2,4-bis(diphenyl Phosphino)pentane (SKEWPHOS), 1-[1',2-bis(diphenylphosphino)ferrocene]ethylenediamine (BPPFA), 2,2'-bis(dicyclohexylphosphino)- 5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl, ((4,4'-bis-1,3-benzodioxol) -5,5'-diyl)bis(diphenylphosphino)(SEGPHOS), 2,3-bis(diphenylphosphino)butane (CHIRAPHOS), 1-[2-(2-substituted phosphino)bis Ferrocene]ethyl-2 substituted phosphines (JOSIPHOS) and the like, and mixtures thereof. As the above-mentioned BINAP, derivatives of BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) are also included, and as the above-mentioned BIPHEMP, BIPHEMP (2,2'-dimethyl -6,6'-bis(diphenylphosphino)biphenyl) derivatives. Among the above-mentioned coordination compounds, it is easier to form the compound represented by the general formula (3) and/or its complex through the step (I), and it is easier to improve the conversion rate of the step (II), and the final obtained From the standpoint of the yield and selectivity of the compound represented by the general formula (1), and the ease of reducing by-products, the multidentate ligand system is better, 2,2'-bipyridine, 4,4' -(tert-butyl)bipyridine, 4,4'-bis(trifluoromethyl)-2,2'-bipyridine, 5,5'-bis(trifluoromethyl)-2,2'-bipyridine Pyridine, 6,6'-bis(trifluoromethyl)-2,2'-bipyridine, 4,4'-bis(methoxycarbonyl)-2,2'-bipyridine, 4,4'-bis Methyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, 4,4' -Dicyano-2,2'-bipyridine, phenanthroline, etc. are more preferred, 2,2'-bipyridine, 4,4'-bis(trifluoromethyl)-2,2'-bipyridine, 5 ,5'-bis(trifluoromethyl)-2,2'-bipyridine, 4,4'-bis(methoxycarbonyl)-2,2'-bipyridine, 4,4'-dimethyl- 2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, and phenanthroline are more preferred.

In the case of using a ligand compound, the amount used is easier to form the compound represented by general formula (3) and/or its complex through step (I), and it is easier to increase the conversion rate of step (II) , The yield, selectivity, etc. of the compound represented by the general formula (1) finally obtained, and from the viewpoint of easily reducing by-products, are usually 0.2 to 5.0 mol with respect to 1 mol of the inorganic material containing copper The otic system is better, the 0.3-3.0 mol system is more preferable, and the 0.5-2.0 mol system is even better.

(1-1-5) Reaction The step (I) in the present invention can adopt either the batch type in which the raw materials are loaded into the reactor at one time, or the continuous type in which the product is taken out from the reactor while continuously supplying the raw materials into the reactor. one way. Since the reaction of step (I) is not so fast, it is better to adopt a batch system.

(1-1-6) Reaction temperature In step (I) in the present invention, the reaction temperature can be set to milder conditions than before, and it is easier to form the compound represented by general formula (3) and/or its complex through step (I) , and it is easy to increase the conversion rate of step (II), the yield and selectivity of the compound represented by the general formula (1) finally obtained, and it is easy to reduce by-products, usually 0 ~ 200 ° C The temperature is better, the temperature at 5-150°C is more preferable, and the temperature at 10-80°C is even better.

(1-1-7) Reaction time Reaction time (maintenance time at the highest reaching temperature), by making the reaction fully carry out, and it is easier to form the compound represented by general formula (3) and/or its complex by step (I) , and it is easy to improve the conversion rate of step (II), the yield and selectivity of the compound represented by the general formula (1) finally obtained, and it is easy to reduce the by-products, 1 minute to 48 hours is Preferably, 5 minutes to 24 hours is more preferable. Although the above-mentioned reaction time is the preferred reaction time in the case of using a batch type, the reaction time can also be adjusted appropriately in the case of a continuous type. In this case, from the viewpoint of easily reducing by-products, 1 minute to 48 hours is also preferable, and 5 minutes to 24 hours is more preferable.

(1-1-8) Reaction pressure The reaction pressure of the step (I) in the present invention is easier to form the compound represented by the general formula (3) and/or its complexes through the step (I), and it is easier to improve the conversion rate of the step (II) , the yield and selectivity of the compound represented by the general formula (1) finally obtained, and from the viewpoint of easily reducing by-products, -2 to 2 MPa is better, -1 to 1 MPa is more preferred, - 0.5-0.5MPa is more preferable. In addition, in the present invention, the case where the pressure is not specifically indicated is defined as the gauge pressure.

In the reaction of step (I) in the present invention, as a reactor for reacting the compound represented by the general formula (4) with the inorganic material containing copper, if it can withstand the above-mentioned temperature and pressure, its shape and structure The system is not particularly limited. As the reactor, for example, a vertical reactor, a horizontal reactor, a multi-tubular reactor, etc. are mentioned. As a material of a reactor, glass, stainless steel, iron, nickel, iron-nickel alloy etc. are mentioned, for example.

(1-1-9) Example of reaction Regarding the environment for performing the step (I) in the present invention, an inert gas environment is preferable from the viewpoint of suppressing deterioration of the compound represented by the general formula (4) and the inorganic material including copper.

Nitrogen, helium, argon, etc. are mentioned as this inert gas. Among these inert gases, nitrogen-based gases are preferable from the viewpoint of cost suppression.

After the reaction is finished, the compound and/or its complexes represented by the general formula (3) can be obtained according to the usual method for purification if necessary. In addition, the next step may be directly carried out without performing purification.

(1-1-10) Purpose compound Hereby, the purpose compound that generates in step (1) is general formula (3): [In the formula, R represents a ^{perfluoroalkyl} group. ] represents the compound and/or its complex.

In the step (I), when a coordination compound is used, a copper complex in which the coordination compound is coordinated to the compound represented by the general formula (3) is produced.

For example, in the case of using monodentate or bidentate ligands as ligand compounds, the general formula (7A) or (7B) is generated:

[In the formula, R is ^the same as above. R ⁷ represents the above-mentioned monodentate ligand. R ⁸ represents the above-mentioned two ligands. Dashed lines indicate coordinate bonding. ] represents the compound.

In the general formula (3), R ⁶ is as described above.

That is, the compound represented by the general formula (3) of the target compound produced in step (I) specifically includes CF ₃ Cu, CF ₃ CF ₂ Cu, CF ₃ CF ₂ CF ₂ Cu and the like.

On the other hand, in the case of using a ligand compound in step (I), the target compound, for example, can be mentioned

wait.

[1-2] Step (II) In the production method of the present invention, in step (II), the compound represented by the general formula (3) and/or its complex is reacted with the compound represented by the general formula (2) in a solvent to form a general A compound represented by formula (1).

(1-2-1) Starting compound (general formula (2)) The starting compounds that can be used in step (II) of the present invention, as above, are of general formula (2):

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different, and represent a hydrogen atom or a fluorine atom. However, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ represents a fluorine atom. X ¹ represents a bromine atom or a chlorine atom. ] represents the compound.

In the general formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms or fluorine atoms. However, from the point of view that it is easy to increase the conversion rate of step (II), the yield and selectivity of the compound represented by the general formula (1) finally obtained, and to reduce by-products, R ¹ and R ² , R ³ , R ⁴ and R ⁵ at least one is a fluorine atom. Also, for the same reason, at least two of R ¹ , R ² , R ³ , R ⁴ and R ⁵ are preferably fluorine atoms, and at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ More preferably, three of them are fluorine atoms, more preferably at least four of R ¹ , R ² , R ³ , R ⁴ and R ⁵ are fluorine atoms, R ¹ , R ² , R ³ , R ⁴ and R ⁵ It is especially preferable that all are fluorine atom systems.

In the general formula (2), ^X1 is a bromine atom or a chlorine atom, from the viewpoints of easily improving the conversion rate of the step (II), the yield of the compound represented by the general formula (1) finally obtained, selectivity, etc. See, the bromine atom system is preferred.

In addition, in the general formula (2), in the case where X is a fluorine atom, the reaction of the step (II) does not occur.

Also, in the general formula (2), when X is an iodine atom, a dimerization reaction occurs, and the general formula (6) is easily generated:

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above. ], so the yield, selectivity, etc. of the compound represented by the general formula (1) finally obtained cannot be improved, and the reaction cannot be efficiently carried out.

The compound represented by the general formula (2) as a starting compound, specifically, may include

wait.

As the compound represented by the above general formula (2), known or commercially available compounds can be used. Moreover, the compound represented by the said general formula (2) may be used individually or in combination of 2 or more types.

(1-2-2) Copper compounds and/or complexes thereof In addition, the compound represented by the general formula (3) and/or its complex used in step (II) can be obtained in the above step (I), or can be produced by different production methods. By.

Therefore, the compounds represented by the general formula (3) and/or complexes thereof that can be used can be used as described in the above (1-1-10).

In the step (II) of the present invention, the usage amount of the compound represented by the general formula (3) and/or its complex is not particularly limited, however, it is easy to improve the conversion rate of the step (II), and the final result From the viewpoints of the yield and selectivity of the compound represented by the general formula (1) obtained, relative to 1 mole of the compound represented by the general formula (2), it is preferably 0.05 to 5.0 moles, and 0.1 to 5.0 moles. 3.0 molar is better, and 0.2 to 2.0 molar is even better.

In addition, in the case of performing step (II) without isolating the compound represented by the general formula (3) and/or its complex after the above-mentioned step (I), based on the same reason as above, compared with the general 1 mole of the compound represented by formula (2) is to use 0.05 to 5.0 moles of the compound represented by general formula (4), preferably to use 0.1 to 3.0 moles, more preferably to use 0.2 to 2.0 moles, and 0.05-5.0 moles of inorganic materials containing copper are used, preferably 0.1-3.0 moles are used, more preferably 0.2-2.0 moles are used.

(1-2-3) Reaction In the reaction of the step (II) of the present invention, in the case of using the compound represented by the general formula (3), the compound represented by the above general formula (2), the general formula (3) obtained by the step (I) ) represented by the compound follows the following reaction formula:

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and X are the same as above. ], it is better to obtain the compound represented by the general formula (1).

(1-2-4)Solvent As the solvent that can be used in the step (II), it is not particularly limited, however, especially, the compound represented by the general formula (2), the compound represented by the general formula (3) and/or its complex From the viewpoint of dissolution, polar organic solvents are preferred. Also, from the viewpoints of improving the conversion rate of the step (II), the yield of the compound represented by the general formula (1) finally obtained, the selectivity, etc., a polar solvent containing nitrogen is more preferable. As such a solvent, for example, amide compounds (N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N- -Diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, 1,3-dimethyl-3,4,5,6-tetrahydro pyrimidone, triamide hexamethylphosphate, etc.), amine compounds (triethylamine, 1-methylpyrrolidinium, etc.), pyridine compounds (pyridine, picoline, etc.), quinoline compounds (quinoline, methylquinoline, etc.) phylloline, etc.), etc. Among them, amide compounds, pyridine Compounds are better, amide compounds are better, N,N-dimethylformamide, N,N-diethylformamide, N,N-diisopropylformamide, N-formamide Base-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, 1,3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric triamide, etc. More preferably, N,N-dimethylformamide, N,N-diethylformamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, etc. , N,N-dimethylformamide, N-methyl-2-pyrrolidone and the like are even more preferred.

As these solvents, known or commercially available ones can be used. In addition, these solvents may be used alone or in combination of two or more.

In addition, as these solvents, the same solvent as that in the step (I) may be used as it is, or a solvent other than the solvent in the step (I) or different therefrom may be used.

The amount of solvent used is not particularly limited if it is the amount of solvent, and it can be set as an excess amount. It is easy to improve the conversion rate of step (II) and the yield and selectivity of the compound represented by the general formula (1) obtained at last. etc., and from the viewpoint of easily reducing by-products, relative to 100 parts by mass of the compound represented by the general formula (2), 100 to 10,000 parts by mass is preferable, 200 to 1,000 parts by mass is more preferable, and 300 to 800 parts by mass is more preferable. The quality portion is even better.

(1-2-5) reaction Step (II) in the present invention can adopt either a batch method in which raw materials are charged into the reactor at one time, or a continuous method in which the product is taken out from the reactor while continuously feeding the raw materials into the reactor. one way. Since the reaction of step (II) is not so fast, it is better to adopt a batch system.

(1-2-6) Reaction temperature In the step (II) among the present invention, the reaction temperature can be set as the milder condition than before, by easily improving the conversion rate of step (II), the productive rate of the compound represented by the general formula (1) finally obtained, From the viewpoint of selectivity, etc., and ease of reducing by-products, usually 0 to 200°C is preferred, 5 to 150°C is more preferred, and 10 to 80°C is still more preferred.

(1-2-7) Reaction time Reaction time (maintenance time at the highest reaching temperature) is to make the reaction fully carry out, and it is easy to improve the conversion rate of step (II) and the yield of the compound represented by the general formula (1) finally obtained , selectivity, etc., and from the viewpoint of easily reducing by-products, 1 minute to 48 hours is preferable, and 5 minutes to 24 hours is more preferable. Although the above-mentioned reaction time is the preferred reaction time in the case of using a batch type, the reaction time can also be adjusted appropriately in the case of a continuous type. In this case, from the viewpoint of easily reducing by-products, 1 minute to 48 hours is also preferable, and 5 minutes to 24 hours is more preferable.

(1-2-8) Reaction pressure The reaction pressure of step (II) in the present invention is easy to increase the conversion rate of step (II), the yield and selectivity of the compound represented by the general formula (1) finally obtained, and it is easy to reduce by-products From this point of view, -2 to 2 MPa is more preferable, -1 to 1 MPa is more preferable, and -0.5 to 0.5 MPa is even more preferable. In addition, in the present invention, the case where the pressure is not specifically indicated is defined as the gauge pressure.

In the reaction of step (II) in the present invention, as the reactor that makes the compound represented by general formula (2) react with the compound represented by general formula (3) and/or its complex compound, if it can tolerate The shape and structure of the above-mentioned temperature and pressure are not particularly limited. As the reactor, for example, a vertical reactor, a horizontal reactor, a multi-tubular reactor, etc. are mentioned. As a material of a reactor, glass, stainless steel, iron, nickel, iron-nickel alloy etc. are mentioned, for example. In addition, step (II) in the present invention may use the reactor used in the above-mentioned step (I), and may also use another reactor different from the reactor used in the above-mentioned step (I).

(1-2-9) Example of reaction Step (II) in the present invention can be carried out after step (I), and can also be carried out separately from step (I).

Regarding the environment in which step (II) in the present invention is carried out, from the viewpoint of suppressing the deterioration of the compound represented by the general formula (2) and the compound represented by the general formula (3) and/or its complexes, in It is preferred under an inert gas environment.

Examples of the inert gas include nitrogen, helium, argon and the like. Among these inert gases, nitrogen-based gases are preferable from the viewpoint of cost suppression.

After the reaction, if necessary, it can also be purified according to the usual method to obtain the target compound represented by the general formula (1).

(1-2-10) Target compound Thus, the target compound generated in step (II) is the general formula (1):

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as above. ] The compound represented by the compound represented.

In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as described above.

That is, the compound represented by the general formula (1) of the target compound generated in step (II), specifically, can include

wait.

The compound represented by the general formula (1) obtained in this way can be effectively used as etching gas, cleaning gas, synthetic intermediate (constructive element for organic synthesis) for forming the most advanced microstructure of semiconductors, liquid crystals, etc. , For example, for the introduction of structural components of polyfluorophenyl, etc.) in various applications. The building blocks for organic synthesis are as described later.

2. Composition Carrying out in the same way as above, although the compound represented by general formula (1) can be obtained, there are also compounds represented by general formula (1) and general formula (5):

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above. ] represented by the compound, and/or the general formula (6):

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above. ] The case where the indicated compound is obtained in the form of a composition.

In general formula (5), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above. As above, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a fluorine atom. Also, as above, at least two of R ¹ , R ² , R ³ , R ⁴ and R ⁵ are preferably fluorine atoms, and at least three of R ¹ , R ² , R ³ , R ⁴ and R ⁵ It is more preferably a fluorine atom system, at least four of R ¹ , R ² , R ³ , R ⁴ and R ⁵ are a fluorine atom system, and even more preferably, all of R ¹ , R ² , R ³ , R ⁴ and R ⁵ are It is particularly preferably a fluorine atom system.

That is, the compound represented by the general formula (5), specifically, can include

wait.

In this case, in the composition of the present invention, by adding a small amount of the compound represented by the general formula (5), the etching rate of the amorphous carbon layer (ACL) and the etching rate of the silicon oxide film (SiO ₂ ) can be reduced. The speed ratio (SiO ₂ /ACL) becomes larger and enables the silicon oxide film (SiO ₂ ) to be selectively etched more easily than the amorphous carbon layer (ACL).

Therefore, when the total amount of the composition of the present invention is set as 100 mol%, the content of the compound represented by the general formula (1) is 10.0-99.9 mol%, and can also be set as 20.0-99.9 mol%, 30.0 ～99.9 mol%, 40.0～99.9 mol%, 50.0～99.8 mol%, 60.0～99.7 mol%, 70.0～99.6 mol%, 80.0～99.4 mol%, etc.

Also, the composition of the present invention, as described above, may also contain a compound represented by general formula (5) in which a halogen atom (chlorine atom or bromine atom) is removed from the compound represented by general formula (2) of the starting material . Although the compound represented by this general formula (5) is also useful as an etching gas, cleaning gas, synthesis intermediate, etc., in order to make amorphous carbon The ratio (SiO ₂ /ACL) of the etching rate of the silicon oxide film (ACL) to the etching rate of the silicon oxide film (SiO ₂ ) becomes larger and makes the silicon oxide film (SiO ₂ ) easier to select than the amorphous carbon layer (ACL) For etching, the content of the compound represented by the general formula (5) is preferably in a small amount.

Therefore, when the total amount of the composition of the present invention is set as 100 mol%, the content of the compound represented by the general formula (5) is preferably 0.1-90.0 mol%, and can also be set as 0.1-80.0 mol% %, 0.1～70.0 mol%, 0.1～60.0 mol%, 0.2～50.0 mol%, 0.3～40.0 mol%, 0.4～30.0 mol%, 0.6～20.0 mol%, 0.7～10.0 mol% , 0.8-5.0 mole%, etc.

In the general formula (6), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above.

That is, the compound represented by the general formula (6), specifically, can include

wait.

The content of the compound represented by the general formula (6) is preferably 70.0 mol% or less when the total amount of the composition of the present invention is 100 mol%, more preferably 40.0 mol% or less, Below 10.0 mol% is especially preferred. In addition, the content of the compound represented by the general formula (6) may be 0.1% or more when the total amount of the composition of the present invention is 100 mol%.

Also, the total content of the compound represented by the above-mentioned general formula (5) and the compound represented by the general formula (6) is obtained from the ratio of the etching rate of the amorphous carbon layer (ACL) to the etching rate of the silicon oxide film (SiO ₂ ). From the viewpoint of (SiO ₂ /ACL), etc., when the total amount of the composition of the present invention is 100 mol%, it is 0.1 to 90.0 mol%, and may be 0.1 to 80.0 mol%, or 0.1 ～70.0 mol%, 0.1～60.0 mol%, 0.2～50.0 mol%, 0.3～40.0 mol%, 0.4～30.0 mol%, 0.6～20.0 mol%, etc.

Such a composition of the present invention can be effectively used for etching gas, cleaning gas, and synthetic intermediates (constructive components for organic synthesis, such as for introducing polyfluorine In various uses such as the structural member of the phenyl group) and the like). It can be effectively used in various applications such as building blocks for organic synthesis and cleaning gases. In addition, the term "building block for organic synthesis" refers to a substance that can be a precursor of a compound having a highly reactive skeleton. For example, if the composition of the present invention is reacted with a fluorine-containing organosilicon compound such as CF ₃ Si(CH ₃ ) ₃ , a perfluoroalkyl group such as a CF ₃ group is introduced, and it can be converted into a detergent or a Substances of fluorine-containing pharmaceutical intermediates.

The above is the description of the embodiment of the present invention, but various changes can be made in the form or details without departing from the spirit and scope of the claims. [Example]

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

In addition, in this example, unless otherwise specified, the reaction was carried out at room temperature (25° C.).

Examples 1-5 Add 10 g of solvent (pyridine, N-methyl-2-pyrrolidone (NMP) or N,N-dimethylformamide (DMF)) and 0.71 g (11 mmol) of copper powder to the autoclave, And put the lid on. CF ₃ I (2.2 g, 11 mmol) was added thereto, and stirred for 1 hour.

Afterwards, the reaction solution was analyzed by ¹⁹ F-NMR, and a peak was confirmed at -26 ppm. Compared with FNMR_UWLU098378 (Spectral Data were obtained from John Wiley & Sons, Inc.), it was confirmed that CF ₃ Cu was produced.

Thereafter, pentafluorobromobenzene (2.5 g, 10 mmol) was added to the autoclave, and stirred at the temperature shown in Table 1 for 12 hours to allow the reaction to proceed.

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

The results of mass analysis and structural analysis can confirm the generation

as an object.

Example 6 The reaction was carried out in the same manner as in Example 1, except that phenanthroline (11 mmol) was added. Specifically, the reaction was carried out as follows.

10 g of pyridine, 0.71 g (11 mmol) of copper powder, and phenanthroline (11 mmol) were added to the autoclave, and the lid was closed. CF ₃ I (2.2 g, 11 mmol) was added thereto, and stirred for 1 hour. By the same method as in Examples 1 to 5, it was confirmed that the following compounds were produced in the system.

Thereafter, pentafluorobromobenzene (2.5 g, 10 mmol) was added to the autoclave, and stirred at the temperature shown in Table 1 for 12 hours to allow the reaction to proceed.

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

Comparative Example 1 10 g of a solvent (pyridine), 0.71 g (11 mmol) of copper powder, and pentafluorobromobenzene (2.5 g, 10 mmol) were added to an autoclave, and the lid was closed. CF ₃ I (2.5 g, 13.2 mmol) was added thereto, and stirred at 50° C. for 12 hours to allow the reaction to proceed.

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

Based on the results of mass analysis and structural analysis, confirm its composition.

The results are shown in Table 1.

In addition, in Table 1, C ₇ F ₈ , C ₆ F ₅ H and C ₁₂ F ₁₀ mean the following compounds.

express .

Example 7 The mixture obtained in Example 1 was refined by a conventional method to obtain a composition comprising 99 mol% of C ₇ F ₈ (perfluorotoluene) and 1 mol% of C ₆ F ₅ H (pentafluorobenzene) thing. It was measured under the etching conditions of ICP (Inductive Coupled Plasma), discharge power of 1000W, bias power of 300W, pressure of 10mTorr, electron density of 8×10 ¹⁰ to 2×10 ¹¹ cm ^-3 , and electron temperature of 5 to 7eV. The etching rate of a silicon oxide (SiO ₂ ) film with a thickness of 1000 μm on a silicon substrate and an amorphous carbon film (ACL) with a thickness of 5000 μm formed on a silicon substrate is the ratio of the etching rate of the SiO2 film to the ACL at that time (SiO ₂ Etching rate of film/etching rate of ACL) was regarded as the selectivity ratio to ACL. In addition, the SiO ₂ film was formed according to a conventional method, and the ACL was formed based on the reported contents (Producer (registered trademark) APFTM PECVD - Applied Materials). As a result, the selectivity ratio (etching rate of _SiO2 film/etching rate of ACL) to ACL was 3.2.

Claims (12)

A kind of manufacturing method, it is general formula (1): [In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different, and represent a hydrogen atom or a fluorine atom; however, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ 1 represents a fluorine atom; ^R represents a method for producing a compound represented by a perfluoroalkyl group], wherein, having (II) in a solvent, the general formula (3): [wherein, R ⁶ represents a perfluoroalkyl group] The compound and/or its complex represented by the general formula (2): [wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above; X ¹ represents a bromine atom or a chlorine atom] reacting the compound represented by the aforementioned general formula (1) Step (II) of generation. The production method as described in claim 1, wherein, before the aforementioned step (II), (I) is provided in the solvent, so that the general formula (4): [wherein, R ⁶ is the same as above; X ² represents a bromine atom or an iodine atom] The compound represented by it reacts with an inorganic material containing copper to make the compound represented by the aforementioned general formula (3) and/or its aluminum Step (I) of compound generation. The production method as described in claim 1 or 2, wherein the carbon number of the aforementioned R ⁶ is 1-5. The production method described in any one of Claims 1 to 3, wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are all fluorine atoms. The production method according to any one of claims 1 to 4, wherein the inorganic material containing copper is copper. The production method according to any one of claims 1 to 5, wherein the solvent is an organic compound containing nitrogen. The production method described in any one of Claims 2 to 6, which further adds a coordination compound in the aforementioned step (I). According to the production method described in Claim 7, the aforementioned coordination compound is a coordination compound in which the coordination atom is a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom. The production method described in any one of claims 1 to 8, wherein the reaction temperature in the aforementioned step (II) is 0 to 200°C. A composition comprising the general formula (1): [In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different, and represent a hydrogen atom or a fluorine atom; however, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ 1 represents a fluorine atom; R ⁶ represents a perfluoroalkyl] compound represented by the general formula (5): [wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above] the compound represented, and/or the general formula (6): [wherein, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same as the above-mentioned compounds], and when the total amount of the composition is set to 100 mol%, the aforementioned general formula (1 ) The content of the compound represented by ) is 10.0-99.9 mol%. The composition as described in Claim 10, wherein the total content of the compound represented by the aforementioned general formula (5) and the compound represented by the aforementioned general formula (6) is equal to 100 mol% of the total amount of the composition 0.01 to 90.0 mole %. The composition as described in claim 10 or 11 is used as cleaning gas, etching gas, or synthesis intermediate.