Charge-transporting thin film-forming composition containing fluorine-containing aniline derivative

Abstract

To provide a fluorinated aniline derivative that is suitable for use as a material for forming charge-transporting thin films for electronic components such as organic EL elements.SOLUTION: For example, fluorinated aniline derivatives are represented by the following formulae (H1) and (H2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a fluorine-containing aniline derivative. [Background technology]

[0002] Palladium-catalyzed cross-coupling of amines with halides or pseudohalides to form C-N bonds is useful for the synthesis of aromatic amines and the formation of heterocycles. This cross-coupling has become an important technique in many fields, including pharmaceuticals and materials (Non-Patent Document 1), and extensive research has been conducted on the catalysts used in this reaction and the reaction process.

[0003] On the other hand, fluorine has the highest electronegativity of all elements, so its introduction into a molecule can significantly change the electronic state of the entire molecule. In addition, its atomic radius is similar to that of a hydrogen atom, so even if a fluorine atom is introduced into a molecule instead of a hydrogen atom, the change in molecular size can be suppressed compared to when other atoms or substituents are introduced. For this reason, research on fluorides has been actively conducted, and many reports have been published on fluorides for use in medicines and electronic materials. For example, in the field of electronic materials, it has been reported that amine compounds having fluorine atoms in the molecule are suitable as charge transport materials (Patent Document 1).

[0004] Under these circumstances, methods for synthesizing fluoroaryl compounds having an amino group have been reported, such as the reaction of an aromatic amine with a perfluoroarylboronic acid using copper acetate as a catalyst (Non-Patent Document 2), the reaction of formanilide with perfluorobenzene in the presence of lithium hydroxide (Non-Patent Document 3), and the reaction of aniline with perfluorobenzene in the presence of t-BuONa (Non-Patent Document 4). However, in all of these reactions, the amino group, which is the reactive site, is present in the aromatic compound that does not have a fluorine atom, of the two raw materials used in the coupling reaction.

[0005] There have been few reports of a coupling reaction between a fluoroarylamine compound having a fluorine atom and an amino group and a haloaryl compound. For example, Non-Patent Document 5 reports a method of coupling a fluoroarylamine compound and a haloaryl compound using a special palladium carbene complex as a catalyst. However, this method has problems such as the high cost of the catalyst and a low yield of the target product. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2008 / 032617 [Non-patent literature]

[0007] [Non-Patent Document 1] Chem. Rev. 2016, 116, 12564-12649 [Non-patent document 2] Angew. Chem. Int. Ed. 2014, 53, 3223 [Non-patent document 3] Journal of Fluorine Chemistry, 74(2), 177-9; 1995 [Non-patent document 4] RSC Advances, 5(10), 7035-7048; 2015 [Non-Patent Document 5] Angew. Chem. Int. Ed. 2014, 53, 3223 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluorine-containing aniline derivative suitable as a material for forming a charge transporting thin film for electronic devices such as organic EL devices. [Means for solving the problem]

[0009] As a result of extensive research to achieve the above object, the present inventors have found that a coupling reaction between an amino group of a fluorinated aromatic amine compound and a chlorine atom, bromine atom, iodine atom, or pseudohalogen group of a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon proceeds efficiently in the presence of a specific palladium catalyst, a specific ligand, and a base, and that a secondary amine compound having a fluoroaryl moiety in the molecule can be selectively obtained in good yield, thereby completing the present invention.

[0010] That is, the present invention provides: 1. A fluorine-containing aniline derivative represented by formula (T1) (excluding the compounds represented by the following formulas [1] and [2]), [ka] [In the formula, X 211 is a divalent group represented by the following formula (A02-1): [ka] (In the formula, a 21 and a 23 represent the number of fluorine atoms substituted on the aromatic ring, and each independently represents an integer of 1 to 4, a 22 and a 24 is the Z substituted on the aromatic ring. 02 , which are all 0.) Y 211 and Y 212 are the same and represent a monovalent group represented by any one of formulas (B01) to (B21). [ka] [ka] [ka] (In the formula, L 11is -S-, -O-, -CO-, -CH2-, -(CH2)2-, -C(CH3)2-, -CF2-, -(CF2)2-, -C(CF3)2-, a fluorene-9,9-diyl group, -NH- or -NZ 100 - represents L 12 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, L 13 and L 14 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, Z 100 represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, Z 101 ~Z 107 and Z 109 ~Z 121 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, Z 108 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, provided that Z present on different benzene rings 108 may be bonded to each other to form a ring, Ar 1 each independently represents an aryl group having 6 to 20 carbon atoms, Ar 2 represents a single bond or an arylene group having 6 to 20 carbon atoms. [ka] 2. The above a 21 and a 23 is an integer of 2 to 4, 3. The above a 21 and a 23 is an integer of 3 to 4, 4. The above X 211is a divalent group represented by the following formula (A02-1-1): [ka] 5. The above Y 211 and Y 212 and (B08) and (B18) are each a monovalent group represented by any one of the formulae (B01), (B02), (B04), (B08) and (B18), 6. A fluorine-containing aniline derivative of formula 1 represented by any one of the following formulas: [ka] (In the formula, t-Bu represents a t-butyl group.) 7. A fluorine-containing aniline derivative of formula 1 represented by any one of the following formulas: [ka] 8. A charge transporting substance comprising any one of the aniline derivatives 1 to 7. 9. A composition for forming a charge-transporting thin film, comprising the charge-transporting substance of 8 and an organic solvent. 10. The charge transport thin film forming composition according to 9, which contains a dopant substance. 11. A charge transporting thin film obtained from the charge transporting thin film forming composition according to 9 or 10. 12. An electronic device comprising the charge transport thin film of 11. 13. An organic electroluminescence device comprising the charge transport thin film of 11. 14. The organic electroluminescence device of 13, wherein the charge transporting thin film is a hole injection layer or a hole transport layer. to provide. [Effects of the Invention]

[0011] According to the method for producing a fluorinated aromatic secondary amine compound of the present invention, a secondary amine compound having a fluoroaryl moiety in the molecule (a fluorinated aniline derivative) can be produced efficiently, in high yield, and inexpensively from a fluorinated aromatic amine compound and a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon using a commercially available palladium catalyst and a ligand having a biphenyl skeleton. Furthermore, in this reaction, the polymerization reaction proceeds by using a bifunctional compound, either a fluorinated aromatic amine compound or a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudo-halogenated aromatic hydrocarbon, and polymers such as oligoaniline derivatives or polyaniline derivatives having a fluoroaryl moiety in the molecule can be efficiently produced. The fluorine-containing amine compounds such as fluorine-containing aniline derivatives and polymers obtained by the production method of the present invention have excellent transparency due to the presence of fluorine atoms in the molecule and also exhibit charge transport properties, and therefore can be suitably used alone or in combination with other charge transport materials or dopant substances as materials for forming charge transport thin films for electronic devices such as organic EL devices. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in more detail below. [1] Method for producing fluorinated aromatic secondary amine compounds The method for producing a fluorinated aromatic secondary amine compound according to the present invention comprises a step of reacting a fluorinated aromatic primary amine compound with a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon in the presence of a catalyst, a ligand, and a base.

[0013] (1) Catalyst The catalyst used in the present invention contains a zero-valent palladium complex of dibenzylideneacetone. Specific examples of the zero-valent palladium complex of dibenzylideneacetone include bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), and tris(dibenzylideneacetone)(chloroform)dipalladium(0). Among these, bis(dibenzylideneacetone)palladium(0) is preferred. The amount of the dibenzylideneacetone palladium zero-valent complex used is not particularly limited as long as it is an amount that allows the target coupling reaction to proceed, but the amount is preferably 0.0001 to 0.2 mol, more preferably 0.005 to 0.15 mol, still more preferably 0.01 to 0.12 mol, and even more preferably 0.02 to 0.1 mol, of palladium metal relative to 1 mol of NH at the amine site of the fluorinated aromatic primary amine compound.

[0014] In the present invention, other metal catalysts may be used together with the dibenzylideneacetone palladium zero-valent complex, as long as the effects of the present invention are not impaired. Other metal catalysts include, for example, copper catalysts such as copper chloride, copper bromide, and copper iodide; and palladium catalysts such as Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium), Pd(PPh3)2Cl2 (bis(triphenylphosphine)dichloropalladium), Pd(Pt-Bu3)2 (bis(tri(t-butylphosphine))palladium), and Pd(OAc)2 (palladium acetate). When these other metal catalysts are used, the amount used cannot be generally defined, but is usually less than 100 mol % based on the palladium zero-valent complex of dibenzylideneacetone.

[0015] (2)Ligand The ligand used in the present invention includes a biphenylphosphine compound represented by the following formula (L).

[0016] [ka]

[0017] In formula (L), R 1each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 2 ~R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms; R 6 ~R 8 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or NR 9 Represents two groups, R 9 each independently represents an alkyl group having 1 to 20 carbon atoms.

[0018] The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, and icosyl groups; and cyclic alkyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, and adamantyl groups.

[0019] Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl groups. Specific examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, and n-decyloxy groups.

[0020] Among these, from the viewpoint of obtaining the target substance with good reproducibility, R 1 are each independently preferably a relatively bulky group, and are preferably a branched alkyl group having 3 to 20 carbon atoms in which the carbon atom on which the bond is located is a secondary carbon atom or a tertiary carbon atom, a cyclic alkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. From the viewpoint of solubility in a solvent and stability, a branched alkyl group having 3 to 5 carbon atoms or a cyclic alkyl group having 5 to 7 carbon atoms is more preferred, and a t-butyl group or a cyclohexyl group is even more preferred. In addition, two R 1 are preferably the same from the viewpoint of ease of synthesis.

[0021] In addition, from the viewpoint of compound stability and reproducibility of obtaining the target product, R 2 ~R 5 are each independently preferably a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, and R 2 and R 5 are each independently a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, R 3 and R 4 However, the combination of hydrogen atoms is more preferable, and R 2 ~R 5 However, all hydrogen atoms are more preferred.

[0022] Furthermore, from the viewpoint of compound stability and reproducibility of obtaining the target product, R 6 ~R 8 is preferably a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms in which the carbon atom on which the bond is located is a primary or secondary carbon atom, or an alkoxy group having 1 to 20 carbon atoms; and from the viewpoint of solubility in a solvent and stability, a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms is more preferred, and a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a methoxy group, or an isopropoxy group is even more preferred.

[0023] In particular, R 6 and R 8is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and more preferably a hydrogen atom, a methyl group, an isopropyl group, a methoxy group, or an isopropoxy group. R 7 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an isopropyl group.

[0024] Ligands that can be suitably used in the present invention include, but are not limited to, those represented by the following formulas (L1) to (L7).

[0025] [ka] (In the formula, Me represents a methyl group, i-Pr represents an isopropyl group, t-Bu represents a t-butyl group, and Cy represents a cyclohexyl group.)

[0026] The ligand represented by the formula (L) above is commercially available, and examples thereof include JohnPhos, CyjohnPhos, DavePhos, XPhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, tBuDavePhos, PhDavePhos, 2'-Dicyclohexylphosphino-2,4,6-trimethoxybiphenyl, BrettPhos, tBuBrettPhos, AdBrettPhos, Me3(OMe)tBuXPhos, (2-Biphenyl)di-1-adamantylphosphine, RockPhos, and CPhos, which are commercially available from Aldrich as Buchwald ligands, etc. The ligand represented by the above formula (L) can also be synthesized by a known method.

[0027] The amount of the ligand represented by formula (L) used is preferably 1 to 2 equivalents relative to the catalyst used. In particular, if it is less than 1 equivalent, palladium black may be produced.

[0028] In the present invention, other ligands may be used together with the ligand represented by formula (L) as long as the effects of the present invention are not impaired. Specific examples of other ligands include tertiary phosphines such as triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine, di-t-butyl(phenyl)phosphine, di-t-butyl(4-dimethylaminophenyl)phosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, and 1,1′-bis(diphenylphosphino)ferrocene; and tertiary phosphites such as trimethyl phosphite, triethyl phosphite, and triphenyl phosphite. When other ligands are used, the amount used cannot be generally defined, but is usually less than 100 mol % relative to the ligand represented by formula (L).

[0029] (3) Fluorinated aromatic primary amine compounds Since the production method of the present invention is characterized by the above-mentioned catalyst and ligand, there are no particular limitations on the fluorinated aromatic primary amine compound that is the raw material used in the coupling reaction. The fluorinated aromatic primary amine compound may be a monoamine compound or a diamine compound, and examples thereof include those represented by the following formulae (X1) and (X2).

[0030] [ka] (In the formula, Ar F1 represents a fluoroaryl group, and Ar F2 represents a fluorinated arylene group.

[0031] The fluoroaryl group may be an aryl group in which at least one hydrogen atom has been substituted with a fluorine atom, but it is preferable that two or more hydrogen atoms have been substituted with fluorine atoms. The fluorinated arylene group may be an arylene group in which at least one hydrogen atom has been substituted with a fluorine atom, but it is preferable that two or more hydrogen atoms have been substituted with fluorine atoms. That is, the fluorinated aromatic primary amine compound used in the present invention is preferably a fluorinated aromatic primary monoamine compound or diamine compound having two or more fluorine atoms in the molecule.

[0032] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group; 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl, 5-naphthacenyl, 2-chrysenyl, 1-pyrenyl, 2-pyrenyl, pentacenyl, benzopyrenyl, triphenylene, and the like. Examples include groups derived by removing one hydrogen atom on the aromatic ring of a fused-ring aromatic hydrocarbon compound, such as a phenylenyl group; and groups derived by removing one hydrogen atom on the aromatic ring of a ring-linked hydrocarbon compound, such as biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, para-terphenyl-4-yl, meta-terphenyl-4-yl, ortho-terphenyl-4-yl, 1,1'-binaphthyl-2-yl, and 2,2'-binaphthyl-1-yl groups. The arylene group is preferably an arylene group having 6 to 20 carbon atoms, and specific examples thereof include 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene groups; 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6-anthracenediyl, 1,7-anthracenediyl, and 1,8-anthracenediyl. Examples of the aryl group include groups derived by removing two hydrogen atoms from an aromatic ring of a fused-ring aromatic hydrocarbon compound, such as anthracenediyl, 2,3-anthracenediyl, 2,6-anthracenediyl, 2,7-anthracenediyl, 2,9-anthracenediyl, 2,10-anthracenediyl, and 9,10-anthracenediyl groups; and groups derived by removing two hydrogen atoms from an aromatic ring of a ring-linked hydrocarbon compound, such as a biphenyl-4,4'-diyl group and a para-terphenyl-4,4"-diyl group.

[0033] (4) Chlorinated, brominated, or iodinated aromatic hydrocarbons or pseudohalogenated aromatic hydrocarbons The chlorinated, brominated, or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon may be a compound having one reactive site that reacts with the amino group of a fluorinated aromatic primary amine, such as a monochloro, monobromo, or monoiodine, or monopseudohalogen compound, or a compound having two or more reactive sites that react with the amino group of a fluorinated aromatic primary amine, such as a dichloro, dibromo, or diiodine, or dipseudohalogen compound, and examples thereof include those represented by the following formulae (Y1) and (Y2).

[0034] [ka] (In the formula, Ar 4 represents an aryl group, and Ar 5 represents an arylene group, and each X independently represents a chlorine atom, a bromine atom, an iodine atom, or a pseudohalogen group.

[0035] The aryl group and arylene group include the same as those described above. Examples of the pseudohalogen group include (fluoro)alkylsulfonyloxy groups such as a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a nonafluorobutanesulfonyloxy group; and aromatic sulfonyloxy groups such as a benzenesulfonyloxy group and a toluenesulfonyloxy group. From the viewpoint of reactivity, X is preferably a bromine atom or an iodine atom.

[0036] In particular, the chlorinated, brominated or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon used in the present invention is preferably a mono- or dichloroaromatic hydrocarbon, a mono- or dibromoaromatic hydrocarbon, or a mono- or diiodoaromatic hydrocarbon, and more preferably a mono- or dibromoaromatic hydrocarbon or a mono- or diiodoaromatic hydrocarbon.

[0037] (5) Bases The base is not particularly limited, and examples thereof include simple alkali metals such as lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, sodium t-butoxy, potassium t-butoxy, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; alkali metal hydrides, alkali metal hydroxides, alkoxy alkali metals, alkali metal carbonates, and alkali metal bicarbonates; alkaline earth metal carbonates such as calcium carbonate; organic lithiums such as n-butyllithium, s-butyllithium, t-butyllithium, lithium diisopropylamide (LDA), lithium 2,2,6,6-tetramethylpiperidine (LiTMP), and hexamethyldisilazane lithium (LHMDS); and amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine. However, preferred are lithium amide reagents obtained by lithiating secondary amines such as LDA, LiTMP, and LHMDS, and alkoxy alkali metals such as t-butoxylithium.

[0038] (6) Coupling reaction In the production method of the present invention, the charging ratio of the fluorinated aromatic primary amine compound to the chlorinated, brominated, or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon is preferably about 1.0 to 1.2 mol of the reactive site of the aromatic hydrocarbon, which is chlorine, bromine, or iodine, or pseudohalogen, relative to 1 mol of the NH group of the fluorinated aromatic primary amine compound. For example, in terms of the ratio of amounts of substances (mol), in the reaction between formula (X1) and formula (Y1), a ratio of (Y1) to (X1) of about 1 to 1.2 is preferable; in the reaction between formula (X1) and formula (Y2), a ratio of (Y1) to (X1) of about 0.5 to 0.6 is preferable; in the reaction between formula (X2) and formula (Y1), a ratio of (Y1) to (X2) of about 2 to 2.4 is preferable; and in the reaction between formula (X2) and (Y2), a ratio of (Y2) to (X2) of about 1 to 1.2 is preferable.

[0039] The coupling reaction of the present invention is carried out in a solvent when all of the raw material compounds are solids or from the viewpoint of efficiently obtaining the target fluorinated aromatic secondary amine compound. When a solvent is used, the type thereof is not particularly limited as long as it does not adversely affect the reaction. Specific examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, 1,2-dimethicone, etc.), and the like. Examples of suitable solvents include dimethyl ketones (dimethyl ethane, 1,2-diethoxyethane, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.), amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), lactams and lactones (N-methylpyrrolidone, γ-butyrolactone, etc.), ureas (N,N-dimethylimidazolidinone, tetramethylurea, etc.), sulfoxides (dimethyl sulfoxide, sulfolane, etc.), and nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents may be used alone or in combination of two or more. In particular, in the present invention, it is preferable to use ethers as the solvent, and it is more preferable to use dioxane.

[0040] The lower limit of the reaction temperature cannot be specified in general because it varies depending on the reactivity of the reaction substrates, etc., but the coupling reaction usually proceeds well at 45°C or higher. In particular, to further improve reactivity, the reaction temperature is preferably 60°C or higher, more preferably 75°C or higher, and even more preferably 90°C or higher, and it is particularly suitable to carry out the reaction under heating and reflux of the solvent. On the other hand, the upper limit of the reaction temperature cannot be specified in general because it varies depending on the boiling point of the solvent used, but it is usually about 200°C or lower. After the reaction is completed, the reaction mixture is worked up in a conventional manner to obtain the desired fluorinated aromatic secondary amine compound.

[0041] [2] Fluorine-containing aniline derivatives One of the fluorine-containing aniline derivatives according to the present invention is represented by the following formula (T1).

[0042] [ka]

[0043] In the above formula (T1), X 211 represents a divalent group represented by any one of the formulae (A01-1) to (A09).

[0044] [ka]

[0045] where L 01 is -S-, -O-, -CO-, -CH2-, -(CH2)2-, -C(CH3)2-, -CF2-, -(CF2)2-, -C(CF3)2-, a fluorene-9,9-diyl group, -NH- or -NZ 10 - represents. L 02 and L 03 are each independently a hydrogen atom, Z 11 an alkyl group having 1 to 20 carbon atoms which may be substituted with 11 an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z 12 represents an aryl group having 6 to 20 carbon atoms which may be substituted with, but is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and more preferably a hydrogen atom, a methyl group, or a phenyl group. Specific examples of the alkyl group and aryl group include the same as those mentioned above. Specific examples of alkenyl groups having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, and n-1-eicosenyl groups.

[0046] L 04 is a hydrogen atom, Z 11 an alkyl group having 1 to 20 carbon atoms which may be substituted with 11 an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z 12 Specific examples of these alkyl groups, alkenyl groups and aryl groups are the same as those mentioned above. 04 is preferably a hydrogen atom or a phenyl group. Z' represents a substituent of an aromatic ring, and each Z' is independently 11 an alkyl group having 1 to 20 carbon atoms which may be substituted with 11 an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z 12 Specific examples of these alkyl groups, alkenyl groups and aryl groups include those similar to those mentioned above.

[0047] Z 01 ~Z 09 represents a substituent of an aromatic ring, each of which independently represents a chlorine atom, a bromine atom, a nitro group, a cyano group, Z 11 an alkyl group having 1 to 20 carbon atoms which may be substituted with 11 an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z 12 represents an aryl group having 6 to 20 carbon atoms which may be substituted by 10 is Z 11 an alkyl group having 1 to 20 carbon atoms which may be substituted with 11 an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z12 represents an aryl group having 6 to 20 carbon atoms which may be substituted by 11 are each independently a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or Z 13 represents an aryl group having 6 to 20 carbon atoms which may be substituted by 12 are each independently a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or Z 13 an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 13 represents an alkenyl group having 2 to 20 carbon atoms which may be substituted by 13 represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group or a cyano group, and specific examples of these alkyl groups, alkenyl groups and aryl groups include those similar to those mentioned above. Among them, Z 01 ~Z 09 When Z is present, it is preferably a nitro group or an alkyl group having 1 to 5 carbon atoms which may be substituted with a fluorine atom. 10 is preferably a phenyl group which may be substituted with a fluorine atom. In addition, the substituent Z of the aromatic ring p When there are a plurality of (p=′, 01 to 09), they may be the same or different.

[0048] a 11 , a 13 , a 21 , a 23 , a 31 , a 33 , a 41 , a 51 , a 61 , a 71 , a 73 , a 81 , a 83 , a 91 and a 93 represents the number of fluorine atoms substituted on the aromatic ring, and a 12 , a 14 , a 22 , a 24 , a 32 , a 34 , a 42 , a 52 , a 62, a 72 , a 74 , a 82 , a 84 , a 92 and a 94 is the Z substituted on the aromatic ring. 01 ~Z 09 represents the number of 75 and a 76 represents the number of Z's substituted on the aromatic ring. a 11 is an integer between 2 and 4, and a 12 is an integer between 0 and 2, and a 11 +a 12 Satisfies ≦4. a 13 is an integer between 2 and 4, and a 14 is an integer between 0 and 2, and a 13 +a 14 Satisfies ≦4. a 21 and a 23 are each independently an integer of 1 to 4, 22 and a 24 are each independently an integer of 0 to 3, and a 21 +a 22 ≦4 and a 23 +a 24 Satisfies ≦4. a 31 and a 33 are each independently an integer of 1 to 4, 32 and a 34 are each independently an integer of 0 to 3, and a 31 +a 32 ≦4 and a 33 +a 34 Satisfies ≦4. a 41 is an integer from 1 to 6, and a 42 is an integer between 0 and 5, and a 41 +a 42 Satisfies ≦6. a 51 is an integer from 1 to 8, and a 52 is an integer from 0 to 7, and a 51 +a 52 Satisfies ≦8. a61 is an integer from 1 to 8, and a 62 is an integer from 0 to 7, and a 61 +a 62 Satisfies ≦8. a 71 and a 73 are each independently an integer of 1 to 3, 72 and a 74 are each independently an integer of 0 to 2, and a 71 +a 72 ≦3 and a 73 +a 74 ≦3, and a 75 and a 76 are each independently an integer of 0 to 4. a 81 and a 83 are each independently an integer of 1 to 3, 82 and a 84 are each independently an integer of 0 to 2, and a 81 +a 82 ≦3 and a 83 +a 84 Satisfies ≦3. a 91 and a 93 are each independently an integer of 1 to 3, 92 and a 94 are each independently an integer of 0 to 2, and a 91 +a 92 ≦3 and a 93 +a 94 Satisfies ≦3. In particular, a 41 , a 51 , a 61 is preferably an integer of 2 or more. Also, a 12 , a 14 , a 22 , a 24 , a 32 , a 34 , a 42 , a 52 , a 62 , a 72 , a 74 , a 82 , a 84 , a 92and a 94 is preferably 0, and a 75 and a 76 is preferably 0.

[0049] Among these, X 211 is preferably a divalent group represented by formula (A02), more preferably a divalent group represented by the following formula (A02-1), and considering use as a charge transporting substance, even more preferably a perfluorobiphenylene group represented by formula (A02-1-1).

[0050] [ka] (In the formula, a 21 ~a 24 and Z 02 has the same meaning as above.)

[0051] [ka]

[0052] On the other hand, Y 211 and Y 212 each independently represents a monovalent group represented by any one of formulas (B01) to (B21).

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] where L 11is -S-, -O-, -CO-, -CH2-, -(CH2)2-, -C(CH3)2-, -CF2-, -(CF2)2-, -C(CF3)2-, a fluorene-9,9-diyl group, -NH- or -NZ 100 - represents. L 12 is a hydrogen atom, Z 130 an alkyl group having 1 to 20 carbon atoms which may be substituted with 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z 131 Specific examples of these alkyl groups, alkenyl groups and aryl groups are the same as those mentioned above. 12 is preferably a hydrogen atom or a phenyl group. L 13 and L 14 are each independently a hydrogen atom, Z 130 an alkyl group having 1 to 20 carbon atoms which may be substituted with 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z 131 Specific examples of these alkyl groups, alkenyl groups and aryl groups are the same as those mentioned above. 13 and L 14 As the group, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms is preferable, and a hydrogen atom, a methyl group, or a phenyl group is more preferable.

[0057] Z 100 is Z 130 an alkyl group having 1 to 20 carbon atoms which may be substituted with 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z 131 It represents an aryl group having 6 to 20 carbon atoms which may be substituted with one of the following, but a phenyl group which may be substituted with a fluorine atom is preferred. Z 101 ~Z 107 and Z 109 ~Z 121are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or Z 130 an alkyl group having 1 to 20 carbon atoms which may be substituted with 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z 131 represents an aryl group having 6 to 20 carbon atoms which may be substituted by 108 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or Z 130 an alkyl group having 1 to 20 carbon atoms which may be substituted with 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z 131 represents an aryl group having 6 to 20 carbon atoms which may be substituted with Z 108 may be bonded to each other to form a ring, and Z 130 are each independently a fluorine atom, a chlorine atom, a bromine atom or Z 132 represents an aryl group having 6 to 20 carbon atoms which may be substituted by 131 are each independently a fluorine atom, a chlorine atom, a bromine atom, Z 132 an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 132 represents an alkenyl group having 2 to 20 carbon atoms which may be substituted by 132 represents a fluorine atom, a chlorine atom, or a bromine atom, and specific examples of these alkyl groups, alkenyl groups, and aryl groups include those similar to those mentioned above. 101 ~Z 107 and Z 109 ~Z 121 is preferably a hydrogen atom. 108 is a hydrogen atom or at least one pair of Z present at the ortho position of the nitrogen atom on different benzene rings. 108 A single bond between two groups is preferred. 108 As an example of formula (B08) in which a single bond is formed between two groups, there can be mentioned one represented by the following formula (B08'). In addition, Z q (q=101 to 121) may be the same or different.

[0058] [ka]

[0059] Ar 1 are each independently an aryl group having 6 to 20 carbon atoms, and examples of the aryl group include the same as those mentioned above. 1 is preferably a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, and more preferably a phenyl group. Ar 2 represents a single bond or an arylene group having 6 to 20 carbon atoms. Specific examples of the arylene group having 6 to 20 carbon atoms include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, and 2,7-naphthalenediyl groups. Among these, Ar 2 is preferably a single bond or a 1,4-phenylene group.

[0060] In particular, considering the ease of synthesis, Y 211 and Y 212 are preferably the same monovalent group, and more preferably both are monovalent groups represented by any one of formulas (B01), (B02), (B04), (B08) and (B18).

[0061] Another fluorine-containing aniline derivative according to the present invention is represented by the following formula (T2).

[0062] [ka]

[0063] In formula (T2), X 221 and X 222 each independently represents a monovalent group represented by any one of formulas (C01) to (C09).

[0064] [ka]

[0065] where b 11 , b 21 , b 23 , b 31 , b 33 , b 41 , b 51 , b 61 , b 71 , b 73 , b 81 , b 83 , b 91 and b 93 represents the number of fluorine atoms substituted on the aromatic ring, and b 12 , b 22 , b 24 , b 32 , b 34 , b 42 , b 52 , b 62 , b 72 , b 74 , b 82 , b 84 , b 92 and b 94 is the Z substituted on the aromatic ring. 01 ~Z 09 represents the number of 75 and b 76 represents the number of Z's substituted on the aromatic ring. b 11 is an integer between 2 and 5, and b 12 is an integer from 0 to 3, and b 11 +b 12 Satisfies ≦5. b 21 is an integer from 1 to 4, and b 23 is an integer from 1 to 5, and b 22 is an integer from 0 to 3, and b 24 is an integer from 0 to 4, and b 21 +b 22 ≦4 and b 23 +b 24 Satisfies ≦5. b 31 is an integer from 1 to 4, and b 33 is an integer from 1 to 5, and b 32 is an integer from 0 to 3, and b 34is an integer from 0 to 4, and b 31 +b 32 ≦4 and b 33 +b 34 Satisfies ≦5. b 41 is an integer from 1 to 7, and b 42 is an integer from 0 to 6, and b 41 +b 42 Satisfies ≦7. b 51 is an integer from 1 to 9, and b 52 is an integer from 0 to 8, and b 51 +b 52 Satisfies ≦9. b 61 is an integer from 1 to 9, and b 62 is an integer from 0 to 8, and b 61 +b 62 Satisfies ≦9. b 71 is an integer from 1 to 3, and b 73 is an integer from 1 to 4, and b 72 is an integer between 0 and 2, and b 74 is an integer from 0 to 3, and b 71 +b 72 ≦3 and b 73 +b 74 ≦4, b 75 and b 76 are each independently an integer of 0 to 4. b 81 is an integer from 1 to 3, and b 83 is an integer from 1 to 4, and b 82 is an integer between 0 and 2, and b 84 is an integer from 0 to 3, and b 81 +b 82 ≦3 and b 83 +b 84 Satisfies ≦4. b 91 is an integer from 1 to 3, and b 93 is an integer from 1 to 4, and b 92 is an integer between 0 and 2, and b 94 is an integer from 0 to 3, and b 91 +b 92 ≦3 and b 93 +b94 Satisfies ≦4. In particular, b 41 , b 51 , b 61 is preferably an integer of 2 or more. Also, b 12 , b 22 , b 24 , b 32 , b 34 , b 42 , b 52 , b 62 , b 72 , b 74 , b 82 , b 84 , b 92 and b 94 is preferably 0, and b 75 and b 76 is preferably 0. In addition, L 01 ~L 04 , Z′ and Z 01 ~Z 09 has the same meaning as above.

[0066] In particular, considering the ease of synthesis and charge transport properties, X 221 and X 222 are preferably the same monovalent group, more preferably both are a monovalent group represented by formula (C01), and even more preferably both are a monovalent group represented by the following formula (C01-1).

[0067] [ka]

[0068] On the other hand, Y 221 represents a divalent group represented by any one of the formulas (D01-1) to (D21).

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] In the formula, Ar 3 each independently represents an arylene group having 6 to 20 carbon atoms, and specific examples of this arylene group include those similar to those mentioned above. Also, L 11 ~L 14 , Z 101 ~Z 121 , and Ar 1 has the same meaning as above.

[0074] Among these, Y 221 is preferably a divalent group represented by formula (D02), more preferably a divalent group represented by formula (D02-1) below, and even more preferably a biphenylene group represented by formula (D02-1-1) below.

[0075] [ka] (In the formula, Z 102 has the same meaning as above.)

[0076] The fluorine-containing aniline derivatives of the present invention do not include compounds represented by the following formulas [1] to

[13] .

[0077] [ka]

[0078] Specific examples of the fluorine-containing aniline derivative of the present invention include those represented by the following formulae, but are not limited thereto.

[0079] [ka] (In the formula, t-Bu represents a t-butyl group.)

[0080] [3] Polymer The polymer according to the present invention contains a repeating unit represented by the following formula (P1-2).

[0081] [ka]

[0082] In formula (P1-2), X 211 The groups are the same as those exemplified for the fluorine-containing aniline derivatives, and the preferred ranges thereof are also the same as those mentioned above. Also, Y 221 The group may be the same as those exemplified for the fluorine-containing aniline derivatives, and among these, a divalent group represented by any one of formulas (D02), (D17) and (D19) is preferred.

[0083] The molecular weight of the polymer of the present invention is not particularly limited, but in consideration of the conductivity and solubility in organic solvents when used as a charge transport material, the weight average molecular weight is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 5,000 to 30,000. The weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography.

[0084] Specific examples of the polymer of the present invention include those represented by the following formulae, but are not limited thereto.

[0085] [ka] (In the formula, each m independently represents an integer of 2 or more.)

[0086] [4] Method for producing fluorine-containing aniline derivatives and polymers The fluorine-containing aniline derivatives and polymers of the present invention explained above can be synthesized by the method for producing a fluorinated aromatic secondary amine of the present invention already described above. For example, the fluorine-containing aniline derivative can be obtained by reacting a fluorinated aromatic primary diamine represented by the formula (X2) with 2 equivalents of a chlorinated, brominated, or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon represented by the formula (Y1) in the presence of a zero-valent palladium complex of dibenzylideneacetone, a ligand represented by the formula (L), and a base, or by reacting a fluorinated aromatic primary amine represented by the formula (X1) with 0.5 equivalents of a dichlorinated, dibrominated, or diiodinated aromatic hydrocarbon or dipseudohalogenated aromatic hydrocarbon represented by the formula (Y2). On the other hand, the polymer can be obtained by reacting a fluorinated aromatic primary diamine compound represented by the above formula (X2) with a dichlorinated, dibrominated, or diiodinated aromatic hydrocarbon or dipseudohalogenated aromatic hydrocarbon represented by the above formula (Y2) in the presence of a palladium zero-valent complex of dibenzylideneacetone, a ligand represented by the above formula (L), and a base. In polymer synthesis, increasing the amount of catalyst increases the molecular weight, so the molecular weight of the resulting polymer can be adjusted by adjusting the amount of catalyst.

[0087] [5] Charge transport material, charge transport composition, and charge transport thin film The above-mentioned fluorine-containing aniline derivatives and polymers of the present invention have excellent transparency due to the presence of fluorine atoms in the molecules, and exhibit electrical conductivity either alone or in combination with a dopant substance, and therefore can be suitably used as charge-transporting substances. A charge-transporting composition can be easily prepared by dissolving the fluorine-containing aniline derivatives or polymers of the present invention in a solvent. For example, the charge-transporting composition of the present invention may contain a charge-transporting substance consisting of the above-mentioned fluorine-containing aniline derivative or polymer, and an organic solvent. Depending on the application of the resulting thin film, the composition may contain a dopant substance for the purpose of improving the charge-transporting ability, etc. The dopant substance is not particularly limited as long as it is soluble in at least one solvent used in the composition.

[0088] Specific examples of dopant substances include strong inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid; aluminum chloride (III) (AlCl3), titanium tetrachloride (IV) (TiCl4), boron tribromide (BBr3), boron trifluoride ether complex (BF3·OEt2), iron chloride (III) (FeCl3), copper chloride (II) (CuCl2), antimony pentachloride (V) (SbCl5), arsenic pentafluoride (V) (AsF5), and fluorine pentafluoride (V). Lewis acids such as phosphorus fluoride (PF5) and tris(4-bromophenyl)aluminum hexachloroantimonate (TBPAH); benzenesulfonic acid, tosylic acid, camphorsulfonic acid, hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, dodecylbenzenesulfonic acid, naphthalenedisulfonic acids such as 1,5-naphthalenedisulfonic acid, 1,3,5-naphthalenetrisulfonic acid, and 1,3,6-naphthalene Examples of the oxidizing agent include organic strong acids such as naphthalene trisulfonic acid (e.g., trisulfonic acid), polystyrene sulfonic acid, 1,4-benzodioxane disulfonic acid compounds described in WO 2005 / 000832, naphthalene or anthracene sulfonic acid compounds described in WO 2006 / 025342, and aryl sulfonic acid compounds such as dinonylnaphthalene sulfonic acid compounds described in JP 2005-108828 A; organic oxidizing agents such as 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and iodine; and inorganic oxidizing agents such as heteropoly acids (e.g., phosphomolybdic acid, phosphotungstic acid, and phosphotungstomolybdic acid) described in WO 2010 / 058777, and these may be used in combination.

[0089] Among these, arylsulfonic acid compounds are preferred, and arylsulfonic acid compounds represented by formula (H1) or (H2) are suitable. The molecular weight of the arylsulfonic acid compound used as a dopant substance is preferably 3000 or less, more preferably 2500 or less, in consideration of solubility in organic solvents.

[0090] [ka]

[0091] A 1 represents O or S, with O being preferred. A 2 represents a naphthalene ring or an anthracene ring, with a naphthalene ring being preferred. A 3 represents a divalent to tetravalent perfluorobiphenyl group, and p represents A 1 and A 3 It is an integer that satisfies 2≦p≦4, but A 3 is a perfluorobiphenyldiyl group, preferably a perfluorobiphenyl-4,4'-diyl group, and p is preferably 2. q is A 2 represents the number of sulfonic acid groups bonded to q, and is an integer satisfying 1≦q≦4, with 2 being optimal.

[0092] A 4 ~A 8 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated alkenyl group having 2 to 20 carbon atoms, 4 ~A 8 At least three of the are halogen atoms.

[0093] Examples of halogenated alkyl groups having 1 to 20 carbon atoms include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, and 1,1,2,2,3,3,4,4,4-nonafluorobutyl groups.

[0094] Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include perfluorovinyl, perfluoropropenyl (perfluoroallyl), and perfluorobutenyl groups. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, with a fluorine atom being preferred. Other examples of the alkyl group having 1 to 20 carbon atoms include the same as those mentioned above.

[0095] Among these, A 4 ~A 8 is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms, and A 4 ~A 8 At least three of A are preferably fluorine atoms, and are selected from the group consisting of a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, and a fluorinated alkenyl group having 2 to 5 carbon atoms, and 4 ~A 8 At least three of A are preferably fluorine atoms, and A is preferably a hydrogen atom, a fluorine atom, a cyano group, a perfluoroalkyl group having 1 to 5 carbon atoms, or a perfluoroalkenyl group having 1 to 5 carbon atoms. 4 , A 5 and A 8 It is even more preferred that is a fluorine atom. The perfluoroalkyl group is a group in which all hydrogen atoms of an alkyl group have been substituted with fluorine atoms, and the perfluoroalkenyl group is a group in which all hydrogen atoms of an alkenyl group have been substituted with fluorine atoms.

[0096] r represents the number of sulfonic acid groups bonded to the naphthalene ring and is an integer satisfying 1≦r≦4, preferably 2 to 4, and most preferably 2.

[0097] Specific examples of suitable aryl sulfonic acid compounds are listed below, but the present invention is not limited to these.

[0098] [ka]

[0099] The organic solvent is not particularly limited as long as it can dissolve or disperse the charge transporting substance and the dopant substance, and examples thereof include benzene, toluene, o-xylene, m-xylene, p-xylene, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, cyclohexanol, ethylene glycol, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1, Examples of the solvent include 4-butanediol, propylene glycol, hexylene glycol, tetrahydrofurfuryl alcohol, butyl cellosolve, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl carbitol, diacetone alcohol, γ-butyrolactone, ethyl lactate, and n-hexyl acetate. These may be used alone or in combination of two or more.

[0100] The charge transporting composition of the present invention usually has a viscosity of 1 to 50 mPa·s at 25°C and a surface tension of 20 to 50 mN / m at 25°C. The viscosity and surface tension of the charge transport composition of the present invention can be adjusted by changing the types of organic solvents used, their ratios, solids concentration, etc., taking into consideration various factors such as the coating method used and the desired film thickness.

[0101] The solids concentration of the charge transport composition of the present invention is set appropriately taking into consideration the viscosity and surface tension of the composition, the thickness of the thin film to be produced, and the like, but is usually about 0.1 to 15.0 mass %, and from the viewpoint of suppressing aggregation of the charge transport substance in the composition, it is preferably 10.0 mass % or less, more preferably 8.0 mass % or less, and even more preferably 5 mass % or less. The solid content in the solid content concentration referred to here means the components other than the solvent contained in the charge transporting composition of the present invention.

[0102] The charge transporting composition of the present invention can be produced by mixing the charge transporting substance of the present invention, an organic solvent, and an optional dopant substance, in any order. When preparing the composition, heating may be carried out as appropriate within a range that does not cause decomposition or deterioration of the components. In the present invention, from the viewpoint of obtaining a thin film with higher flatness with good reproducibility, it is desirable to dissolve the charge transporting substance and the like in an organic solvent and then filter the resultant mixture using a filter or the like on the order of submicrometers.

[0103] The charge transporting composition described above can be applied to a substrate and baked to form the charge transporting thin film of the present invention on the substrate. The method for applying the composition is not particularly limited, and examples thereof include dipping, spin coating, transfer printing, roll coating, brush coating, inkjet coating, spraying, and slit coating. It is preferable to adjust the viscosity and surface tension of the composition depending on the application method.

[0104] When the charge transporting composition of the present invention is used, the firing atmosphere is not particularly limited, and a thin film having a uniform film surface and high charge transport properties can be obtained not only in an atmospheric atmosphere (air) but also in an inert gas such as nitrogen or in a vacuum, but is usually fired in air. The baking conditions are not particularly limited, but may be, for example, heated and baked using a hot plate. Typically, the baking temperature is set within the range of 100 to 260°C, and the baking time is set within the range of 1 minute to 1 hour, taking into consideration the desired charge transport properties, etc. Furthermore, if necessary, multi-stage baking at two or more different temperatures may be performed.

[0105] The thickness of the charge-transporting thin film is not particularly limited, but is preferably 5 to 300 nm when used as a functional layer of an organic EL device. Methods for changing the thickness include changing the solid concentration in the charge-transporting composition and changing the amount of liquid during application.

[0106] Since the fluorine-containing aniline derivative or polymer of the present invention contains fluorine atoms, it can also be used as an additive to be added to a charge-transporting composition containing other charge-transporting substances, mainly for the purpose of improving the coating property, improving the transparency of the obtained film, and adjusting the film properties such as adjusting the wettability of the film surface.

[0107] [6] Organic electroluminescence (EL) elements The organic EL device of the present invention has a pair of electrodes and the above-described charge transporting thin film of the present invention between these electrodes. Representative configurations of organic EL devices include, but are not limited to, the following (a) to (f). In the following configurations, an electron blocking layer or the like can be provided between the light-emitting layer and the anode, and a hole blocking layer or the like can be provided between the light-emitting layer and the cathode, as necessary. In addition, the hole injection layer, hole transport layer, or hole injection transport layer may also function as an electron blocking layer or the like, and the electron injection layer, electron transport layer, or electron injection transport layer may also function as a hole blocking layer or the like. (a) Anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode (b) Anode / hole injection layer / hole transport layer / light-emitting layer / electron injection transport layer / cathode (c) Anode / hole injection transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode (d) Anode / hole injection transport layer / light-emitting layer / electron injection transport layer / cathode (e) Anode / hole injection layer / hole transport layer / light-emitting layer / cathode (f) Anode / hole injection transport layer / light-emitting layer / cathode

[0108] The terms "hole injection layer," "hole transport layer," and "hole injection transport layer" refer to layers formed between the light-emitting layer and the anode, which have the function of transporting holes from the anode to the light-emitting layer. When only one layer of a hole-transporting material is provided between the light-emitting layer and the anode, it is the "hole injection transport layer." When two or more layers of a hole-transporting material are provided between the light-emitting layer and the anode, the layer closest to the anode is the "hole injection layer," and the remaining layers are "hole transport layers." In particular, the hole injection (transport) layer is a thin film that is excellent not only in accepting holes from the anode but also in injecting holes into the hole transport (light-emitting) layer. The terms "electron injection layer," "electron transport layer," and "electron injection transport layer" refer to layers formed between the light-emitting layer and the cathode, which have the function of transporting electrons from the cathode to the light-emitting layer. When only one layer of an electron-transporting material is provided between the light-emitting layer and the cathode, it is the "electron injection transport layer." When two or more layers of electron-transporting materials are provided between the light-emitting layer and the cathode, the layer closest to the cathode is the "electron injection layer," and the other layers are "electron transport layers." The "light-emitting layer" is an organic layer that has a light-emitting function, and when a doping system is used, it contains a host material and a dopant material. In this case, the host material mainly functions to promote the recombination of electrons and holes and confine excitons within the light-emitting layer, while the dopant material functions to efficiently emit light from the excitons obtained by the recombination. In the case of a phosphorescent element, the host material mainly functions to confine excitons generated by the dopant within the light-emitting layer.

[0109] The charge transport thin film of the present invention can be suitably used as an organic functional film provided between an anode and an emitting layer in an organic EL device, and can be more suitably used as a hole injection layer, a hole transport layer, or a hole injection transport layer, and can be even more suitably used as a hole injection layer. When an organic EL device is produced using the charge transporting composition of the present invention, the materials to be used and the production method thereof are as follows, but are not limited thereto.

[0110] An example of a method for producing an OLED device having a hole injection layer made of a thin film obtained from the charge-transporting composition of the present invention is as follows: It is preferable to previously subject the electrodes to surface treatment such as washing with alcohol, pure water, or UV ozone treatment or oxygen plasma treatment, within a range that does not adversely affect the electrodes. A hole injection layer is formed on an anode substrate using the charge transport composition by the above method. The substrate is then introduced into a vacuum deposition apparatus, and a hole transport layer, a light-emitting layer, an electron transport layer / hole blocking layer, an electron injection layer, and a cathode metal are sequentially deposited. Alternatively, instead of forming the hole transport layer and the light-emitting layer by deposition in this method, these layers are formed by a wet process using a hole transport layer-forming composition containing a hole transport polymer and a light-emitting layer-forming composition containing a light-emitting polymer. If necessary, an electron blocking layer may be provided between the light-emitting layer and the hole transport layer.

[0111] Anode materials include transparent electrodes such as indium tin oxide (ITO) and indium zinc oxide (IZO), and metal anodes made of metals such as aluminum or their alloys, preferably planarized. Polythiophene derivatives and polyaniline derivatives with high charge transport properties can also be used. Other metals that may be used to form the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.

[0112] Examples of materials for forming the hole transport layer include triarylamines such as (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spiro dimer, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine (α-NPD), 4,4',4"-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), and 4,4',4"-tris[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA), and oligothiophenes such as 5,5"-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2':5',2"-terthiophene (BMA-3T).

[0113] Materials for forming the light-emitting layer include low-molecular-weight light-emitting materials such as metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, metal complexes of (2-hydroxyphenyl)benzothiazole, and silole derivatives; and systems in which a light-emitting material and an electron transfer material are mixed with a polymer compound such as poly(p-phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], poly(3-alkylthiophene), or polyvinylcarbazole. When forming a light-emitting layer by vapor deposition, the layer may be co-deposited with a light-emitting dopant. Examples of the light-emitting dopant include metal complexes such as tris(2-phenylpyridine)iridium(III) (Ir(ppy)), naphthacene derivatives such as rubrene, quinacridone derivatives, and fused polycyclic aromatic rings such as perylene.

[0114] Examples of materials for forming the electron transport layer / hole blocking layer include oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, and pyrimidine derivatives.

[0115] Materials for forming the electron injection layer include, but are not limited to, metal oxides such as lithium oxide (Li2O), magnesium oxide (MgO), and alumina (Al2O3), and metal fluorides such as lithium fluoride (LiF) and sodium fluoride (NaF). Examples of the cathode material include aluminum, magnesium-silver alloy, and aluminum-lithium alloy. Examples of materials for forming the electron blocking layer include tris(phenylpyrazole)iridium.

[0116] Hole-transporting polymers include poly[(9,9-dihexylfluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene)], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,1'-biphenylene-4,4-diamine)], poly[(9,9-bis{1'-penten-5'-yl}fluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene)], and poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine]-endcapped with Examples thereof include polysilcisquinoxane and poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)].

[0117] Examples of light-emitting polymers include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), polyphenylenevinylene derivatives such as poly(2-methoxy-5-(2'-ethylhexoxy)-1,4-phenylenevinylene) (MEH-PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

[0118] The organic EL device of the present invention may be sealed, if necessary, with a moisture scavenger or the like in accordance with a conventional method in order to prevent deterioration of the characteristics. [Example]

[0119] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0120] 〔Device〕 Measurement of the physical properties of the samples was carried out under the following conditions using the following equipment. (1) Liquid chromatography (reaction tracking) Equipment: Shimadzu Corporation UV-VIS detector: SPD-20A Column oven: CTO-20A Degassing unit: DGU-20A Liquid delivery unit: LC-20AB Autosampler: SIL-20A Column: Poroshell 120 EC-C18 (2.7 μm, 3.0 × 50 mm, Agilent) Column temperature: 40℃ Solvent: acetonitrile / water Acetonitrile concentration: 40% (0-0.01 min) → 40%-100% (0.01-5 min) → 100% (5-15 min) (volume ratio) Detector: UV (2) Gel permeation chromatography (measuring the molecular weight of polymers) Equipment: Shimadzu Corporation UV-VIS detector: SPD-20A Differential refractometer detector: RID-20A Column oven: CTO-20A Degassing unit: DGU-20A Liquid delivery unit: LC-20AD Autosampler: SIL-20A Column: Shodex KF-G + KF-804L Column temperature: 40℃ Solvent: tetrahydrofuran Detector: UV (3) Application of composition: Spin coater MS-A100, manufactured by Mikasa Co., Ltd. (4) Fabrication of element: Multifunctional deposition system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd. (5) Measurement of current density of element: IVL measurement system manufactured by Tech World Co., Ltd. (6) Glass transition temperature (Tg) measurement device: Perkin Elmer Diamond DSC Measurement conditions: Nitrogen atmosphere Heating rate: 5°C / min (40-300°C) (7) 5% weight loss temperature (Td5%) measurement Equipment: Rigaku Corporation TG8120 Measurement conditions: In air Heating rate: 10°C / min (40-500°C) (8) Automatic column chromatography device (preparation of target product): 2-channel parallel purification device Purif-espoir2 manufactured by Shoko Scientific Co., Ltd. (9) NMR: Bruker Avance III 500MHz Internal Standard 19 F-NMR chemical shift correction Trifluorotoluene=-64ppm 13 C-NMR chemical shift correction Acetone-d6=206.68ppm Chloroform-d1=77.23ppm N,N-Dimethylformamide-d7=163.15ppm Tetrahydrofuran-d8=67.57ppm

[0121] 〔reagent〕 The reagents used in the following examples and comparative examples are as follows: Pd(PPh3)4 [Tokyo Chemical Industry Co., Ltd.] Pd(DBA)2 [Tokyo Chemical Industry Co., Ltd.] Pd(dppf)Cl2 [Tokyo Chemical Industry Co., Ltd.] t-BuONa [Kishida Chemical Co., Ltd.] BINAP [Tokyo Chemical Industry Co., Ltd.] Cesium carbonate [Junsei Chemical Co., Ltd.] Magnesium sulfate [Kishida Chemical Co., Ltd.] Potassium acetate [Junsei Chemical Co., Ltd.] Lithium hexamethyldisilazide (LHMDS) 1.3 mol / L tetrahydrofuran solution [Tokyo Chemical Industry Co., Ltd.] Lithium hexamethyldisilazide (LHMDS) 1 mol / L toluene solution [Aldrich] RuPhos [Aldrich] t-BuXPhos [Aldrich] SPhos [Aldrich] t-BuMePhos [Aldrich] JhonPhos [Aldrich] CyJhonPhos [Aldrich] N,N-Dimethylformamide [Junsei Chemical Co., Ltd.] Ethyl acetate [Tokyo Chemical Industry Co., Ltd. or Junsei Chemical Co., Ltd.] Toluene [Junsei Chemical Co., Ltd. or Kanto Chemical Co., Ltd.] Dioxane [Kanto Chemical Co., Ltd.] Hexane [Junsei Chemical Co., Ltd.] Tetrahydrofuran [Junsei Chemical Co., Ltd.] Tetrahydrofurfuryl alcohol [Kanto Chemical Co., Ltd.] Pentafluoroaniline [Tokyo Chemical Industry Co., Ltd.] Fluorobenzene [Tokyo Chemical Industry Co., Ltd.] Chlorobenzene [Tokyo Chemical Industry Co., Ltd.] Bromobenzene [Tokyo Chemical Industry Co., Ltd.] Iodobenzene [Tokyo Chemical Industry Co., Ltd.] Bromopentafluorobenzene [Tokyo Chemical Industry Co., Ltd.] 2-Fluoroaniline [Tokyo Chemical Industry Co., Ltd.] 4-Bromoanisole [Tokyo Chemical Industry Co., Ltd.] 4,4'-Diaminooctafluorobiphenyl [Tokyo Chemical Industry Co., Ltd.] 1-Bromo-4-t-butylbenzene [Tokyo Chemical Industry Co., Ltd.] 1-Bromonaphthalene [Junsei Chemical Co., Ltd.] 2-Bromonaphthalene [Tokyo Chemical Industry Co., Ltd.] 4-Bromotriphenylamine [Tokyo Chemical Industry Co., Ltd.] 4-Iodotriphenylamine [Tokyo Chemical Industry Co., Ltd.] 4-Bromo-4'-(diphenylamino)biphenyl [Fujifilm Wako Pure Chemical Industries, Ltd.] 2-Bromo-9,9′-spirobi[9H-fluorene] [Tokyo Chemical Industry Co., Ltd.] 4,4'-Dibromobiphenyl [Tokyo Chemical Industry Co., Ltd.] 1,4-Dibromobenzene [Tokyo Chemical Industry Co., Ltd.] 3,6-Dibromo-9-phenylcarbazole [Fujifilm Wako Pure Chemical Industries, Ltd.] 2,7-Dibromo-9,9-dimethylfluorene [Tokyo Chemical Industry Co., Ltd.] 4-Fluorobromobenzene [Tokyo Chemical Industry Co., Ltd.]

[0122] [1] Synthesis of Fluorinated Aromatic Secondary Amine Compounds (1) Reaction of pentafluoroaniline with 4-bromoanisole [ka]

[0123] [Comparative Example 1-1] A 30 mL reaction flask equipped with a reflux column was charged with 0.05 mmol (57.8 mg) of Pd(PPh3), 1.2 mmol (115.3 mg) of t-BuONa, and 1.2 mmol (219.7 mg) of pentafluoroaniline, and the system was purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added and stirred at room temperature for 5 minutes. The mixture was then heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). Liquid chromatography of a trace amount of the solution collected from the flask confirmed peaks attributable to the raw materials, but no peaks attributable to the target product.

[0124] [Comparative Example 1-2] A 30 mL reaction flask equipped with a reflux column was charged with 0.05 mmol (57.8 mg) of Pd(PPh3), 0.075 mmol (46.7 mg) of (±)BINAP, 1.2 mmol (391.0 mg) of cesium carbonate, and 1.2 mmol (219.7 mg) of pentafluoroaniline. The system was then purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added and stirred at room temperature for 5 minutes. The mixture was then heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). Liquid chromatography of a trace amount of the solution collected from the flask confirmed peaks attributable to the raw materials, but no peaks attributable to the target product.

[0125] [Comparative Example 1-3] A 30 mL reaction flask equipped with a reflux column was charged with 0.05 mmol (57.8 mg) of Pd(PPh3)4, 0.075 mmol (46.7 mg) of (±)BINAP, and 1.2 mmol (219.7 mg) of pentafluoroaniline. The system was then purged with nitrogen. 4 mL of dioxane, 1 mmol (187.0 mg) of 4-bromoanisole, and 0.923 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) were added. The mixture was stirred at room temperature for 5 minutes, then heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). Liquid chromatography of a trace amount of the solution collected from the flask confirmed peaks attributable to the starting materials, but no peaks attributable to the target product.

[0126] [Comparative Example 1-4] The procedure was the same as in Comparative Example 1-3, except that 0.075 mmol (35.0 mg) of RuPhos represented by the following formula (L2) was used instead of (±)BINAP. In liquid chromatography using a small amount of solution collected from the flask, peaks attributable to the raw material were confirmed, but no peaks attributable to the target product were confirmed.

[0127] [ka] (In the formula, i-Pr represents an isopropyl group, and Cy represents a cyclohexyl group.)

[0128] [Comparative Example 1-5] A 30 mL reaction flask equipped with a reflux column was charged with 20.05 mmol (28.8 mg) of Pd(DBA) and 1.2 mmol (219.7 mg) of pentafluoroaniline, and the system was purged with nitrogen. 4 mL of dioxane, 1 mmol (187.0 mg) of 4-bromoanisole, and 0.923 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) were added. The mixture was stirred at room temperature for 5 minutes, then heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). Liquid chromatography of a trace amount of the solution collected from the flask confirmed peaks attributable to the raw materials, but no peaks attributable to the target product.

[0129] [Comparative Examples 1-6] A 30 mL reaction flask equipped with a reflux column was charged with 20.05 mmol (28.8 mg) of Pd(DBA), 0.075 mmol (46.7 mg) of (±)BINAP, 1.2 mmol (219.7 mg) of pentafluoroaniline, and 1.2 mmol (391.0 mg) of cesium carbonate. The system was then purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added and stirred at room temperature for 5 minutes. The mixture was then heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). Liquid chromatography of a trace amount of the solution collected from the flask confirmed peaks attributable to the raw materials, but no peaks attributable to the target product.

[0130] [Comparative Example 1-7] A 30 mL reaction flask equipped with a reflux column was charged with 20.05 mmol (28.8 mg) of Pd(DBA), 0.075 mmol (46.7 mg) of (±)BINAP, and 1.2 mmol (219.7 mg) of pentafluoroaniline. The system was then purged with nitrogen. 4 mL of dioxane, 1 mmol (187.0 mg) of 4-bromoanisole, and 0.923 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) were added. The mixture was stirred at room temperature for 5 minutes, then heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). Liquid chromatography of a trace amount of the solution collected from the flask confirmed peaks attributable to the starting material, but no peaks attributable to the target product.

[0131] [Example 1-1] A 30 mL reaction flask equipped with a reflux column was charged with 20.05 mmol (28.8 mg) of Pd(DBA), 0.075 mmol (35.0 mg) of RuPhos, 1.2 mmol (391.0 mg) of cesium carbonate, and 1.2 mmol (219.7 mg) of pentafluoroaniline. The system was then purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added and stirred at room temperature for 5 minutes. 0.923 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (1.2 mmol of LHMDS) was then added and stirred at room temperature for 5 minutes. The mixture was then heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, a small amount of the solution was sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. At this time, no noticeable peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 97 / 3) to separate and isolate the target fraction. Finally, the solvent was removed from the collected fractions at 80° C. under reduced pressure to obtain 67.2 mg of the target product (yield 26%). 1 H NMR (500.13 MHz, CDCl3): δ = 3.76 (s, 3H), 5.14 (brs, 1H), 6.72-6.75 (m, 6H), 6.8 (d, J = 9.0 Hz, 2 H) 13 C NMR (125.77 MHz, CDCl3): δ = 55.8, 114.7, 119.5, 120.1, 135.4, 136.3, 138.5, 140.6, 155.9 19 F NMR (470.53 MHz, CDCl3): δ = -167.6 (t, J = 21.7 Hz, 1F), -164.5 (td, J = 21.7, 5.2 Hz, 2F), -153.3 (brd, 2F); IR (neat) ν~ = 3314 (w), 3063 (w), 2968 (w), 1694 (s), 1670 (m), 1653 (m), 1609 (m), 1590 (m), 1503 (s), 1460 (m), 1440 (s), 1414 (m), 1295 (m), 1196 (m), 1176 (m), 1138 (w), 1119 (m), 1106 (m), 1073 (w), 1022 (m), 1008 (m), 982 (s), 905 (m), 845 (m), 765 (s), 753 (m), 735 (m), 697 (m) HRMS (ESI): Calcd for C 13 H8F5NO (M+H) + 289.0526, found 290.0589.

[0132] [Example 1-2] The reaction and post-treatment were carried out in the same manner as in Example 1-1, except that 1.2 mmol (115.3 mg) of t-BuONa was used instead of cesium carbonate, to obtain 286.1 mg of the target compound (yield >99%).

[0133] [Examples 1-3] A 30 mL reaction flask equipped with a reflux column was charged with 20.05 mmol (28.8 mg) of Pd(DBA), 0.075 mmol (35.0 mg) of RuPhos, and 1.2 mmol (219.7 mg) of pentafluoroaniline. The system was then purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added and stirred at room temperature for 5 minutes. 0.923 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was then added and stirred at room temperature for 5 minutes. The mixture was then heated and stirred in a 110 °C bath for 3 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 97 / 3) to separate and isolate the target fraction. Finally, the solvent was removed from the collected fractions at 80°C under reduced pressure to obtain 287.3 mg of the target product (yield >99%).

[0134] [Examples 1-4] The reaction and post-treatment were carried out in the same manner as in Example 1-3, except that 0.2 mmol (93.3 mg) of RuPhos was used and the reaction time was changed to 5 hours, to obtain 286.0 mg of the target product (yield >99%).

[0135] [Examples 1-5] The reaction and post-treatment were carried out in the same manner as in Example 1-3, except that 0.075 mmol (31.8 mg) of t-BuXPhos represented by the following formula (L4) was used instead of RuPhos and the reaction time was changed to 5 hours, thereby obtaining 243.9 mg of the target compound (yield 84%).

[0136] [ka] (In the formula, i-Pr represents an isopropyl group, and t-Bu represents a t-butyl group.)

[0137] [Examples 1-6] The reaction and post-treatment were carried out in the same manner as in Example 1-3, except that 0.075 mmol (30.8 mg) of SPhos represented by the following formula (L1) was used instead of RuPhos and the reaction time was changed to 5 hours, thereby obtaining 246.0 mg of the target product (yield 85%).

[0138] [ka] (In the formula, Me represents a methyl group, and Cy represents a cyclohexyl group.)

[0139] [Examples 1-7] The reaction and post-treatment were carried out in the same manner as in Example 1-3, except that 0.075 mmol (23.4 mg) of t-BuMePhos represented by the following formula (L5) was used instead of RuPhos and the reaction time was set to 5 hours, thereby obtaining 246.3 mg of the target compound (yield 85%).

[0140] [ka] (In the formula, Me represents a methyl group, and t-Bu represents a t-butyl group.)

[0141] [Examples 1-8] The reaction and post-treatment were carried out in the same manner as in Example 1-3, except that 0.075 mmol (22.4 mg) of JhonPhos represented by the following formula (L6) was used instead of RuPhos and the reaction time was set to 5 hours, thereby obtaining 268.2 mg of the target product (yield 95%).

[0142] [ka] (In the formula, t-Bu represents a t-butyl group.)

[0143] [Examples 1-9] The reaction and post-treatment were carried out in the same manner as in Example 1-3, except that 0.075 mmol (26.3 mg) of CyJhonPhos represented by the following formula (L7) was used instead of RuPhos and the reaction time was 5 hours, thereby obtaining 208.9 mg of the target product (yield 73%).

[0144] [ka] (In the formula, Cy represents a cyclohexyl group.)

[0145] Table 1 shows a summary of the above Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-7.

[0146] [Table 1] (Example 1-4: Amount of RuPhos used: 0.2 mmol)

[0147] (2) Reaction of pentafluoroaniline with aryl halides [ka]

[0148] [Comparative Example 1-8] A 30 mL reaction flask equipped with a reflux column was charged with 20.05 mmol (28.8 mg) of Pd(DBA), 0.075 mmol (35.0 mg) of RuPhos, and 1.2 mmol (219.7 mg) of pentafluoroaniline. The system was then purged with nitrogen. 4 mL of dioxane and 1 mmol (96.1 mg) of fluorobenzene were added and stirred at room temperature for 5 minutes. Next, 0.923 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was added and stirred at room temperature for 5 minutes. The mixture was then heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). Liquid chromatography was performed using a small amount of the solution collected from the flask. In addition to the peaks attributable to the starting materials, numerous other prominent peaks unattributable to the target product were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 97 / 3) to separate and separate fractions other than the fraction containing mainly the raw material. Finally, the solvent was removed from the collected fractions under reduced pressure at 80°C to obtain a solid. 1 The H-NMR spectrum showed numerous peaks that could not be assigned to either the raw material or the target product. This mixture contained multiple by-products, and it was determined that it would be difficult to isolate the target product from it, so no further purification was attempted.

[0149] [Examples 1-10] A 30 mL reaction flask equipped with a reflux column was charged with 20.05 mmol (28.8 mg) of Pd(DBA), 0.075 mmol (35.0 mg) of RuPhos, and 1.2 mmol (219.7 mg) of pentafluoroaniline. The system was then purged with nitrogen. 4 mL of dioxane and 1 mmol (112.6 mg) of chlorobenzene were added and stirred at room temperature for 5 minutes. 0.923 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was then added and stirred at room temperature for 5 minutes. The mixture was then heated and stirred in a 110 °C bath for 3 hours (internal temperature: 92 °C). During the reaction, a small amount of the solution was sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 97 / 3) to separate and isolate the target fraction. Finally, the solvent was removed from the collected fractions at 80° C. under reduced pressure to obtain 195.7 mg of the target product (yield 81%).

[0150] [Examples 1-11] The reaction and post-treatment were carried out in the same manner as in Example 1-10, except that 1 mmol (157.0 mg) of bromobenzene was used instead of chlorobenzene and the reaction time was changed to 5 hours, to obtain 256.6 mg of the target product (yield >99%).

[0151] [Examples 1-12] The reaction and post-treatment were carried out in the same manner as in Example 1-10, except that toluene was used instead of dioxane, 1.2 mL of a 1 mol / L LHMDS toluene solution (equivalent to 1.2 mmol of LHMDS) was used instead of a 1.3 mol / L LHMDS tetrahydrofuran solution, and the reaction time was 5 hours, to obtain 243.5 mg of the target product (yield 94%).

[0152] [Examples 1-13] The reaction and post-treatment were carried out in the same manner as in Example 1-10, except that 1 mmol (204.0 mg) of iodobenzene was used instead of chlorobenzene, to obtain 257.4 mg of the target compound (yield >99%).

[0153] [Examples 1-14] [ka]

[0154] A 30 mL reaction flask equipped with a reflux column was charged with 20.05 mmol (28.8 mg) of Pd(DBA), 0.075 mmol (35.0 mg) of RuPhos, 1.2 mmol (219.7 mg) of pentafluoroaniline, and 1 mmol (175.0 mg) of 4-fluorobromobenzene. The system was then purged with nitrogen. 4 mL of dioxane was added and stirred for 5 minutes. 0.923 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was then added. The mixture was stirred at room temperature for 5 minutes, followed by heating and stirring in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 97 / 3) to separate and isolate the target fraction. Finally, the solvent was removed from the collected fractions at 50° C. under reduced pressure to obtain 242.9 mg of the target product (yield 88%). 1H NMR (500.13 MHz, CDCl3): δ = 5.39 (brs, 1H), 6.84 (m, 2h), 7.00 (brt, 2H) 13 C NMR (125.77 MHz, CDCl3): δ = 116.0, 116.2, 118.9, 119.0,138.3, 157.8, 159.7 19 F NMR (470.53 MHz, CDCl3): δ -165.6 (brt, 1F), -164.0 (brdt, F), 151.8 (brd, 2F), 122.6 (brs, 1 F); IR (neat)ν~ = 3425.6 (m), 1656.9 (w), 1504.5 (s), 1205.5 (s), 1153.4 (m), 1101.4 (m), 1008.8 (s), 997.9 (s), 827.5 (s), 748.4 (m), 717.5 (m), 702.1 (m), 669.3 (m), 636.5 (m)

[0155] Table 2 shows a summary of the above Examples 1-10 to 1-14 and Comparative Example 1-8.

[0156] [Table 2]

[0157] (3) Reaction of mono- and tetrafluoroanilines with 4-bromoanisole [ka]

[0158] [Examples 1-15] A 30 mL reaction flask equipped with a reflux column was charged with 20.05 mmol (28.8 mg) of Pd(DBA) and 0.075 mmol (35.0 mg) of RuPhos. The system was then purged with nitrogen. 4 mL of dioxane was added, followed by 1.2 mmol (133.3 mg) of 2-fluoroaniline and 1 mmol (187.0 mg) of 4-bromoanisole. The mixture was stirred at room temperature for 5 minutes. 0.923 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was then added. The mixture was stirred at room temperature for 5 minutes, followed by heating and stirring in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, a small amount of the solution was sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 97 / 3) to separate and isolate the target fraction. Finally, the solvent was removed from the collected fractions at 80° C. under reduced pressure to obtain 217.6 mg of the target product (yield 98%). 1H NMR (500.13 MHz, CDCl3): δ = 3.84 (s, 3H), 5.68 (brs, 1H), 6.77-6.79 (m, 1H), 6.93 (d, J = 9.0 Hz, 2H), 7.00 (brt, 1H), 7.07-7.12 (m, 2H); 7.15 (d, J = 9.0 Hz, 2H) 13 C NMR (125.77 MHz, CDCl3): δ = 55.7, 114.9, 115.2, 115.3, 119.1, 123.3, 124.5, 134.1, 134.7, 152.4, 156.1 19 F NMR (470.53 MHz, CDCl3): δ -136.1 (brs); IR (neat) ν~ = 3382 (m), 3010 (w), 2938 (w), 2906 (w), 2838 (w), 1617 (m), 1585 (w), 1504 (s), 1477 (m), 1464 (m), 1455 (m), 1442 (m), 1332 (m), 1296 (m), 1288 (m), 1255 (m), 1233 (s), 1222 (s), 1180 (s), 1171 (m), 1109 (m), 1095 (s), 1029 (s), 1008 (m), 925 (w), 917 (w), 886 (w), 838 (m), 821 (s), 757 (m), 742 (s), 707 (m), 696 (w) HRMS (ESI): Calcd for C 13 H 12 FNO (M+H) + 217.0903, found 218.0963.

[0159] [Example 1-16] The reaction and post-treatment were carried out in the same manner as in Example 1-15, except that 1.2 mmol (133.3 mg) of 3-fluoroaniline was used instead of 2-fluoroaniline, to obtain 210.6 mg of the target product (yield 97%). 1H NMR (500.13 MHz, CDCl3): δ = 3.79 (s, 3H), 5.57 (brs, 1H), 6.47 (ddd, J = 8.3, 2.3, 0.9 Hz, 1H), 6.56 (dt, J = 11.4, 2.3 Hz, 1H), 6.59 (ddd, J = 8.3, 2.2, 0.9 Hz, 1H), 6.87 (d, J = 8.9, 6.7 Hz, 2H), 7.07 (dd, J = 8.9, 6.7 Hz, 2H), 7.11 (td, J = 8.3, 6.7 Hz, 2H) 13 C NMR (125.77 MHz, CDCl3): δ = 55.7, 101.9, 105.9, 111.0, 1145.0, 123.6, 130.6, 134.8, 147.7, 156.2, 164.2 19 F NMR (470.53 MHz, CDCl3): δ = -113.7 (ms) IR (neat): ν~ = 3361 (m), 3043 (w), 2966(w), 2915 (w), 2839 (w), 1600 (s), 1584 (m), 1526 (m), 1506 (s), 1490 (s), 1465 (m), 1334 (m), 1290 (m), 1251 (m), 1181 (w), 1174 (w), 1168 (w), 1138 (s), 1109 (s), 1072 (w), 827 (m), 755 (m), 742 (s) HRMS (ESI): Calcd for C 13 H 12 FNO (M+H) + 217.0903, found 218.0969.

[0160] [Example 1-17] The reaction and post-treatment were carried out in the same manner as in Example 1-15, except that 1.2 mmol (133.3 mg) of 4-fluoroaniline was used instead of 2-fluoroaniline, to obtain 161.7 mg of the target product (yield 74%). 1 H NMR (500.13 MHz, CDCl3): δ = 3.79 (s, 3H), 5.36 (brs, 1H), 6.84-7.25 (m, 8H) 13 C NMR (125.77 MHz, CDCl3): δ = 55.8, 115.0, 116.0, 118.0, 121.4, 136.8, 141.4, 155.3, 157.4 19 F NMR (470.45 MHz, CDCl3): δ = -125.6(s) IR (neat): ν~ = 3392 (w), 3037 (w), 2955 (w), 2934 (w), 2834 (w), 1603 (w), 1590 (w), 1497 (s), 1464 (m), 1442 (m), 1316 (m), 1295 (m), 1245 (m), 1213 (s), 1179 (m), 1154 (w), 1109 (w), 1098 (w), 1034 (m), 818 (s), 773 (m), 696 (w) HRMS (ESI): Calcd for C 13 H 12 FNO (M+H) + 217.0903, found 218.0965.

[0161] [Example 1-18] The reaction and post-treatment were carried out in the same manner as in Example 1-15, except that 1.2 mmol (154.9 mg) of 2,6-difluoroaniline was used instead of 2-fluoroaniline, to obtain 216.2 mg of the target product (yield 92%). 1 H NMR (500.13 MHz, CDCl3): δ = 3.77 (s, 3H), 5.37 (brs, 1H), 6.81 (brs, 4H), 6.91-6.93 (m, 3H) 13C NMR (125.77 MHz, CDCl3): δ = 55.8, 112.0, 114.6, 118.8, 121.0, 121.9, 137.1, 154.9, 156.1 19 F NMR (470.45 MHz, CDCl3): δ = -123.4 (m) IR (neat): ν~ = 3411 (w), 2935 (w), 2835 (w), 1623 (w), 1598 (w), 1504 (s), 1456 (m), 1406 (w), 1294 (m), 1233 (s), 1179 (m), 1111 (w), 1060 (w), 1033 (m), 999 (s), 818 (m), 778 (w), 758 (m), 728 (w), 707 (w), 695 (w) HRMS (ESI): Calcd for C 13 H 11 F2NO (M+H) + 235.0809, found 236.0867.

[0162] [Example 1-19] A 30 mL reaction flask equipped with a reflux column was charged with 20.05 mmol (28.8 mg) of Pd(DBA), 0.075 mmol (35.0 mg) of RuPhos, and 1.2 mmol (176.5 mg) of 2,4,6-trifluoroaniline, and the system was purged with nitrogen. 4 mL of dioxane was added, followed by 1 mmol (187.0 mg) of 4-bromoanisole. After stirring for 5 minutes, 0.923 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was added and the mixture was heated and stirred in a 110 °C bath for 4 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 97 / 3) to separate and isolate the target fraction. Finally, the solvent was removed from the collected fractions at 80° C. under reduced pressure to obtain 237.4 mg of the target product (yield 91%). 1 H NMR (500.13 MHz, CDCl3): δ = 3.76 (s, 3H), 5.14 (brs, 1H), 6.72-6.75 (m, 3H), 6.80 (d, J = 9.0 Hz, 2H) 13 C NMR (125.77 MHz, CDCl3): δ = 55.8, 100.9, 114.7, 117.4, 117.9, 137.6, 154.8, 156.7, 157.8 19 F NMR (470.45 MHz, CDCl3): δ = -119.8 (brs), -116.9 (brs) IR (neat): ν~ = 3396 (w), 3083 (w), 2913 (w), 2837 (w), 1636 (w), 1608 (w), 1504 (s), 1442 (m), 1288 (w), 1235 (s), 1173 (m), 1116 (s), 1030 (s), 996 (s), 837 (s), 817 (s) HRMS (ESI): Calcd for C13 H 10 F3NO (M+H) + 253.0714, found 254.0772.

[0163] [Example 1-20] The reaction and post-treatment were carried out in the same manner as in Example 1-19, except that 1.2 mmol (154.9 mg) of 2,3,5,6-tetrafluoroaniline was used instead of 2,4,6-trifluoroaniline, to obtain 243.9 mg of the target product (yield 90%). 1 H NMR (500.13 MHz, CDCl3): δ = 3.79 (s, 3H), 5.56 (brs, 1H), 6.63 (tt, J = 10.0, 7.1Hz, 1H), 6.84 (d, J = 8.9 Hz, 2H), 6.92 (brd, J = 8.9 Hz, 2H) 13 C NMR (125.77 MHz, CDCl3): δ = 55.8, 96.8, 114.6, 121.1, 124.6, 134.9, 139.4, 146.8, 156.2 19 F NMR (470.45 MHz, CDCl3): δ = -154.00, -154.08 (m, 2F), -141.49, -141.57 (m, 2F); IR (neat): ν~ = 3398 (m), 3083 (w), 2927 (w), 2845 (w), 1646 (m), 1613 (w), 1526 (s), 1507 (s), 1497 (s), 1456 (s), 1409 (m), 1294 (m), 1261 (m), 1241 (s), 1172 (s), 1120 (m), 1112 (m), 1077 (m), 1031 (m), 949 (s), 820 (s), 804 (m), 769 (m), 726 (m), 709 (m), 691 (m) HRMS (ESI): Calcd for C 13 H9F4NO (M+H) +271.0620, found 272.0694.

[0164] The results of Examples 1-15 to 1-20 are summarized in Table 3. The results of Example 1-3 are also shown.

[0165] [Table 3]

[0166] [Example 1-21] A 30 mL reaction flask equipped with a reflux column was charged with 20.2 mmol (115.0 mg) of Pd(DBA), 0.3 mmol (140.0 mg) of RuPhos, and 2.5 mmol (656.3 mg) of 4,4'-diaminooctafluorobiphenyl, and the system was purged with nitrogen. To this was added 8 mL of dioxane, followed by 4.8 mmol (753.6 mg) of bromobenzene. After stirring for 5 minutes, 3.7 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 4.8 mmol of LHMDS) was added and the mixture was heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 90 / 10) to separate and isolate the target fraction. Finally, the solvent was removed from the collected fractions at 80°C under reduced pressure to obtain 0.88 g of the target product (yield 92%). 1 H NMR (500.13 MHz, CDCl3): δ = 5.45 (brs, 1H), 6.85 (brd, 2H), 7.02 (brt, 1H), 7.30 (brt, 2H) 13 C NMR (125.77 MHz, CDCl3): δ = 116.7, 122.2, 129.5, 142.3 19 F NMR (470.53 MHz, CDCl3): δ = -164.9 (brt, 1F), -164.1 (dt, J = 22.1, 5.8 Hz, 2F), -150.7 (brd, 2F), IR (neat): ν~ = 3408.2 (m), 1602.9 (m), 1521.8 (s), 1500.6 (s), 1483.3 (s), 1462.0 (S), 1421.54 (S), 1315.5 (m), 1292.31 (m)

[0167] [Example 1-22] The reaction and post-treatment were carried out in the same manner as in Example 1-21, except that 4.8 mmol (1023.0 mg) of 1-bromo-4-t-butylbenzene was used instead of bromobenzene, to obtain 1.07 g of the target product (yield 91%). 1 H NMR (500.13 MHz, Acetone): δ = 1.31 (s, 18H), 7.03 (d, J = 8.7 Hz, 4H), 7.36 (d, J = 8.7 Hz, 4H), 7.78 (brs, 2H) 1313C NMR (125.77 MHz, Acetone): δ = 31.9, 34.8, 98.5, 118.9, 125.9, 126.6, 140.4, 141.2, 146.0 19 19F NMR (470.45 MHz, Acetone): δ = -152.67 (brd, F), -143.45 - (-143.1) (m, 4F) IR (neat): ν~ = 3406 (w), 3394 (w), 2966 (w), 2909 (w), 2869 (w), 1651 (m), 1610 (m), 1487 (s), 1449 (m), 1403 (w), 1394 (w), 1364 (w), 1291 (w), 1263 (m), 1243 (m), 1191 (w), 1125 (w), 1115 (w), 1082 (m), 996 (m), 976 (s), 829 (m), 821 (s), 728 (m), 723 (s) HRMS (ESI): Calcd for C 32 H 28 F8N2(M + H) + 592.2125, found 593.2170.

[0168] [Example 1 - 23] A 30 mL reaction flask equipped with a reflux column was charged with 20.2 mmol (115.0 mg) of Pd(DBA), 0.3 mmol (140.0 mg) of RuPhos, 2.5 mmol (656.3 mg) of 4,4'-diaminooctafluorobiphenyl, and 4.8 mmol (1388.2 mg) of 4-bromo-4'-t-butylbiphenyl. The system was then purged with nitrogen. 8 mL of dioxane was added and stirred for 5 minutes. 3.7 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 4.8 mmol of LHMDS) was then added and heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 90 / 10) to separate and isolate the target fraction. Finally, the solvent was removed from the collected fractions at 80° C. under reduced pressure to obtain 892.6 mg of the target product (yield 60%). 1 H NMR (500.13 MHz, THF): δ = 1.38 (s, 18H), 7.09 (brd, 4H), 7.47 (brd, 4H), 7.56 (brt, 8H), 8.07 (brs, 2H) 13C NMR (125.77 MHz, THF): δ =31.9, 34.8, 98.5, 118.9, 125.9, 126.6, 140.4, 141.2, 146.0 19 F NMR (470.45 MHz, THF): δ = -152.14 (brd, F), -143.24, -143.29 (m, 4F) IR (neat): ν~ = 3421 (w), 3030 (w), 2960 (w), 2902 (w), 2866 (w), 1651 (m), 1608 (m), 1510 (s), 1484 (s), 1457 (s), 1452 (s), 1394 (w), 1366 (w), 1359 (w), 1314 (w), 1293 (w), 1262 (m), 1238 (w), 1198 (w), 1184 (w), 1121 (w), 1114 (w), 1085 (m), 997 (m), 972 (m), 816 (s), 778(w), 746 (w), 739 (w), 721 (s), 667 (w) HRMS (ESI): Calcd for C 44 H 36 F8N2(M+H) + 744.2751, found 745.2794.

[0169] [Example 1-24] The reaction and post-treatment were carried out in the same manner as in Example 1-23, except that 4.8 mmol (993.9 mg) of 1-bromonaphthalene was used instead of 4-bromo-4'-t-butylbiphenyl, to obtain 617.0 mg of the target product (yield 68%). 1 H NMR (500.13 MHz, DMF): δ = 7.27 (brd, 2H), 7.51 (t, J = 7.8 Hz, 2H), 7.59-7.64 (m, 4H), 7.74 (brd, 2H), 8.00-8.03 (m, 2H), 8.47-8.50 (m, 2H), 8.82 (brs, 2H) 13C NMR (125.77 MHz, DMF): δ = 98.3, 116.5, 124.0, 124.6, 126.8, 126.9, 127.4, 127.7, 128.6, 129126.9, 127.4, 127.7, 128.6, 129, 135.6, 141.4, 146.1 19 F NMR (470.45 MHz, DMF): δ =-153.18 (brd, J = 13.9 Hz, 4F), -143.45-(-143.35) (m, 4F) IR (neat): ν~ = 3396 (w), 3373 (w), 3063 (w), 1653 (m), 1595 (m), 1577 (w), 1522 (m), 1496 (s), 1489 (s), 1466 (s), 1430 (m), 1401 (m), 1391 (m), 1274 (m), 1267 (m), 1251 (w), 1241 (w), 1168 (w), 1154 (w), 1131 (w), 1106 (m), 1088 (w), 1075 (w), 1040 (w), 1017 (w), 986 (s), 955 (s), 794 (s), 772 (s), 727 (s) HRMS (ESI): Calcd for C 32 H 16 F8N2(M+H) + 580.1186, found 581.1249.

[0170] [Example 1-25] The reaction and post-treatment were carried out in the same manner as in Example 1-23, except that 4.8 mmol (993.9 mg) of 2-bromonaphthalene was used instead of 4-bromo-4'-t-butylbiphenyl, to obtain 770.2 mg of the target product (yield 53%). 1 H NMR (500.13 MHz, DMSO): δ = 7.23-7.35 (m, 6H), 7.43 (brt, 2H), 7.77 (brd, 2H), 7.83 (brt, 4H), 9.00 (brs, 2H) 13 C NMR (125.77 MHz, DMSO): δ = 98.2, 111.9, 119.9, 124.2, 124.4, 126.9, 127.0, 128.0, 129.0, 129.4, 134.3, 140.3, 140.9, 144.9 19 F NMR (470.45 MHz, DMSO): δ =-148.08 (brd, 4F), -140.33 (brd, 4F) IR (neat): ν~ = 3412 (m), 3054 (w), 1651 (m), 1627 (s), 1602 (m), 1591 (w), 1506 (s), 1484 (s), 1456 (s), 1425 (m), 1290, 1276, 1264, 1225 (s), 1183 (m), 1132 (m), 1091 (s), 999 (s), 967 (s), 846 (s), 823 (s), 746 (s), 732 (s), 708 (m), 641 (m) HRMS (ESI): Calcd for C 32 H 16 F8N2(M+H) + 580.1186, found 581.1249.

[0171] [Example 1-26] The reaction and post-treatment were carried out in the same manner as in Example 1-23, except that 4.8 mmol (1556.2 mg) of 4-bromotriphenylamine was used instead of 4-bromo-4'-t-butylbiphenyl, to obtain 1417.3 mg of the target product (yield 87%). 1 H NMR (500.13 MHz, Acetone): δ = 6.98 (t, J = 7.3, 4H), 7.05 (m, 16H), 7.26 (dd, J = 8.6, 7.3 Hz, 8H), 8.86 (brs, 2H) 13C NMR (125.77 MHz, Acetone): δ = 99.1, 120.9, 123.7, 124.7, 126.2, 127.3, 130.7, 139.4, 141.7, 143.8, 146.5, 149.6 19 F NMR (470.45 MHz, Acetone): δ = -152.72 (brd, J = 13.9 Hz, 4F), -143.27 (m, 4F) IR (neat): ν~ = 3394 (w), 3023 (w), 1649 (m), 1586 (m), 1485 (s), 1410 (m), 1333 (w), 1319 (w), 1293 (w), 1273 (m), 1260 (m), 1235 (m), 1175 (w), 1156 (w), 1152 (w), 1132 (w), 1118 (w), 1112 (w), 1085 (m), 995 (m), 974 (m), 968 (m), 899 (w), 891 (w), 826 (m), 817 (m), 749 (s), 739 (m), 722 (m), 714 (m), 693 (s) HRMS (ESI): Calcd for C 48 H 30 F8N4(M+H) + 814.2343, found 814.2312.

[0172] [Example 1-27] The reaction and post-treatment were carried out in the same manner as in Example 1-23, except that 4.8 mmol (1781.9 mg) of 4-iodotriphenylamine was used instead of 4-bromo-4'-t-butylbiphenyl, to obtain 1101.3 mg of the target product (yield 68%).

[0173] [Example 1-28] The reaction and post-treatment were carried out in the same manner as in Example 1-23, except that 4.8 mmol (1921.5 mg) of 4-bromo-4'-(diphenylamino)biphenyl was used instead of 4-bromo-4'-t-butylbiphenyl, to obtain 1903.1 mg of the target product (yield 99%).

[0174] [Example 1-29] The reaction and post-treatment were carried out in the same manner as in Example 24, except that 4.8 mmol (1897.4 mg) of 2-bromo-9,9'-spirobi[9H-fluorene] was used instead of 4-bromo-4'-t-butylbiphenyl, to obtain 1.88 g of the target product (yield 98%). 1 H NMR (500.13 MHz, Acetone): δ = 6.39 (brs, 2H), 6.62 (dd, J = 7.5, 1.0 Hz, 2H), 6.73 (dd, J = 7.5, 1.0 Hz, 4H), 7.05-7.09 (m, 4H), 7.16 (td, J = 7.5, 1.0 Hz, 4 H), 7.36 (td, J = 7.5, 1.0 Hz, 2H), 7.40 (td, J = 7.5, 1.0 Hz, 4 H), 7.82 (s, 2H), 7.89 (brdd, 4 H) 7.97 (brd, J = 7.5, 4 H) 13 C NMR (125.77 MHz, Acetone): δ = 66.9, 99.0, 114.6, 118.0, 120.5, 121.1, 121.5, 124.5, 124.8, 125.1, 127.9, 128.6, 128.88, 136.9, 141.2, 142.7, 142.8, 142.9, 145.8, 149.4, 149.9, 151.0 19 F NMR (470.45 MHz, Acetone): δ = -152.3 (brd, 4F), -143.2 (m, 4F) IR (neat): ν~ = 3391 (w), 3063 (w), 3042 (w), 3015 (w), 1653 (m), 1614 (m), 1488 (s), 1446 (s), 1346 (w), 1299 (m), 1290 (m), 1284 (m), 1267 (m), 1215 (m), 1167 (w), 1153 (w), 1120 (m), 1089 (m), 1078 (m), 979 (m), 967 (m), 851 (w), 821 (m), 750 (s), 735 (s), 725 (s), 717 (s), 636 (m) HRMS (ESI): Calcd for C 62 H 32 F8N2(M+H) + 956.2438, found 812.4212.

[0175] [Example 1-30] [ka]

[0176] A 100 mL reaction flask equipped with a reflux column was charged with 0.45 mmol (367.5 mg) of Pd(dppf)Cl2, 45 mmol (4416.3 mg) of potassium acetate, 15 mmol (4833.2 mg) of 3-bromo-N-phenylcarbazole, and 11 mmol (4190.0 mg) of bis(pinacolato)diboron. The system was then purged with nitrogen. 150 mL of N,N-dimethylformamide was added and stirred for 5 minutes, followed by heating and stirring in a 90°C bath for 3 hours. The reaction was monitored by TLC using a small amount of reaction mixture collected from the system. The reaction mixture was cooled to room temperature, and then the solvent was removed from the cooled reaction mixture under reduced pressure to concentrate it. The concentrate was placed in a separatory funnel together with 50 mL of ion-exchanged water and washed, and then 50 mL of chloroform was added thereto for extraction. The organic layer was recovered from the separatory funnel and then dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the resulting filtrate was concentrated. The resulting concentrate was subjected to column chromatography (developing solvent: hexane / ethyl acetate = 100 / 0 → 96 / 4) to separate and collect fractions containing the target product. Finally, the solvent was removed from the collected fractions under reduced pressure to give 4.21 g of N-phenylcarbazol-3-yl-boronic acid pinacolato (yield 76%). 1 H NMR (500.13 MHz, CDCl3): δ = 1.41(s, 12H), 7.29 (ddd, J = 7.9, 6.0, 2.0 Hz, 1H), 7.37 (brd, J = 8.2 Hz, 1H), 7.40 (m, 2H), 7.48 (t, J = 7.5 Hz, 1H), 7.55 (m, 2H), 7.61 (m, 2H), 8.76 (dd, J = 8.2, 1.2 Hz, 2H), 8.18 (d, J = 7.6 Hz, 1H), 8.64 (s, 1H)

[0177] [ka]

[0178] A 50 mL reaction flask equipped with a reflux column was charged with 0.09 mmol (104.1 mg) of Pd(PPh3), 9 mmol (359.9 mg) of sodium hydroxide, 3 mmol (1107.8 mg) of N-phenylcarbazol-3-yl-boronic acid pinacolato, and 3.3 mmol (1184.7 mg) of 4-bromo-4'-iodobiphenyl. The system was then purged with nitrogen. 13.5 mL of a 2 / 1 (v / v) mixture of tetrahydrofuran and water was added and stirred for 5 minutes. After stirring, the mixture was heated and stirred in a 50°C bath for 5 hours. The reaction was monitored by TLC using a small amount of reaction mixture collected from the system. The reaction mixture was cooled to room temperature, and then the solvent was removed from the cooled reaction mixture under reduced pressure to concentrate it. The concentrate was placed in a separatory funnel together with 50 mL of ion-exchanged water and washed, and then 50 mL of tetrahydrofuran was added thereto for extraction. The organic layer was recovered from the separatory funnel and then dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the resulting filtrate was concentrated. The resulting concentrate was subjected to column chromatography (developing solvent: hexane / ethyl acetate = 100 / 0 → 96 / 4) to separate and collect fractions containing the target product. Finally, the solvent was removed from the collected fractions under reduced pressure to obtain 810 mg of 4-bromo-4'-(N-phenylcarbazol-3-yl)-biphenyl (yield 57%). 1 H NMR (500.13 MHz, CDCl3): δ = 7.30-7.33 (m, 1H), 7.43 (m, 2H), 7.50 (m, 4H), 7.57-7.70 (m, 9H), 7.79 (d, J = 8.5 Hz, 2H), 8.20 (d, J = 7.9Hz, 1H), 8.39 (brs, 1H)

[0179] A 30 mL reaction flask equipped with a reflux column was charged with 20.5 mmol (28.8 mg) of Pd(DBA), 0.75 mmol (35.0 mg) of RuPhos, and 0.5 mmol (164.1 mg) of 4,4'-diaminooctafluorobiphenyl. The system was then purged with nitrogen. 8 mL of dioxane was added, followed by 1.05 mmol (498.1 mg) of 4-bromo-4'-(N-phenylcarbazol-3-yl)-biphenyl. After stirring for 5 minutes, 0.923 mL (1.2 mmol) of a 1.3 mol / L LHMDS solution in tetrahydrofuran was added and the mixture was heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. At this time, no noticeable peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 90 / 10) to separate and isolate the target fraction. Finally, the solvent was removed from the collected fractions at 80° C. under reduced pressure to obtain 457 mg of the target product (yield 82%). 1 H NMR (500.13 MHz, CDCl3): δ = 5.94 (brs, 2H), 7.11 (brd, 2H), 7.32(brquin, 1H), 7.43 (brd, 2H), 7.48-7.51 (m, 2H), 7.60-7.66 (m, 6H), 7.70-7.72 (brm, 3H), 7.80-7.82 (m, 3H), 8.21 (brd, 2H), 8.41 (brs, 1H)

[0180] [Example 1-31] [ka]

[0181] A 100 mL reaction flask equipped with a reflux column was charged with 0.45 mmol (367.5 mg) of Pd(dppf)Cl, 45 mmol (4416.3 mg) of potassium acetate, 15 mmol (5929.5 mg) of 2-bromo-9,9'-spirobi[9H-fluorene], and 16.5 mmol (4190.0 mg) of bis(pinacolato)diboron. The atmosphere in the system was purged with nitrogen. 150 mL of N,N-dimethylformamide was added and stirred for 5 minutes. The mixture was then heated and stirred in a 90°C bath for 3 hours. The reaction was monitored by TLC using a small amount of reaction mixture collected from the system. After the reaction mixture was cooled to room temperature, the solvent was removed from the cooled reaction mixture under reduced pressure, and the concentrate was placed in a separatory funnel together with 50 mL of deionized water for washing, followed by extraction with 50 mL of chloroform, and the organic layer was recovered from the separatory funnel. The recovered organic layer was then dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the resulting filtrate was concentrated. The resulting concentrate was subjected to column chromatography (developing solvent: hexane / ethyl acetate = 100 / 0 → 96 / 4) to separate and collect fractions containing the target product. Finally, the solvent was removed from the collected fractions under reduced pressure to give 1.85 g of 9,9′-spirobi[9H-fluoren]-2-yl-boronic acid pinacolato (yield 28%). 1 H NMR (500.13 MHz, CDCl3): δ = 1.25 (s, 12H), 6.68 (brd, J = 7.5 Hz 1H), 6.71 (brd, J = 7.5 Hz, 2H), 7.09 (dt, J = 7.5, 1.1 Hz 2H), 7.11 (dt, J = 7.5, 1.1 Hz 1H), 7.18 (brs, 1H), 7.35 (dt, J = 7.5, 1.1 Hz 1H), 7.36 (dt, J = 7.5, 1.1 Hz 2H), 7.33-7.37 (m, 5H)

[0182] [ka]

[0183] A 50 mL reaction flask equipped with a reflux column was charged with 0.09 mmol (104.1 mg) of Pd(PPh3), 9 mmol (359.9 mg) of sodium hydroxide, 3 mmol (1327.1 mg) of 9,9'-spirobi[9H-fluoren]-2-yl-boronic acid pinacolato, and 3.3 mmol (1184.7 mg) of 4-bromo-4'-iodobiphenyl. The system was purged with nitrogen. 13.5 mL of a 2 / 1 (v / v) tetrahydrofuran / water mixture was added and stirred for 5 minutes. After stirring, the mixture was heated and stirred in a 50°C bath for 5 hours. The reaction was monitored by TLC using a small amount of reaction mixture collected from the system. The reaction mixture was cooled to room temperature, and then the solvent was removed from the cooled reaction mixture under reduced pressure to concentrate it. The concentrate was placed in a separatory funnel together with 50 mL of ion-exchanged water and washed, and then 50 mL of tetrahydrofuran was added thereto for extraction. The organic layer was recovered from the separatory funnel and then dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the resulting filtrate was concentrated. The resulting concentrate was subjected to column chromatography (developing solvent: hexane / ethyl acetate = 100 / 0 → 96 / 4) to separate and collect fractions containing the target product. Finally, the solvent was removed from the collected fractions under reduced pressure to obtain 836.4 mg of 2-(4'-bromobiphenyl-4-yl)-9,9'-spirobi[9H-fluorene] (yield: 51%). 1 H NMR (500.13 MHz, CDCl3): δ = 6.73 (d, J = 7.6 Hz, 1H), 6.78 (d, J = 7.6 Hz, 2H), 6.97 (s, 1H), 7.12 (brt, 3H), 7.36-7.42 (m, 5 H), 7.49 (s, 4H), 7.53 (d,2H), 7.66 (dd, J = 7.9, 1.8 Hz, 1H), 7.86 (d, J = 7.6 Hz, 2 H), 7.87 (d, J = 7.6 Hz, 1 H), 7.92 (d, J = 7.9 Hz, 1H)

[0184] A 30 mL reaction flask equipped with a reflux column was charged with 20.5 mmol (28.8 mg) of Pd(DBA), 0.75 mmol (35.0 mg) of RuPhos, and 0.5 mmol (164.1 mg) of 4,4'-diaminooctafluorobiphenyl. The system was then purged with nitrogen. To the reaction mixture was added 8 mL of dioxane, followed by 1.05 mmol (574.9 mg) of 2-(4'-bromobiphenyl-4-yl)-9,9'-spirobi[9H-fluorene]. After stirring for 5 minutes, 0.923 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was added and the mixture was heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peak attributable to the raw material decreased while the area of ​​the peak attributable to the target product increased. No prominent peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 90 / 10) to separate and isolate the target fraction. Finally, the solvent was removed from the collected fractions at 80° C. under reduced pressure to obtain 532 mg of the target product (yield 86%). 1H NMR (500.13 MHz, CDCl3): δ = 6.78 (brd, 2H), 6.83 (brd, 4H), 7.05 (brm, 6H), 7.15 (brt, 6H), 7.41 (brt, 6H), 7.54 (brm, 12H), 7.70 (brd, 2H), 7.90 (brd, 6H), 7.95 (brd, 2H), 13 C NMR (125.77 MHz, CDCl3): δ = 118.7, 120.2, 120.3, 120.5, 122.8, 124.3, 124.4, 126.9, 127.1, 127.6, 127.8, 128.0, 128.1, 135.5, 139.4, 139.7, 140.4, 140.6, 141.3, 141.6, 142.0, 18.9, 149.4, 149.8 19 F NMR (470.45 MHz, CDCl3): δ =-151.41 (brd, 4F), -140.63 (m, 4F) IR (neat): ν~ = 3387.0 (w), 3059.1 (w), 3030.2 (w), 2953.0 (w), 2926.0 (w), 2856.6 (w), 1653.0 (m), 1606.7 (m), 1485.2 (s), 1446.6 (s), 1236.4 (m), 1085.9 (m), 975.98 (m), 813.96 (s), 750.31 (s), 727.16 (s)

[0185] Table 4 shows a summary of the above Examples 1-21 to 1-31.

[0186] [Table 4]

[0187] (4) Reaction of pentafluoroaniline with 4,4'-dibromobiphenyl [ka]

[0188] [Example 1-32] A 30 mL reaction flask equipped with a reflux column was charged with 20.1 mmol (57.5 mg) of Pd(DBA), 0.15 mmol (69.8 mg) of RuPhos, and 1 mmol (312.7 mg) of 4,4'-dibromobiphenyl, and the system was purged with nitrogen. 8 mL of dioxane and 2.4 mmol (439.3 mg) of pentafluoroaniline were added and stirred for 5 minutes. After stirring, 1.84 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 2.4 mmol of LHMDS) was added and the mixture was heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 50 mL of saturated aqueous ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (eluent: hexane / ethyl acetate = 100 / 0 → 90 / 10) to separate and isolate the target fraction. Finally, the solvent was removed from the collected fractions at 80° C. under reduced pressure to obtain 451.7 mg of the target product (yield 58%). 1H NMR (500.13 MHz, DMSO): δ = 6.86 (brd, J = 8.1 Hz, 4H), 7.45 (brd, J =8.1 Hz, 4H), 8.32 (brs, 2H) 13 C NMR (125.77 MHz, DMSO): δ =116.1, 118.1, 126.9, 132.4, 137.0, 138.3, 142.3, 142.7 19 F NMR (470.45 MHz, DMSO): δ =-165.04 (brt, 2F), -163.81 (brt, 4F), -148.47 (brd, 4H) IR (neat): ν~ = 3410 (m), 3029 (w), 1611 (m), 1577 (w), 1517 (s), 1502 (s), 1482 (s) 1446 (s), 1327 (m), 1277 (m), 1238 (m), 1183 (m), 1159 (m), 1136 (m), 977 (s), 817 (s), 779 (m), 727 (m), 710 (m); HRMS (ESI)

[0189] (5) Reaction of Pentafluoroaniline with Bromobenzene: Effect of Base [ka]

[0190] [Example 1-33] The reaction and post-treatment were carried out in the same manner as in Example 1-11, except that pentafluoroaniline (1 mmol), bromobenzene (2.4 mmol), and 1.85 mL of a 1.3 mol / L LHMDS tetrahydrofuran solution (corresponding to 2.4 mmol of LHMDS) were used, to obtain 179.8 mg of the target product (yield 69%).

[0191] [Example 1-34] The reaction and post-treatment were carried out in the same manner as in Example 1-11, except that pentafluoroaniline (2.4 mmol), bromobenzene (1 mmol), and 1.85 mL of a 1.3 mol / L LHMDS tetrahydrofuran solution (corresponding to 2.4 mmol of LHMDS) were used, to obtain 193.6 mg of the target product (yield 75%).

[0192] A summary of Examples 1-33 and 1-34 is shown in Table 5. These results show that the presence of an excess of base in the system tends to decrease the yield.

[0193] [Table 5]

[0194] (6) Polymer synthesis [ka]

[0195] [Example 2-1] A 30 mL reaction flask equipped with a reflux column was charged with 20.08 mmol (46.0 mg) of Pd(DBA), 0.12 mmol (56.0 mg) of RuPhos, and 4.2 mmol (1378.3 mg) of 4,4'-diaminooctafluorobiphenyl. The system was then purged with nitrogen. 8 mL of dioxane and 10 mmol (943.6 mg) of 1,4-dibromobenzene were added and stirred for 5 minutes. 7.1 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 9.2 mmol of LHMDS) was then added and heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 100 mL of saturated aqueous ammonium chloride and 50 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 30 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was added dropwise to 500 mL of a 2 / 1 (v / v) mixture of hexane and toluene. The resulting solid was collected by filtration, and the residue was dried at 80°C under reduced pressure to obtain 0.47 g of the target product. 1 H NMR (500.13 MHz, DMSO): δ = 7.08 (brd, J = 7.7 Hz, 4H), 7.56 (brd, J = 7.7 Hz, 4H), 8.68 (brs, 2H) 13 C NMR (125.77 MHz, DMSO): δ = 97.2, 117.6, 123.9, 126.1, 127.8, 128.5, 132.9, 140.0, 140.7, 144.2 19 F NMR (470.45 MHz, DMSO): δ =-148.76 (d, J = 17.3 Hz, 4F), -140.67 (s, 4F) IR (neat): ν~ = 3421 (w), 3398 (w), 3030 (w), 1652 (m), 1610 (m), 1575 (w), 1482 (s), 1410 (m), 1394 (m), 1291 (m), 1261 (s), 1234 (s), 1183 (m), 1118 (m), 1085 (s), 995 (s), 973 (s), 938 (m), 812 (s), 721 (s)

[0196] [Example 2-2] The reaction and post-treatment were carried out in the same manner as in Example 2-1, except that 20.4 mmol (230.0 mg) of Pd(DBA) and 0.6 mmol (280.0 mg) of RuPhos were used, to obtain 1.60 g of the target product.

[0197] A summary of Examples 2-1 and 2-2 is shown in Table 6. As shown in Table 6, it is clear that the molecular weight of the resulting polymer can be controlled by changing the amount of catalyst.

[0198] [Table 6]

[0199] [ka]

[0200] [Example 2-3] [ka]

[0201] A 30 mL reaction flask equipped with a reflux column was charged with 20.5 mmol (287.5 mg) of Pd(DBA), 0.75 mmol (350.0 mg) of 4,4'-diaminooctafluorobiphenyl, 2.5 mmol (820.4 mg) of 4,4'-dibromobiphenyl, and 2.38 mmol (742.9 mg) of 4,4'-dibromobiphenyl. The system was then purged with nitrogen. 8 mL of dioxane was added and stirred for 5 minutes. 7.1 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 9.2 mmol of LHMDS) was then added and heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 100 mL of saturated aqueous ammonium chloride and 50 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 30 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was added dropwise to 500 mL of a hexane / toluene mixed solvent (2 / 1 (v / v)). The resulting solid was recovered by filtration, and the residue was dried at 80 °C under reduced pressure to obtain 1.01 g of the target product. The resulting polymer had Mw = 32,000, Mn = 15,000, and Mw / Mn = 2.13. ΔT5 was 321.6 °C, and no Tg was observed.

[0202] [Example 2-4] [ka]

[0203] A 30 mL reaction flask equipped with a reflux column was charged with 20.3 mmol (172.5 mg) of Pd(DBA), 0.45 mmol (210.0 mg) of RuPhos, 1.5 mmol (492.3 mg) of 4,4'-diaminooctafluorobiphenyl, and 1.43 mmol (572.3 mg) of 3,6-dibromo-9-phenylcarbazole, and the system was purged with nitrogen. 8 mL of dioxane was added and stirred for 5 minutes. 2.54 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 3.3 mmol of LHMDS) was then added and heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 100 mL of saturated aqueous ammonium chloride and 50 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 30 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was added dropwise to 500 mL of a hexane / toluene mixed solvent (2 / 1 (v / v)). The resulting solid was recovered by filtration, and the residue was dried at 80 °C under reduced pressure to obtain 928 mg of the target product. The resulting polymer had Mw = 12,000, Mn = 7,000, and Mw / Mn = 1.71. ΔT5 was 340.1 °C, and no Tg was observed. 1 H NMR (500.13 MHz, THF): δ = 5.39 (d, J = 8.5 Hz, 2H), 5.52 (d, J = 8.5 Hz, 2H), 5.62 (brs, H), 5.80 (brs, 4H), 6.07 (d, 2H), 7.62 (brd, J = 8.0Hz, 2H), 8.06 (brs, 2H) 13 C NMR (125.77 MHz, THF): δ = 96.7, 110.8, 113.5, 121.4, 124.6, 126.2, 127.7, 127.8, 128.2, 129.1, 129.8, 130.9, 136.0, 139.1, 139.4, 140.2, 146.3 19 F NMR (470.45 MHz, THF): δ =-151.34 (brd, 4F), -145.89 (brd, 4F) IR (neat): ν~ = 3403 (w), 3029 (w), 2927 (w), 1651 (m), 1597 (w), 1483 (s), 1460 (s), 1364 (w), 1328 (w), 1291 (w), 1282 (w), 1211 (m), 1166 (w), 1121 (w), 1080 (m), 1027 (w), 994 (m), 976 (s), 951 (m), 939 (m), 925 (w), 863 (w), 757 (m), 723 (s)

[0204] [Example 2-5] [ka]

[0205] A 30 mL reaction flask equipped with a reflux column was charged with 20.4 mmol (230.0 mg) of Pd(DBA), 0.6 mmol (280.0 mg) of RuPhos, 2 mmol (656.3 mg) of 4,4'-diaminooctafluorobiphenyl, and 1.90 mmol (670.6 mg) of 2,7-dibromo-9,9-dimethylfluorene, and the system was purged with nitrogen. 8 mL of dioxane was added and stirred for 5 minutes. 3.2 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 4.2 mmol of LHMDS) was then added and heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 100 mL of saturated aqueous ammonium chloride and 50 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 30 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was added dropwise to 500 mL of a 2 / 1 (v / v) mixed solvent of hexane and toluene. The resulting solid was collected by filtration and dried at 80°C under reduced pressure to obtain 926 mg of the target product. The resulting polymer had Mw = 20,000, Mn = 11,000, and Mw / Mn = 1.82. ΔT5 was 340.1°C, and no Tg was observed. 1 H NMR (500.13 MHz, THF): δ = 1.52 (s, 6H), 7.02 (brd, J = 8.0 Hz, 2H), 7.18 (s, 2H), 7.62 (brd, J = 8.0 Hz, 2H), 8.06 (brs, 2H) 13 C NMR (125.77 MHz, THF): δ = 26.6, 46.5, 97.1, 113.1, 117.4, 119.3, 125.0, 127.9, 128.7, 133.8, 139.9, 140.7, 145.1, 154.3 19 F NMR (470.45 MHz, THF): δ =-151.76 (brd, 4F), -142.20 (brd, 4F) IR (neat): ν~ = 3423 (w), 2958 (w), 2925 (w), 2859 (w), 1651 (m), 1613 (w), 1587 (w), 1518 (m), 1485 (s), 1464 (s), 1417 (m), 1295 (m), 1259 (w), 1239 (m), 1220 (w), 1195 (w), 1089 (m), 995 (m), 979 (s), 971 (s), 809 (m), 724 (m), 718 (m)

[0206] [Example 2-6] [ka]

[0207] A 30 mL reaction flask equipped with a reflux column was charged with 20.3 mmol (172.5 mg) of Pd(DBA), 0.45 mmol (210.0 mg) of RuPhos, 1.5 mmol (492.3 mg) of 4,4'-diaminooctafluorobiphenyl, and 1.43 mmol (480 mg) of 9,10-dibromoanthracene, and the system was purged with nitrogen. 8 mL of dioxane was added and stirred for 5 minutes. 2.54 mL of a 1.3 mol / L LHMDS solution in tetrahydrofuran (equivalent to 3.3 mmol of LHMDS) was then added and heated and stirred in a 110 °C bath for 5 hours (internal temperature: 92 °C). During the reaction, small amounts of the solution were sampled and the reaction was monitored by liquid chromatography. The area of ​​the peaks attributable to the starting material decreased while the area of ​​the peaks attributable to the target product increased. No significant peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel with 100 mL of saturated aqueous ammonium chloride and 50 mL of ethyl acetate for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous and organic layers were recovered separately. All of the recovered aqueous layers were then combined and placed in a separatory funnel, and 30 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all of the recovered organic layers were combined and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was added dropwise to 500 mL of a 2 / 1 (v / v) mixed solvent of hexane and toluene. The resulting solid was collected by filtration, and the residue was dried at 80°C under reduced pressure to obtain 928 mg of the target product. The resulting polymer had Mw=18,000, Mn=8,100, and Mw / Mn=2.22. 1 H NMR (500.13 MHz, DMSO): δ = 7.60 (brs, 2H), 8.31 (brs, 2H), 9.30 (brs, 1H) 13 C NMR (125.77 MHz, CDCl3): δ = 123.9, 126.4, 128.7, 129.3, 131.3, 135.8, 137.7, 143.5, 145.5 19 F NMR (470.53 MHz, CDCl3): δ = -160.0 (brs, 4F), -143.2 (brs, 4F) IR (neat): ν~ = 3361.9 (w), 1651.1 (m), 1485.1 (s), 1435.0 (m), 1377.2 (m), 12771.1 (w), 1178.5 (w), 1134.1 (w), 1111.0 (w), 1045.4 (w), 970.2 (s), 950.9 (m), 763.8 (s), 723.3 (s)

[0208] [2] Preparation of charge transporting compositions and charge transporting thin films [Example 3-1] 35.9 mg of the naphthyl-containing fluorinated arylamine compound represented by the following formula (H1) synthesized in Example 1-24 and 56.2 mg of the arylsulfonic acid compound represented by the following formula (D2) were weighed into a sample bottle (10 mL), and 3 g of tetrahydrofurfuryl alcohol was added and stirred at room temperature until homogenous, yielding a solution with a solid content of 3% by mass. This solution was applied to an ITO substrate using a spin coater, dried at 80°C for 1 minute in air, and then baked at 230°C for 15 minutes to produce a 50 nm-thick thin film. The ITO substrate was a glass substrate with indium tin oxide (ITO) formed on its surface to a thickness of 50 nm. This thin film was then deposited on top of a vapor deposition apparatus (vacuum degree 4.0 × 10 -5 An aluminum thin film was formed using a vapor deposition method such as HCl (Pa) to obtain a single-layer element. Vapor deposition was performed at a vapor deposition rate of 0.2 nm / sec. The thickness of the aluminum thin film was 80 nm. The arylsulfonic acid compound represented by the following formula (D2) was synthesized according to the method described in WO 2006 / 025342.

[0209] [ka]

[0210] [Example 3-2] 44 mg of the fluorinated arylamine compound having a triphenylamine group represented by the following formula (H2) synthesized in Example 1-26 and 49 mg of the arylsulfonic acid compound represented by the above formula (D2) were weighed into a sample bottle (10 mL), and 3 g of tetrahydrofurfuryl alcohol was added and stirred at room temperature until homogeneous, obtaining a solution with a solid content of 3 mass %. A single-layer element was fabricated in the same manner as in Example 3-1, except for using this solution.

[0211] [ka]

[0212] [Example 3-3] 21.6 mg of the fluorinated arylamine copolymer having a biphenyl skeleton represented by the following formula (H3) synthesized in Example 2-3 and 40 mg of the arylsulfonic acid compound represented by the above formula (D2) were weighed into a sample bottle (10 mL), 3 g of tetrahydrofurfuryl alcohol was added, and the mixture was stirred at room temperature until homogeneous, obtaining a solution with a solid content of 2 mass %. A single-layer element was fabricated in the same manner as in Example 3-1, except for using this solution.

[0213] [ka]

[0214] [Example 3-4] 36 mg of the fluorinated arylamine copolymer having a phenylcarbazole group represented by the following formula (H4) synthesized in Example 2-4 and 57 mg of the arylsulfonic acid compound represented by the above formula (D2) were weighed into a sample bottle (10 mL), and 3 g of tetrahydrofurfuryl alcohol was added and stirred at room temperature until homogeneous, obtaining a solution with a solid content of 3 mass %. A single-layer element was fabricated in the same manner as in Example 3-1, except for using this solution.

[0215] [ka]

[0216] [Examples 3-5] 34 mg of the fluorinated arylamine copolymer having a 9,9-dimethylfluorene group represented by the following formula (H5) synthesized in Example 2-5 and 59 mg of the arylsulfonic acid compound represented by the above formula (D2) were weighed into a sample bottle (10 mL), and 3 g of tetrahydrofurfuryl alcohol was added and stirred at room temperature until homogeneous, obtaining a solution with a solid content of 3 mass %. A single-layer element was fabricated in the same manner as in Example 3-1, except for using this solution.

[0217] [ka]

[0218] The current density of each of the obtained single-layer elements was measured at a driving voltage of 5 V. The results are shown in Table 7.

[0219] [Table 7]

[0220] As shown in Table 7, it is clear that the thin film containing the fluoroarylamine compound or polymer of the present invention as a charge transporting material exhibits good conductivity.

Claims

1. A composition for forming a charge-transporting thin film, comprising a charge-transporting substance consisting of a fluorine-containing aniline derivative represented by formula (T1) (excluding compounds represented by the following formulas [1] and [2]), and an organic solvent. 【Chemistry 1】 [In the formula, X 211 represents a divalent group represented by the following formula (A02-1-1): 【Chemistry 2】 Y 211 and Y 212 are the same and represent a monovalent group represented by any one of formulas (B01), (B02), (B04), (B08), (B08'), and (B18), 【Transformation 3】 【Chemistry 4】 【Transformation 5】 (In the formula, Z 101 , Z 102 , Z 104 and Z 118 each independently represents a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, or n-pentyl group; Z 108 each independently represents a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, or n-pentyl group; Ar 2 represents a single bond, a 1,4-phenylene group, or a biphenyl-4,4'-diyl group. 【Transformation 6】

2. Said Z 101 , Z 102 , Z 104 and Z 118 2. The charge-transporting thin film forming composition according to claim 1, wherein each of the groups independently represents a hydrogen atom or a t-butyl group.

3. Said Z 108 2. The charge-transporting thin film forming composition according to claim 1, wherein is a hydrogen atom.

4. 2. The composition for forming a charge-transporting thin film according to claim 1, wherein the fluorine-containing aniline derivative is represented by any one of the following formulas: 【Transformation 8】 (In the formula, t-Bu represents a t-butyl group.)

5. 2. The composition for forming a charge-transporting thin film according to claim 1, wherein the fluorine-containing aniline derivative is represented by any one of the following formulas: 【Chemistry 9】

6. 2. The charge transporting thin film forming composition according to claim 1, which contains a dopant substance.

7. A charge transporting thin film obtained from the composition for forming a charge transporting thin film according to claim 1 or 6.

8. An electronic device comprising the charge transporting thin film according to claim 7.

9. An organic electroluminescence device comprising the charge transporting thin film according to claim 7.

10. 10. The organic electroluminescence device according to claim 9, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.

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