Method for producing fluorinated aromatic secondary amine compound

Abstract

Disclosed is a method for producing a fluorinated aromatic secondary amine compound, which comprises reacting a fluorinated aromatic primary amine compound with a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudo-halogenated aromatic hydrocarbon in the presence of a catalyst containing a palladium 0-valent complex of dibenzylideneacetone, a ligand represented by formula (L), and a base. A secondary amine compound having a fluoroaryl moiety in the molecule can be easily and efficiently produced by subjecting a fluorinated aromatic amine compound to a coupling reaction with a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudo-halogenated aromatic hydrocarbon without using a special catalyst. (R1 each independently represents an alkyl group having 1-20 carbon atoms or the like, R2 to R5 each independently represent a hydrogen atom or an alkyl group having 1-20 carbon atoms or the like, and R6 to R8 each independently represent a hydrogen atom or an alkyl group having 1-20 carbon atoms or the like. > # imgabs0 #

Description

[0001] This application is a further divisional application of a divisional application filed based on a patent application with an application date of "August 1, 2019", an application number of "201980050340.6", and an invention title of "Method for Producing Fluorinated Aromatic Secondary Amine Compounds" (application date: "August 1, 2019", application number: 202310281868.2, invention title: "Method for Producing Fluorinated Aromatic Secondary Amine Compounds"). Technical Field

[0002] The present invention relates to a method for producing a fluorinated aromatic secondary amine compound. Background Art

[0003] The reaction of cross-coupling an amine using a palladium catalyst with a halide or pseudohalide to form a C-N bond can be used for the synthesis of aromatic amines and the formation of heterocycles. This cross-coupling has become an important technique in many fields such as the pharmaceutical field and the material field (Non-Patent Document 1), and research on the catalysts used in this reaction and the reaction process is also widely carried out.

[0004] On the other hand, fluorine has the highest electronegativity among all elements. Therefore, by introducing it into a molecule, the overall electronic state of the molecule can be significantly changed. Fluorine not only has the above characteristics, but also has the following characteristics: since its atomic radius is on the same order as that of a hydrogen atom, even if a fluorine atom is introduced into the molecule by substituting a hydrogen atom, compared with the case where other atoms or substituents are introduced, the change in the molecular size is suppressed.

[0005] Therefore, research on fluorides has been actively carried out, and a large number of reports on fluorides for pharmaceuticals and electronic materials have been made. 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).

[0006] Under such circumstances, as a method for synthesizing a fluoroaryl compound having an amino group, the reaction of an aromatic amine with a perfluoroarylboronic acid using copper acetate as a catalyst (Non-Patent Document 2), the reaction of N-formylaniline with perfluorobenzene in the presence of lithium hydroxide (Non-Patent Document 3), the reaction of aniline with perfluorobenzene in the presence of t-BuONa (Non-Patent Document 4), etc. have been reported. In these reactions, in both of the two raw materials supplied for the coupling reaction, the amino group as the reaction site is present on the side of the aromatic compound that does not have a fluorine atom.

[0007] There are few reported examples of the coupling reaction between fluoroarylamine compounds having a fluorine atom and an amino group and haloaryl compounds. For example, although 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, there are problems such as high catalyst price and low yield of the target product.

[0008] Prior Art Documents

[0009] Patent Documents

[0010] Patent Document 1: International Publication No. 2008 / 032617

[0011] Non-Patent Documents

[0012] Non-Patent Document 1: Chem. Rev. 2016, 116, 12564 - 12649

[0013] Non-Patent Document 2: Angew. Chem. Int. Ed. 2014, 53, 3223

[0014] Non-Patent Document 3: Journal of Fluorine Chemistry, 74(2), 177 - 9; 1995

[0015] Non-Patent Document 4: RSC Advances, 5(10), 7035 - 7048; 2015

[0016] Non-Patent Document 5: Angew. Chem. Int. Ed. 2014, 53, 3223 Summary of the Invention

[0017] Problems to be Solved by the Invention

[0018] In view of the above actual situation, the present invention has been completed, and an object thereof is to provide a method for coupling a fluorinated aromatic amine compound with a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudo-halogenated aromatic hydrocarbon without using a special catalyst, and simply and efficiently producing a secondary amine compound having a fluoroaryl moiety in the molecule.

[0019] Means for Solving the Problems

[0020] The inventors of the present invention conducted repeated and in-depth studies to achieve the above object, and as a result, found that: in the presence of a specified palladium catalyst, a specified ligand and a base, the coupling reaction of the amino group of the fluorinated aromatic amine compound with the chlorine atom, bromine atom or iodine atom or the pseudo-halogen group of the chlorinated, brominated or iodinated aromatic hydrocarbon or the pseudo-halogenated aromatic hydrocarbon proceeds efficiently, and a secondary amine compound having a fluoroaryl moiety in the molecule is selectively obtained in a high yield, thereby completing the present invention.

[0021] That is, the present invention provides:

[0022] 1. A method for producing a fluorinated aromatic secondary amine compound, the method for producing the fluorinated aromatic secondary amine compound comprising the following steps: reacting a fluorinated aromatic primary amine compound with a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudo-halogenated aromatic hydrocarbon in the presence of a catalyst, a ligand and a base, wherein the catalyst comprises a palladium(0) complex of dibenzylideneacetone, and the ligand comprises a biphenylphosphine compound represented by the following formula (L):

[0023] [Chemical formula 1]

[0024]

[0025] (In the formula, R 1 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 2 to 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, and R 6 to R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an NR 9 2 group, and R 9 each independently represents an alkyl group having 1 to 20 carbon atoms.)

[0026] 2. The method for producing a fluorinated aromatic secondary amine compound according to 1, wherein the catalyst is a palladium(0) complex of dibenzylideneacetone, and the ligand is a biphenylphosphine compound represented by the formula (L).

[0027] 3. The method for producing a fluorinated aromatic secondary amine according to 1 or 2, wherein each of the R 1 is independently a branched or cyclic alkyl group having 3 to 20 carbon atoms in which the carbon atom bonded to the phosphorus atom is a secondary or tertiary carbon atom.

[0028] 4. The method for producing a fluorinated aromatic secondary amine according to 3, wherein each of the R 1 is cyclohexyl or tert-butyl.

[0029] 5. The method for producing a fluorinated aromatic secondary amine according to any one of 1 to 4, wherein each of the R 2 and R 5 independently represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, each of the R 3 and R 4 is a hydrogen atom, and each of the R 6 to R 8 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0030] 6. Process for producing a fluorinated aromatic secondary amine according to any one of 1 to 5, wherein the biphenylphosphine compound represented by the formula (L) is a biphenylphosphine compound represented by any one of the following formulas (L1) to (L4),

[0031] [Chemical formula 2]

[0032]

[0033] (In the formula, Me means methyl, i-Pr means isopropyl, Cy means cyclohexyl, and t-Bu means tert-butyl.)

[0034] 7. Process for producing a fluorinated aromatic secondary amine according to any one of 1 to 6, wherein the palladium(0) complex of dibenzylideneacetone is bis(dibenzylideneacetone)palladium(0),

[0035] 8. Process for producing a fluorinated aromatic secondary amine according to any one of 1 to 7, wherein the fluorinated aromatic primary amine compound is a fluorinated aromatic primary monoamine compound or a diamine compound having two or more fluorine atoms in the molecule,

[0036] 9. Process for producing a fluorinated aromatic secondary amine according to any one of 1 to 8, wherein the chlorinated, brominated or iodinated aromatic hydrocarbon is a monochloroaromatic hydrocarbon or a dichloroaromatic hydrocarbon, a monobromoaromatic hydrocarbon or a dibromoaromatic hydrocarbon, or a monoiodoaromatic hydrocarbon or a diiodoaromatic hydrocarbon,

[0037] 10. A fluoroaniline derivative represented by the formula (T1) or (T2) (however, compounds represented by the following formulas [1] to

[13] are excluded.)

[0038] [Chemical formula 3]

[0039]

[0040] [In the formula, X 211 represents a divalent group represented by any one of the formulas (A01-1) to (A09),

[0041] [Chemical formula 4]

[0042]

[0043] (In the formula, L 01 represents -S-, -O-, -CO-, -CH2-, -(CH2)2-, -C(CH3)2-, -CF2-, -(CF2)2-, -C(CF3)2-, fluoren-9,9-diyl, -NH- or -NZ 10 -,

[0044] L 02 and L 03 each independently represent a hydrogen atom, optionally substituted by Z11 A substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkenyl group having 2 to 20 carbon atoms, or which may be substituted by Z 12 A substituted aryl group having 6 to 20 carbon atoms,

[0045] L 04 represents a hydrogen atom, a substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkenyl group having 2 to 20 carbon atoms, or which may be substituted by Z 11 A substituted aryl group having 6 to 20 carbon atoms, 12 or

[0046] Z′ represents a substituent of an aromatic ring, and each independently represents a substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkenyl group having 2 to 20 carbon atoms, or which may be substituted by Z 11 A substituted aryl group having 6 to 20 carbon atoms, 12 or

[0047] Z 01 ~Z 09 represents a substituent of an aromatic ring, and each independently represents a chlorine atom, a bromine atom, a nitro group, a cyano group, a substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkenyl group having 2 to 20 carbon atoms, or which may be substituted by Z 11 A substituted aryl group having 6 to 20 carbon atoms, 12 or

[0048] Z 10 represents a substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkenyl group having 2 to 20 carbon atoms, or which may be substituted by Z 11 A substituted aryl group having 6 to 20 carbon atoms, 12 or

[0049] Z 11 each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group or a substituted aryl group having 6 to 20 carbon atoms, 13 or

[0050] Z 12 each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 13 or a substituted alkenyl group having 2 to 20 carbon atoms, 13 or

[0051] Z 13 represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group or a cyano group,

[0052] 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 represent the number of fluorine atoms substituted on the aromatic ring.

[0053] 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 represent the number of Z substituted on the aromatic ring. 01 ~Z 09 of.

[0054] a 75 and a 76 represent the number of Z' substituted on the aromatic ring.

[0055] a 11 is an integer from 2 to 4, a 12 is an integer from 0 to 2, and satisfies a 11 +a 12 ≤4.

[0056] a 13 is an integer from 2 to 4, a 14 is an integer from 0 to 2, and satisfies a 13 +a 14 ≤4.

[0057] a 21 and a 23 are each independently an integer from 1 to 4, a 22 and a 24 are each independently an integer from 0 to 3, and satisfy a 21 +a 22 ≤4 and a 23 +a 24 ≤4.

[0058] a 31 and a 33Each independently is an integer from 1 to 4, a 32 and a 34 Each independently is an integer from 0 to 3, and satisfies a 31 + a 32 ≤ 4 and a 33 + a 34 ≤ 4,

[0059] a 41 is an integer from 1 to 6, a 42 is an integer from 0 to 5, and satisfies a 41 + a 42 ≤ 6,

[0060] a 51 is an integer from 1 to 8, a 52 is an integer from 0 to 7, and satisfies a 51 + a 52 ≤ 8,

[0061] a 61 is an integer from 1 to 8, a 62 is an integer from 0 to 7, and satisfies a 61 + a 62 ≤ 8,

[0062] a 71 and a 73 Each independently is an integer from 1 to 3, a 72 and a 74 Each independently is an integer from 0 to 2, and satisfies a 71 + a 72 ≤ 3 and a 73 + a 74 ≤ 3, a 75 and a 76 Each independently is an integer from 0 to 4,

[0063] a 81 and a 83 Each independently is an integer from 1 to 3, a 82 and a 84 Each independently is an integer from 0 to 2, and satisfies a 81 + a 82 ≤ 3 and a 83 + a 84 ≤ 3,

[0064] a 91 and a 93 Each independently is an integer from 1 to 3, a 92 and a 94 Each independently is an integer from 0 to 2, and satisfies a 91 + a 92 ≤ 3 and a 93 + a94 ≤ 3.)

[0065] Y 211 and Y 212 each independently represents a monovalent group represented by any one of formulas (B01) to (B21),

[0066] [Chemical formula 5]

[0067]

[0068] [Chemical formula 6]

[0069]

[0070] [Chemical formula 7]

[0071]

[0072] (In the formula, L 11 represents -S-, -O-, -CO-, -CH2-, -(CH2)2-, -C(CH3)2-, -CF2-, -(CF2)2-, -C(CF3)2-, fluoren-9,9-diyl, -NH- or -NZ 100 -,

[0073] L 12 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 130 or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 131 ),

[0074] L 13 and L 14 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 130 or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 131 ),

[0075] Z 100 represents an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 130 or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 131 ),

[0076] Z 101 to Z 107 and Z 109 to Z 121 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, which may be substituted by Z 130A substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 130 A substituted alkenyl group having 2 to 20 carbon atoms or which may be substituted by Z 131 A substituted aryl group having 6 to 20 carbon atoms,

[0077] Z 108 Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a substituted alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 A substituted alkenyl group having 2 to 20 carbon atoms or which may be substituted by Z 130 A substituted aryl group having 6 to 20 carbon atoms. Zs present on different benzene rings 131 May combine with each other to form a ring, 108

[0078] Z 130 Each independently represents a fluorine atom, a chlorine atom, a bromine atom or a substituted aryl group having 6 to 20 carbon atoms which may be substituted by Z 132

[0079] Z 131 Each independently represents a fluorine atom, a chlorine atom, a bromine atom, a substituted alkyl group having 1 to 20 carbon atoms which may be substituted by Z 132 Or a substituted alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 132

[0080] Z 132 Represents a fluorine atom, a chlorine atom or a bromine atom,

[0081] Ar 1 Each independently represents an aryl group having 6 to 20 carbon atoms,

[0082] Ar 2 Represents a single bond or an arylene group having 6 to 20 carbon atoms.)

[0083] X 221 And X 222 Each independently represents a monovalent group represented by any one of formulas (C01) to (C09),

[0084] [Chemical formula 8]

[0085]

[0086] (In the formula, b 11 、b 21 、b 23 、b 31 、b 33 、b 41 、b 51 、b 61 、b 71 、b 73 、b 81 、b​​​83 and b 91 and b 93 represent the number of fluorine atoms substituted on the aromatic ring.

[0087] b 12 and b 22 and b 24 and b 32 and b 34 and b 42 and b 52 and b 62 and b 72 and b 74 and b 82 and b 84 and b 92 and b 94 represent the number of Z substituted on the aromatic ring. 01 ~Z 09 The number of

[0088] b 75 and b 76 represent the number of Z′ substituted on the aromatic ring.

[0089] b 11 is an integer from 2 to 5, and b 12 is an integer from 0 to 3, and satisfy b 11 +b 12 ≤5,

[0090] 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 satisfy b 21 +b 22 ≤4 and b 23 +b 24 ≤5,

[0091] 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 34 is an integer from 0 to 4, and satisfy b 31 +b 32 ≤4 and b 33 +b 34 ≤5,

[0092] b 41 is an integer from 1 to 7, and b 42 is an integer from 0 to 6, and satisfy b 41 +b 42 ≤7,

[0093] b51 is an integer from 1 to 9, b 52 is an integer from 0 to 8, and satisfies b 51 +b 52 ≤9,

[0094] b 61 is an integer from 1 to 9, b 62 is an integer from 0 to 8, and satisfies b 61 +b 62 ≤9,

[0095] b 71 is an integer from 1 to 3, b 73 is an integer from 1 to 4, b 72 is an integer from 0 to 2, b 74 is an integer from 0 to 3, and satisfies b 71 +b 72 ≤3 and b 73 +b 74 ≤4, b 75 and b 76 are each independently an integer from 0 to 4,

[0096] b 81 is an integer from 1 to 3, b 83 is an integer from 1 to 4, b 82 is an integer from 0 to 2, b 84 is an integer from 0 to 3, and satisfies b 81 +b 82 ≤3 and b 83 +b 84 ≤4,

[0097] b 91 is an integer from 1 to 3, b 93 is an integer from 1 to 4, b 92 is an integer from 0 to 2, b 94 is an integer from 0 to 3, and satisfies b 91 +b 92 ≤3 and b 93 +b 94 ≤4,

[0098] L 01 ~L 04 、Z′ and Z 01 ~Z 07 represent the same meaning as described above.)

[0099] Y 221 represents a divalent group represented by any one of formulas (D01-1) to (D21).

[0100] [Chemical Formula 9]

[0101]

[0102] [Chemical formula 10]

[0103]

[0104] [Chemical formula 11]

[0105]

[0106] [Chemical formula 12]

[0107]

[0108] (In the formula, Ar 3 each independently represents an arylene group having 6 to 20 carbon atoms, L 11 to L 14 , Z 101 to Z 121 and Ar 1 have the same meanings as described above.)]

[0109] [Chemical formula 13]

[0110]

[0111] A fluorinated aniline derivative of 11.10, wherein the X 211 is a divalent group represented by the formula (A02),

[0112] A fluorinated aniline derivative of 12.11, wherein the X 211 is a divalent group represented by the following formula (A02-1):

[0113] [Chemical formula 14]

[0114]

[0115] (In the formula, a 21 to a 24 and Z 02 have the same meanings as described above.)]

[0116] A fluorinated aniline derivative according to any one of 13.10 to 12, wherein the Y 211 and Y 212 are the same monovalent group,

[0117] A fluorinated aniline derivative of 14.13, wherein the Y 211 and Y 212 are each a monovalent group represented by any one of the formulas (B01), (B02), (B04), (B08) and (B18),

[0118] 15.10 Fluoroaniline derivatives, wherein the Y 221 is a divalent group represented by the formula (D02),

[0119] 16.15 Fluoroaniline derivatives, wherein the Y 221 is a divalent group represented by the following formula (D02-1):

[0120] [Chemical formula 15]

[0121]

[0122] 17.10, 15 or 16 Fluoroaniline derivatives, wherein X 221 and X 222 are the same monovalent group,

[0123] 18.17 Fluoroaniline derivatives, wherein X 221 and X 222 are both monovalent groups represented by the above formula (C01),

[0124] 19. A polymer comprising a repeating unit represented by the following formula (P1-2):

[0125] [Chemical formula 16]

[0126]

[0127] [In the formula, X 211 represents a divalent group represented by any one of the formulas (A01-1) to (A09),

[0128] [Chemical formula 17]

[0129]

[0130] (In the formula, L 01 represents -S-, -O-, -CO-, -CH2-, -(CH2)2-, -C(CH3)2-, -CF2-, -(CF2)2-, -C(CF3)2-, fluoren-9,9-diyl, -NH- or -NZ 10 -,

[0131] L 02 and L 03 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 11 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 11 or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 12 ,

[0132] L 04 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z11 A substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkenyl group having 2 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, which may be substituted by Z 12 A substituted aryl group having 6 to 20 carbon atoms,

[0133] Z′ represents a substituent of an aromatic ring, each independently representing a substituted alkyl group having 1 to 20 carbon atoms, a substituted alkenyl group having 2 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkenyl group having 2 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, which may be substituted by Z 12 A substituted aryl group having 6 to 20 carbon atoms,

[0134] Z 01 ~Z 09 represents a substituent of an aromatic ring, each independently representing a chlorine atom, a bromine atom, a nitro group, a cyano group, a substituted alkyl group having 1 to 20 carbon atoms, a substituted alkenyl group having 2 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkenyl group having 2 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, which may be substituted by Z 12 A substituted aryl group having 6 to 20 carbon atoms,

[0135] Z 10 represents a substituted alkyl group having 1 to 20 carbon atoms, a substituted alkenyl group having 2 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 11 A substituted alkenyl group having 2 to 20 carbon atoms, or a substituted aryl group having 6 to 20 carbon atoms, which may be substituted by Z 12 A substituted aryl group having 6 to 20 carbon atoms,

[0136] Z 11 each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or a substituted aryl group having 6 to 20 carbon atoms, which may be substituted by Z 13 A substituted aryl group having 6 to 20 carbon atoms,

[0137] Z 12 each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a substituted alkyl group having 1 to 20 carbon atoms, or a substituted alkenyl group having 2 to 20 carbon atoms, which may be substituted by Z 13 A substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 13 A substituted alkenyl group having 2 to 20 carbon atoms,

[0138] Z 13 represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, or a cyano group,

[0139] 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 represent the number of fluorine atoms substituted on the aromatic ring,

[0140] 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 represent the number of Z 01 ~Z 09 substituted on the aromatic ring,

[0141] a 75 and a 76 represent the number of Z' substituted on the aromatic ring,

[0142] a 11 is an integer from 2 to 4, a 12 is an integer from 0 to 2, and satisfies a 11 + a 12 ≤ 4,

[0143] a 13 is an integer from 2 to 4, a 14 is an integer from 0 to 2, and satisfies a 13 + a 14 ≤ 4,

[0144] a 21 and a 23 are each independently an integer from 1 to 4, a 22 and a 24 are each independently an integer from 0 to 3, and satisfy a 21 + a 22 ≤ 4 and a 23 + a 24 ≤ 4,

[0145] a 31 and a 33 are each independently an integer from 1 to 4, a 32 and a 34 are each independently an integer from 0 to 3, and satisfy a 31 + a 32 ≤ 4 and a 33 + a 34 ≤ 4,

[0146] a 41 is an integer from 1 to 6, a 42 is an integer from 0 to 5, and satisfies a 41 + a 42 ≤ 6,

[0147] a 51 is an integer from 1 to 8, a 52 is an integer from 0 to 7, and satisfies a 51 + a 52 ≤ 8,

[0148] a 61 is an integer from 1 to 8, a 62 is an integer from 0 to 7, and satisfies a 61 + a 62 ≤ 8,

[0149] a 71 and a 73 are each independently an integer from 1 to 3, a 72 and a 74 are each independently an integer from 0 to 2, and satisfy a 71 + a 72 ≤ 3 and a 73 + a 74 ≤ 3, a 75 and a 76 are each independently integers from 0 to 4,

[0150] a 81 and a 83 are each independently an integer from 1 to 3, a 82 and a 84 are each independently an integer from 0 to 2, and satisfy a 81 + a 82 ≤ 3 and a 83 + a 84 ≤ 3,

[0151] a 91 and a 93 are each independently an integer from 1 to 3, a 92 and a 94 are each independently an integer from 0 to 2, and satisfy a 91 + a 92 ≤ 3 and a 93 + a 94 ≤ 3.)

[0152] Y 221 represents a divalent group represented by any one of formulas (D01-1) to (D21).

[0153] [Chemical Formula 18]

[0154]

[0155] [Chemical formula 19]

[0156]

[0157] [Chemical formula 20]

[0158]

[0159] [Chemical formula 21]

[0160]

[0161] (In the formula, L 11 represents -S-, -O-, -CO-, -CH2-, -(CH2)2-, -C(CH3)2-, -CF2-, -(CF2)2-, -C(CF3)2-, fluoren-9,9-diyl, -NH- or -NZ 02 -,

[0162] L 12 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 130 or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 131 ,

[0163] L 13 and L 14 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 130 or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 131 ,

[0164] Z 101 to Z 107 and Z 109 to Z 121 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 130 or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 131 ,

[0165] Z 108 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 130 or an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z131 A substituted aryl group having 6 to 20 carbon atoms, and Z present on different benzene rings 108 may combine with each other to form a ring.

[0166] Z 130 each independently represents a fluorine atom, a chlorine atom, a bromine atom, or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 132

[0167] Z 131 each independently represents a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 132 or an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 132

[0168] Z 132 represents a fluorine atom, a chlorine atom, or a bromine atom.

[0169] Ar 1 each independently represents an aryl group having 6 to 20 carbon atoms.

[0170] Ar 3 each independently represents an arylene group having 6 to 20 carbon atoms.)

[0171] 20. The polymer according to 19, wherein the X 211 is a divalent group represented by the above formula (A02).

[0172] 21. The polymer according to 20, wherein the X 211 is a divalent group represented by the following formula (A02-1).

[0173] [Chemical formula 22]

[0174]

[0175] (In the formula, a 21 to a 24 and Z 02 represent the same meanings as described above.)

[0176] 22. The polymer according to any one of 19 to 21, wherein the Y 221 is a divalent group represented by any one of the above formulas (D02), (D17), and (D19).

[0177] 23. A charge transporting material, which is composed of an aniline derivative according to any one of 10 to 18.

[0178] 24. A charge transporting material, which is composed of a polymer according to any one of 19 to 22.

[0179] ​​25. A charge transport composition comprising the charge transport material of 23 or 24 and an organic solvent,

[0180] 26. The charge transport composition of 25, which comprises a dopant substance,

[0181] 27. A charge transport film obtained from the charge transport composition of 25 or 26,

[0182] 28. An electronic component comprising the charge transport film of 27,

[0183] 29. An organic electroluminescent element comprising the charge transport film of 27,

[0184] 30. The organic electroluminescent element of 29, wherein the charge transport film is a hole injection layer or a hole transport layer.

[0185] Effects of the Invention

[0186] According to the method for producing a fluorinated aromatic secondary amine compound of the present invention, by using a commercially available palladium catalyst and a ligand having a biphenyl skeleton, a secondary amine compound (fluoroaniline derivative) having a fluoroaryl moiety in the molecule can be efficiently, in high yield, and at low cost produced from a fluorinated aromatic amine compound and a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudo-halogenated aromatic hydrocarbon.

[0187] In addition, in this reaction, by using a difunctional compound for both the fluorinated aromatic amine compound and the chlorinated, brominated, or iodinated aromatic hydrocarbon or the pseudo-halogenated aromatic hydrocarbon, a polymerization reaction proceeds, and a polymer such as a low molecular weight polyaniline derivative or a polyaniline derivative having a fluoroaryl moiety in the molecule can be efficiently produced.

[0188] Since the fluoroamine compounds such as fluoroaniline derivatives and polymers obtained by the production method of the present invention have fluorine atoms in the molecule, they are excellent in transparency and also exhibit charge transport properties. Therefore, by using them alone or in combination with other charge transport materials and dopant substances, they can be suitably used as materials for forming charge transport films for electronic components such as organic EL elements. Detailed Description of the Invention

[0189] The present invention will be described in more detail below.

[0190] [1] Method for Producing Fluorinated Aromatic Secondary Amine Compound

[0191] The method for producing a fluorinated aromatic secondary amine compound according to the present invention includes the following steps: reacting a fluorinated aromatic primary amine compound with a chlorinated, brominated, or iodinated aromatic hydrocarbon or a pseudo-halogenated aromatic hydrocarbon in the presence of a catalyst, a ligand, and a base.

[0192] (1) Catalyst

[0193] The catalyst used in the present invention contains a palladium(0) complex of dibenzylideneacetone.

[0194] As specific examples of the palladium(0) complex of dibenzylideneacetone, bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), tris(dibenzylideneacetone)(chloroform)dipalladium(0), etc. can be mentioned. Among these, bis(dibenzylideneacetone)palladium(0) is preferred.

[0195] Regarding the amount of the palladium(0) complex of dibenzylideneacetone used, as long as the amount enables the target coupling reaction to proceed, there is no particular limitation. Relative to the NH of the amine moiety of 1 mol of the fluorinated aromatic primary amine compound, in terms of palladium metal, it 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.

[0196] In addition, in the present invention, within the range that does not impair the effects of the present invention, other metal catalysts can be used together with the palladium(0) complex of dibenzylideneacetone.

[0197] As other metal catalysts, for example, copper catalysts such as copper chloride, copper bromide, copper iodide, etc.; palladium catalysts such as Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium), Pd(PPh3)2Cl2 (bis(triphenylphosphine)dichloropalladium), Pd(P-t-Bu3)2 (bis(tris(tert-butylphosphine))palladium), Pd(OAc)2 (palladium acetate), etc. can be mentioned.

[0198] When using these other metal catalysts, their amounts used cannot be generally specified and are usually less than 100 mol% relative to the palladium(0) complex of dibenzylideneacetone.

[0199] (2) Ligand

[0200] The ligand used in the present invention contains a biphenylphosphine compound represented by the following formula (L).

[0201] [Chemical formula 23]

[0202]

[0203] In formula (L), R 1 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 2 to 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, and R 6 to R 8Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an NR 9 2 group, where R 9 Each independently represents an alkyl group having 1 to 20 carbon atoms.

[0204] Examples of the alkyl group having 1 to 20 carbon atoms include linear, branched, and cyclic alkyl groups. For example, linear or branched alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, and icosyl; 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.

[0205] 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, 9-phenanthryl, etc.

[0206] Specific examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, c-propoxy (cyclopropoxy), n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, etc.

[0207] Among these, from the viewpoint of reproducibly obtaining the target substance, R 1 Each independently is preferably a group with a relatively large volume, preferably a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms in which the carbon atom at the bonding end is a secondary carbon atom or a tertiary carbon atom. Further, from the viewpoints of solubility and stability in a solvent, a branched alkyl group having 3 to 5 carbon atoms and a cyclic alkyl group having 5 to 7 carbon atoms are more preferred, and tert-butyl and cyclohexyl are further preferred.

[0208] Furthermore, from the viewpoint of ease of synthesis, it is preferred that the two R 1 are the same.

[0209] In addition, from the viewpoints of the stability of the compound and reproducibly obtaining the target substance, R 2 to R 5 Each independently is preferably a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, and more preferably R 2 and R 5 Each independently is a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, and R 3 and R 4are combinations of hydrogen atoms, and further preferably R 2 ~R 5 are all hydrogen atoms.

[0210] Furthermore, from the viewpoints of the stability of the compound and obtaining the target substance with good reproducibility, R 6 ~R 8 are preferably hydrogen atom, linear alkyl group having 1 to 20 carbon atoms, branched alkyl group having 3 to 20 carbon atoms in which the carbon atom at the bonding end is a primary carbon atom or a secondary carbon atom, or alkoxy group having 1 to 20 carbon atoms. Furthermore, from the viewpoints of solubility and stability in a solvent, they are more preferably hydrogen atom, linear alkyl group having 1 to 5 carbon atoms, branched alkyl group having 3 to 5 carbon atoms, or alkoxy group having 1 to 5 carbon atoms, and even more preferably hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, methoxy group, or isopropoxy group.

[0211] In particular, as R 6 and R 8 , hydrogen atom, alkyl group having 1 to 5 carbon atoms, or alkoxy group having 1 to 5 carbon atoms are preferred, and hydrogen atom, methyl group, isopropyl group, methoxy group, or isopropoxy group are more preferred.

[0212] As R 7 , hydrogen atom or alkyl group having 1 to 5 carbon atoms is preferred, and hydrogen atom or isopropyl group is more preferred.

[0213] As the ligand preferably used in the present invention, ligands represented by the following formulas (L1) to (L7) can be mentioned, but are not limited thereto.

[0214] [Chemical formula 24]

[0215]

[0216] (In the formula, Me means methyl group, i-Pr means isopropyl group, t-Bu means tert-butyl group, and Cy means cyclohexyl group.)

[0217] The ligand represented by the above formula (L) can be obtained as a commercially available product. For example, 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, CPhos, etc., which are commercially available from Aldrich as Buchwald ligands and the like, can be mentioned.

[0218] In addition, the ligand represented by the above formula (L) can also be synthesized by a known method.

[0219] Regarding the amount of the ligand represented by the formula (L) used, it is preferably 1 to 2 equivalents relative to the catalyst used. In particular, when it is less than 1 equivalent, palladium black may be generated.

[0220] In the present invention, within the range not impairing the effects of the present invention, other ligands can be used together with the ligand represented by the formula (L).

[0221] Specific examples of other ligands include tertiary phosphines such as triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-tert-butylphosphine, di-tert-butyl(phenyl)phosphine, di-tert-butyl(4-dimethylaminophenyl)phosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, and trialkyl phosphites such as trimethyl phosphite, triethyl phosphite, and triphenyl phosphite.

[0222] When using other ligands, their amounts used cannot be generally specified. Usually, it is less than 100 mol% relative to the ligand represented by the formula (L).

[0223] (3) Fluorinated aromatic primary amine compounds

[0224] In the production method of the present invention, due to the characteristics of the above-mentioned catalyst and ligand, there are no particular limitations on the fluorinated aromatic primary amine compound, which is a raw material for the coupling reaction.

[0225] The fluorinated aromatic primary amine compound may be a monoamine compound or a diamine compound. For example, compounds represented by the following formulas (X1) and (X2) can be cited.

[0226] [Chemical formula 25]

[0227] Ar F1 -NH2 (X1) H2N-Ar F2 -NH2 (X2)

[0228] (In the formula, Ar F1 represents a fluorinated aryl group, and Ar F2 represents a fluorinated arylene group.)

[0229] The fluorinated aryl group only needs to have at least one hydrogen atom of the aryl group substituted by a fluorine atom, and it is preferably that two or more hydrogen atoms are substituted by fluorine atoms.

[0230] The fluoroarylene is such that at least one hydrogen atom of the arylene is substituted with a fluorine atom, but it is preferably that two or more hydrogen atoms are substituted with fluorine atoms.

[0231] That is, the fluoroaromatic primary amine compound used in the present invention is preferably a fluoroaromatic primary monoamine compound or a diamine compound having two or more fluorine atoms in the molecule.

[0232] As the aryl group, an aryl group having 6 to 20 carbon atoms is preferred. 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-tetraphenyl, 2-tetraphenyl, 5-tetraphenyl, 2- yl, 1-pyrenyl, 2-pyrenyl, pentaphenyl, benzopyrenyl, benzo[9,10]phenanthryl and other groups derived by removing one hydrogen atom on the aromatic ring of a fused-ring aromatic hydrocarbon compound; biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, m-terphenyl-4-yl, o-terphenyl-4-yl, 1,1'-binaphthalen-2-yl, 2,2'-binaphthalen-1-yl and other groups derived by removing one hydrogen atom on the aromatic ring of a ring-linked hydrocarbon compound, etc.

[0233] As the fluoroarylene, a fluoroarylene having 6 to 20 carbon atoms is preferred. Specific examples thereof include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthylene, 1,8-naphthylene, 2,6-naphthylene, 2,7-naphthylene, 1,2-anthrylene, 1,3-anthrylene, 1,4-anthrylene, 1,5-anthrylene, 1,6-anthrylene, 1,7-anthrylene, 1,8-anthrylene, 2,3-anthrylene, 2,6-anthrylene, 2,7-anthrylene, 2,9-anthrylene, 2,10-anthrylene, 9,10-anthrylene and other groups derived by removing two hydrogen atoms on the aromatic ring of a fused-ring aromatic hydrocarbon compound; biphenyl-4,4'-diyl, p-terphenyl-4,4''-diyl and other groups derived by removing two hydrogen atoms on the aromatic ring of a ring-linked hydrocarbon compound, etc.

[0234] (4) Chlorinated, brominated or iodinated aromatic hydrocarbon or pseudo-halogenated aromatic hydrocarbon

[0235] As the chlorinated, brominated or iodinated aromatic hydrocarbon or pseudo-halogenated aromatic hydrocarbon, it may be a compound having one reaction site that reacts with the amino group of the fluoroaromatic primary amine, such as a monochloro, monobromo or monoiodo or monopseudo-halogen compound, or a compound having two or more reaction sites that react with the amino group of the fluoroaromatic primary amine, such as a dichloro, dibromo or diiodo or dipseudo-halogen compound. Examples thereof include the compounds represented by the following formulas (Y1) and (Y2).

[0236] [Chemical formula 26]

[0237] Ar 4 -X(Y1)X-Ar 5 -X(Y2)

[0238] (In the formula, Ar 4 represents an aryl group, Ar 5 represents an arylene group, and each X independently represents a chlorine atom, a bromine atom, an iodine atom or a pseudohalogen group.)

[0239] As the aryl group and the arylene group, the same groups as those described above can be exemplified.

[0240] As the pseudohalogen group, (fluoro)alkylsulfonyloxy groups such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group, nonafluorobutanesulfonyloxy group, etc.; aromatic sulfonyloxy groups such as benzenesulfonyloxy group, toluenesulfonyloxy group, etc. can be exemplified.

[0241] As X, from the viewpoint of reactivity, a bromine atom and an iodine atom are preferred.

[0242] In particular, the chlorinated, brominated or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon used in the present invention is preferably a monochloroaromatic hydrocarbon or a dichloroaromatic hydrocarbon, a monobromoaromatic hydrocarbon or a dibromoaromatic hydrocarbon, or a monoiodoaromatic hydrocarbon or a diiodoaromatic hydrocarbon, and more preferably a monobromoaromatic hydrocarbon or a dibromoaromatic hydrocarbon, or a monoiodoaromatic hydrocarbon or a diiodoaromatic hydrocarbon.

[0243] (5) Base

[0244] There is no particular limitation on the base. For example, alkali metal elements such as lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate; alkali metal hydrides, alkali metal hydroxides, alkoxy alkali metals, alkali metal carbonates, alkali metal bicarbonates such as calcium carbonate; alkaline earth metal carbonates; organolithiums such as n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide (LDA), lithium 2,2,6,6-tetramethylpiperidine (LiTMP), lithium hexamethyldisilazane (LHMDS); amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, pyridine, etc. are exemplified, but amino lithium reagents for lithiating secondary amines such as LDA, LiTMP, LHMDS and alkoxy alkali metals such as lithium tert-butoxide are preferred.

[0245] (6) Coupling reaction

[0246] In the production method of the present invention, regarding the feed ratio of the fluorinated aromatic primary amine compound to the chlorinated, brominated or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon, with respect to 1 mole of the NH2 group of the fluorinated aromatic primary amine compound, the reaction site of chlorine, bromine or iodine or pseudohalogen as the aromatic hydrocarbon is preferably about 1.0 to 1.2 moles.

[0247] For example, expressed in terms of the molar ratio of substances, in the reaction between formula (X1) and formula (Y1), relative to 1 of (X1), (Y1) is preferably about 1 to 1.2; in the reaction between formula (X1) and (Y2), relative to 1 of (X1), (Y1) is preferably about 0.5 to 0.6; in the reaction between formula (X2) and formula (Y1), relative to 1 of (X2), (Y1) is preferably about 2 to 2.4; and in the reaction between formula (X2) and (Y2), relative to 1 of (X2), (Y2) is preferably about 1 to 1.2.

[0248] In the case where all the starting compounds are solids or from the viewpoint of efficiently obtaining the target fluorinated aromatic secondary amine compound, the coupling reaction of the present invention is carried out in a solvent.

[0249] When a solvent is used, its type is not particularly limited as long as it does not have an adverse effect on 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, tert-butyl methyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 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.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be used alone or in combination of two or more.

[0250] In particular, in the present invention, as the solvent, ethers are preferably used, and dioxane is more preferably used.

[0251] The lower limit of the reaction temperature varies depending on the reactivity of the reaction substrate, etc., so it cannot be generally specified. If it is 45 °C or higher, usually, the coupling reaction proceeds well. In particular, if further improving the reactivity is considered, the reaction temperature is preferably 60 °C or higher, more preferably 75 °C or higher, further preferably 90 °C or higher. In particular, it is preferably carried out under heating and reflux of the solvent. On the other hand, the upper limit of the reaction temperature varies depending on the boiling point of the solvent used, so it cannot be generally specified, and it is usually about 200 °C or lower.

[0252] After the reaction is completed, post-treatment is carried out according to a conventional method, and the target fluorinated aromatic secondary amine compound can be obtained.

[0253] [2] Fluoroaniline derivatives

[0254] One of the fluoroaniline derivatives involved in the present invention is represented by the following formula (T1).

[0255] [Chemical formula 27]

[0256]

[0257] In the above formula (T1), X 211 represents a divalent group represented by any one of formulas (A01-1) to (A09).

[0258] [Chemical formula 28]

[0259]

[0260] Among them, L 01 represents -S-, -O-, -CO-, -CH2-, -(CH2)2-, -C(CH3)2-, -CF2-, -(CF2)2-, -C(CF3)2-, fluoren-9,9-diyl, -NH- or -NZ 10 -.

[0261] L 02 and L 03 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that can be substituted by Z 11 , an alkenyl group having 2 to 20 carbon atoms that can be substituted by Z 11 or an aryl group having 6 to 20 carbon atoms that can be substituted by Z 12 , preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, and more preferably a hydrogen atom, a methyl group, a phenyl group.

[0262] As specific examples of the above alkyl and aryl groups, the same groups as above can be cited.

[0263] As specific examples of the alkenyl group having 2 to 20 carbon atoms, vinyl, 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-ethyl ethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, n-1-eicosenyl, etc. can be cited.

[0264] L 04 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that can be substituted by Z 11 , an alkenyl group having 2 to 20 carbon atoms that can be substituted by Z 11 or an aryl group having 6 to 20 carbon atoms that can be substituted by Z 12A substituted aryl group having 6 to 20 carbon atoms. Specific examples of these alkyl, alkenyl, and aryl groups include the same groups as described above. Among these, L 04 is preferably a hydrogen atom or a phenyl group.

[0265] Z′ represents a substituent of the aromatic ring and each independently represents an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 11 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 11 , or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 12 . Specific examples of these alkyl, alkenyl, and aryl groups include the same groups as described above.

[0266] Z 01 ~Z 09 represent substituents of the aromatic ring and each independently represents a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 11 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 11 , or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 12 . Z 10 represents an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 11 , an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 11 , or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 12 . Z 11 each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 13 . Z 12 each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 13 , or an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 13 . Z 13 represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, or a cyano group. Specific examples of these alkyl, alkenyl, and aryl groups include the same groups as described above.

[0267] Among them, when Z 01 ~Z 09 exist, a nitro group or an alkyl group having 1 to 5 carbon atoms which may be substituted by a fluorine atom is preferred. In addition, Z 10 is preferably a phenyl group which may be substituted by a fluorine atom.

[0268] Furthermore, when there are a plurality of substituents Z p (p = ′, 01 to 09) of the aromatic ring, they may be the same or different from each other.

[0269] a 11 、a 13 、a21 , 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, 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 represents the number of Z substituted on the aromatic ring 01 ~Z 09 , a 75 and a 76 represents the number of Z′ substituted on the aromatic ring.

[0270] a 11 is an integer from 2 to 4, a 12 is an integer from 0 to 2, and satisfies a 11 + a 12 ≤ 4.

[0271] a 13 is an integer from 2 to 4, a 14 is an integer from 0 to 2, and satisfies a 13 + a 14 ≤ 4.

[0272] a 21 and a 23 are each independently an integer from 1 to 4, a 22 and a 24 are each independently an integer from 0 to 3, and satisfy a 21 + a 22 ≤ 4 and a 23 + a 24 ≤ 4.

[0273] a 31 and a 33 are each independently an integer from 1 to 4, a 32 and a 34Each independently is an integer from 0 to 3, and satisfies a 31 + a 32 ≤ 4 and a 33 + a 34 ≤ 4.

[0274] a 41 is an integer from 1 to 6, a 42 is an integer from 0 to 5, and satisfies a 41 + a 42 ≤ 6.

[0275] a 51 is an integer from 1 to 8, a 52 is an integer from 0 to 7, and satisfies a 51 + a 52 ≤ 8.

[0276] a 61 is an integer from 1 to 8, a 62 is an integer from 0 to 7, and satisfies a 61 + a 62 ≤ 8.

[0277] a 71 and a 73 each independently is an integer from 1 to 3, a 72 and a 74 each independently is an integer from 0 to 2, and satisfies a 71 + a 72 ≤ 3 and a 73 + a 74 ≤ 3, a 75 and a 76 each independently is an integer from 0 to 4.

[0278] a 81 and a 83 each independently is an integer from 1 to 3, a 82 and a 84 each independently is an integer from 0 to 2, and satisfies a 81 + a 82 ≤ 3 and a 83 + a 84 ≤ 3.

[0279] a 91 and a 93 each independently is an integer from 1 to 3, a 92 and a 94 each independently is an integer from 0 to 2, and satisfies a 91 + a 92 ≤ 3 and a 93 + a 94 ≤ 3.

[0280] Specifically, a 41 、a 51 、a 61 is preferably an integer of 2 or more.

[0281] In addition, 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 are preferably 0, a 75 and a 76 are preferably 0.

[0282] 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 further preferably a perfluorinated biphenylene group represented by formula (A02-1-1) when considering use as a charge transporting material.

[0283] [Chemical formula 29]

[0284]

[0285] (In the formula, a 21 ~a 24 and Z 02 represent the same meanings as described above.)

[0286] [Chemical formula 30]

[0287]

[0288] On the other hand, Y 211 and Y 212 each independently represent a monovalent group represented by any one of formulas (B01) to (B21).

[0289] [Chemical formula 31]

[0290]

[0291] [Chemical formula 32]

[0292]

[0293] [Chemical formula 33]

[0294]

[0295] wherein, L 11 represents -S-, -O-, -CO-, -CH2-, -(CH2)2-, -C(CH3)2-, -CF2-, -(CF2)2-, -C(CF3)2-, fluoren-9,9-diyl, -NH-, or -NZ 100 -.

[0296] L 12 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 130 or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 131 As specific examples of these alkyl, alkenyl, and aryl groups, the same groups as described above can be cited. Among these, L 12 is preferably a hydrogen atom or a phenyl group.

[0297] L 13 and L 14 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 130 or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 131 As specific examples of these alkyl, alkenyl, and aryl groups, the same groups as described above can be cited. Among these, as L 13 and L 14 it is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and more preferably a hydrogen atom, a methyl group, or a phenyl group.

[0298] Z 100 represents an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 130 or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 131 and is preferably a phenyl group which may be substituted by a fluorine atom.

[0299] Z 101 to Z 107 and Z 109 to Z 121 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130 an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 130 or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 131 Z 108 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 130A substituted alkyl group having 1 to 20 carbon atoms, which may be substituted by Z 130 A substituted alkenyl group having 2 to 20 carbon atoms, or which may be substituted by Z 131 A substituted aryl group having 6 to 20 carbon atoms, provided that Z present on different benzene rings 108 May combine with each other to form a ring, and Z 130 Each independently represents a fluorine atom, a chlorine atom, a bromine atom, or an aryl group having 6 to 20 carbon atoms which may be substituted by Z 132 And Z 131 Each independently represents a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 132 Or an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z 132 And Z 132 Represents a fluorine atom, a chlorine atom, or a bromine atom. As specific examples of these alkyl groups, alkenyl groups, and aryl groups, the same examples as described above may be cited. Among these, Z 101 To Z 107 And Z 109 To Z 121 Are preferably hydrogen atoms. Z 108 Is preferably a hydrogen atom or a single bond formed by the combination of at least one group of Z present at the ortho position of the nitrogen atom on different benzene rings 108 Furthermore, as the formula (B08) in which a single bond is formed between Z 108 , for example, a structure represented by the following formula (B08’) may be cited.

[0300] Furthermore, Z q (q = 101 to 121) may be the same or different from each other.

[0301] [Chemical formula 34]

[0302]

[0303] Ar 1 Each independently represents an aryl group having 6 to 20 carbon atoms. As the aryl group, the same aryl groups as described above may be cited. Among them, Ar 1 Is preferably a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and more preferably a phenyl group.

[0304] Ar 2 Represents a single bond or an arylene group having 6 to 20 carbon atoms. As specific examples of the arylene group having 6 to 20 carbon atoms, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,5-naphthylene, 1,8-naphthylene, 2,6-naphthylene, 2,7-naphthylene, etc. may be cited. Among them, Ar 2 Is preferably a single bond, 1,4-phenylene.

[0305] In particular, considering the ease of synthesis, etc., it is preferable that Y 211 And Y 212They are monovalent groups of the same valence, more preferably monovalent groups each represented by any one of formulas (B01), (B02), (B04), (B08) and (B18).

[0306] In addition, another fluorine-containing aniline derivative according to the present invention is represented by the following formula (T2).

[0307] [Chemical formula 35]

[0308]

[0309] In formula (T2), X 221 and X 222 each independently represent a monovalent group represented by any one of formulas (C01) to (C09).

[0310] [Chemical formula 36]

[0311]

[0312] Among them, 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 represent 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 represent the number of Z 01 ~Z 09 substituted on the aromatic ring, and b 75 and b 76 represent the number of Z' substituted on the aromatic ring.

[0313] b 11 is an integer from 2 to 5, b 12 is an integer from 0 to 3, and b 11 +b 12≤5.

[0314] b 21 is an integer from 1 to 4, b 23 is an integer from 1 to 5, b 22 is an integer from 0 to 3, b 24 is an integer from 0 to 4, and satisfies b 21 +b 22 ≤4 and b 23 +b 24 ≤5.

[0315] b 31 is an integer from 1 to 4, b 33 is an integer from 1 to 5, b 32 is an integer from 0 to 3, b 34 is an integer from 0 to 4, and satisfies b 31 +b 32 ≤4 and b 33 +b 34 ≤5.

[0316] b 41 is an integer from 1 to 7, b 42 is an integer from 0 to 6, and satisfies b 41 +b 42 ≤7.

[0317] b 51 is an integer from 1 to 9, b 52 is an integer from 0 to 8, and satisfies b 51 +b 52 ≤9.

[0318] b 61 is an integer from 1 to 9, b 62 is an integer from 0 to 8, and satisfies b 61 +b 62 ≤9.

[0319] b 71 is an integer from 1 to 3, b 73 is an integer from 1 to 4, b 72 is an integer from 0 to 2, b 74 is an integer from 0 to 3, and satisfies b 71 +b 72 ≤3 and b 73 +b 74 ≤4, b 75 and b 76 are each independently an integer from 0 to 4.

[0320] b 81 is an integer from 1 to 3, b 83 is an integer from 1 to 4, b 82is an integer from 0 to 2, b 84 is an integer from 0 to 3, and satisfies b 81 + b 82 ≤ 3 and b 83 + b 84 ≤ 4.

[0321] b 91 is an integer from 1 to 3, b 93 is an integer from 1 to 4, b 92 is an integer from 0 to 2, b 94 is an integer from 0 to 3, and satisfies b 91 + b 92 ≤ 3 and b 93 + b 94 ≤ 4.

[0322] In particular, b 41 , b 51 , b 61 are preferably integers of 2 or more.

[0323] In addition, 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 are preferably 0, b 75 and b 76 are preferably 0.

[0324] It should be noted that L 01 ~L 04 , Z' and Z 01 ~Z 09 represent the same meaning as described above.

[0325] In particular, considering the ease of synthesis, charge transport properties, etc., X 221 and X 222 are preferably the same monovalent group, more preferably both monovalent groups represented by formula (C01), and even more preferably both monovalent groups represented by the following formula (C01-1).

[0326] [Chemical formula 37]

[0327]

[0328] On the other hand, Y 221A divalent group represented by any one of formulas (D01-1) to (D21).

[0329] [Chemical formula 38]

[0330]

[0331] [Chemical formula 39]

[0332]

[0333] [Chemical formula 40]

[0334]

[0335] [Chemical formula 41]

[0336]

[0337] In the formula, Ar 3 Each independently represents an arylene group having 6 to 20 carbon atoms. Specific examples of the arylene group include the same examples as described above.

[0338] In addition, L 11 to L 14 , Z 101 to Z 121 and Ar 1 represent the same meanings as described above.

[0339] Among these, Y 221 is preferably a divalent group represented by formula (D02), more preferably a divalent group represented by the following formula (D02-1), and still more preferably a biphenylene group represented by the following formula (D02-1-1).

[0340] [Chemical formula 42]

[0341]

[0342] (In the formula, Z 102 represents the same meaning as described above.)

[0343] Furthermore, the fluorine-containing aniline derivative of the present invention does not contain compounds represented by the following formulas [1] to

[13] .

[0344] [Chemical formula 43]

[0345]

[0346] Specific examples of the fluorine-containing aniline derivative of the present invention include compounds represented by the following formulas, but are not limited thereto.

[0347] [Chemical formula 44]

[0348]

[0349] (In the formula, t-Bu represents tert-butyl.)

[0350] [3] Polymer

[0351] The polymer of the present invention includes repeating units represented by the following formula (P1-2).

[0352] [Chemical formula 45]

[0353]

[0354] In formula (P1-2), X 211 Examples of the group include the same groups as those exemplified in the above fluorinated aniline derivatives, and the preferred range is also the same as above.

[0355] In addition, Y 221 Examples of the group include the same groups as those exemplified in the above fluorinated aniline derivatives. Among them, a divalent group represented by any one of formulas (D02), (D17), and (D19) is preferred.

[0356] There is no particular limitation on the molecular weight of the polymer of the present invention. Considering the conductivity when used as a charge transporting material and the solubility in organic solvents, etc., the weight average molecular weight is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 5,000 to 30,000. It should be noted that the weight average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography.

[0357] Specific examples of the polymer of the present invention include those represented by the following formulas, but are not limited thereto.

[0358] [Chemical formula 46]

[0359]

[0360] (In the formula, m each independently represents an integer of 2 or more.)

[0361] [4] Manufacturing methods of fluorinated aniline derivatives and polymers

[0362] The fluorinated aniline derivatives and polymers of the present invention described above can be synthesized using the manufacturing method of the fluorinated aromatic secondary amine of the present invention described above.

[0363] For example, a fluoroaniline derivative can be obtained by reacting a fluoroaromatic primary diamine represented by the above formula (X2) with 2 equivalents of an aromatic hydrocarbon chloride, bromide, or iodide or an aromatic pseudohalide represented by the above formula (Y1), or reacting a fluoroaromatic primary amine represented by the above formula (X1) with 0.5 equivalents of an aromatic hydrocarbon dichloride, dibromide, or diiodide or an aromatic pseudohalide represented by the above formula (Y2) in the presence of a palladium(0) complex of dibenzylideneacetone, a ligand represented by the above formula (L), and a base.

[0364] On the other hand, a polymer can be obtained by reacting a fluoroaromatic primary diamine compound represented by the above formula (X2) with an aromatic hydrocarbon dichloride, dibromide, or diiodide or an aromatic pseudohalide represented by the above formula (Y2) in the presence of a palladium(0) complex of dibenzylideneacetone, a ligand represented by the above formula (L), and a base. Further, in the synthesis of the polymer, since the molecular weight increases by increasing the amount of the catalyst, the molecular weight of the obtained polymer can be adjusted by adjusting the amount of the catalyst.

[0365] [5] Charge transport material, charge transport composition, and charge transport film

[0366] The above-described fluoroaniline derivative and polymer of the present invention have excellent transparency because they have fluorine atoms in the molecule, and exhibit conductivity when used alone or in combination with a dopant substance. Therefore, they can be preferably used as a charge transport material. By dissolving the fluoroaniline derivative and polymer of the present invention in a solvent, a charge transport composition can be easily prepared.

[0367] For example, as the charge transport composition of the present invention, a composition containing a charge transport material composed of the above-described fluoroaniline derivative or polymer and an organic solvent can be exemplified. Depending on the use of the obtained film, a dopant substance can be included for the purpose of improving its charge transport ability and the like.

[0368] The dopant substance is not particularly limited as long as it is soluble in at least one solvent used in the composition.

[0369] As specific examples of the dopant substance, inorganic strong acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid can be cited; Lewis acids such as aluminum(III) chloride (AlCl3), titanium(IV) chloride (TiCl4), boron tribromide (BBr3), boron trifluoride ether complex (BF3·OEt2), iron(III) chloride (FeCl3), copper(II) chloride (CuCl2), antimony(V) pentachloride (SbCl5), arsenic(V) pentafluoride (AsF5), phosphorus pentafluoride (PF5), tris(4-bromophenyl)aluminum hexachloroantimonate (TBPAH), etc.; organic strong acids such as benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, dodecylbenzenesulfonic acid, naphthalenedisulfonic acids such as 1,5-naphthalenedisulfonic acid, naphthalenetrisulfonic acids such as 1,3,5-naphthalenetrisulfonic acid and 1,3,6-naphthalenetrisulfonic acid, polystyrenesulfonic acid, 1,4-benzo dioxanedisulfonic acid compounds described in International Publication No. 2005 / 000832, naphthalene or anthracenesulfonic acid compounds described in International Publication No. 2006 / 025342, dinonylnaphthalenesulfonic acid compounds described in Japanese Patent Application Laid-Open No. 2005-108828, etc. arylsulfonic acid compounds; organic oxidants such as 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), iodine, etc.; inorganic oxidants such as heteropolyacids such as phosphomolybdic acid, phosphotungstic acid, and phosphotungstomolybdic acid described in International Publication No. 2010 / 058777, etc. can be used in combination respectively.

[0370] Among these, arylsulfonic acid compounds are preferred, and arylsulfonic acid compounds represented by the formula (H1) or (H2) are more preferred. Further, regarding the molecular weight of the arylsulfonic acid compound used as the dopant substance, considering solubility in an organic solvent, it is preferably 3000 or less, more preferably 2500 or less.

[0371] [Chemical formula 47]

[0372]

[0373] A 1 represents O or S, preferably O.

[0374] A 2 represents a naphthalene ring or an anthracene ring, preferably a naphthalene ring.

[0375] A 3 represents a 2- to 4-valent perfluorobiphenyl group, p represents the number of bindings of A 1 to A 3 and is an integer satisfying 2 ≤ p ≤ 4, A 3 is a perfluorobiphenylene group, preferably perfluorobiphenyl-4,4'-diyl and p is 2.

[0376] q represents the binding to A 2The combined sulfonic acid group number is an integer satisfying 1 ≤ q ≤ 4, and most preferably 2.

[0377] A 4 ~A 8 Each independently represents 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, and at least 3 of A 4 ~A 8 are halogen atoms.

[0378] Examples of the halogenated alkyl group 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, 1,1,2,2,3,3,4,4,4-nonafluorobutyl, and the like.

[0379] Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include perfluoroethenyl, perfluoropropenyl (perfluoroallyl), perfluorobutenyl, and the like.

[0380] Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, and a fluorine atom is preferred.

[0381] In addition, examples of the alkyl group having 1 to 20 carbon atoms are the same as those described above.

[0382] Among these, it is preferred that A 4 ~A 8 are 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 at least 3 of A 4 ~A 8 are fluorine atoms, more preferably 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, or a fluorinated alkenyl group having 2 to 5 carbon atoms, and at least 3 of A 4 ~A 8 are fluorine atoms, still more 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, and A 4 , A 5 and A 8 are fluorine atoms.

[0383] It should be noted that a perfluoroalkyl group is a group in which all hydrogen atoms of an alkyl group are replaced by fluorine atoms, and a perfluoroalkenyl group is a group in which all hydrogen atoms of an alkenyl group are replaced by fluorine atoms.

[0384] 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.

[0385] Specific examples of the preferred arylsulfonic acid compounds are listed below, but are not limited thereto.

[0386] [Chemical formula 48]

[0387]

[0388] As the organic solvent, there is no particular limitation as long as it can dissolve or disperse the charge transporting substance and the dopant substance. For example, 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-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexanediol, 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, n-hexyl acetate, etc. These can be used alone or in combination of two or more.

[0389] The viscosity of the charge transporting composition of the present invention is generally 1 to 50 mPa·s at 25°C, and the surface tension is generally 20 to 50 mN / m at 25°C.

[0390] Regarding the viscosity and surface tension of the charge transporting composition of the present invention, various factors such as the coating method to be used and the desired film thickness are considered, and adjusted by changing the types of organic solvents used, their ratios, the solid content concentration, etc.

[0391] In addition, the solid content concentration of the charge transporting composition of the present invention is appropriately set in consideration of the viscosity and surface tension of the composition, the thickness of the produced film, etc., and is generally about 0.1 to 15.0% by mass. From the viewpoint of suppressing the aggregation of the charge transporting substance in the composition, it is preferably 10.0% by mass or less, more preferably 8.0% by mass or less, and further preferably 5% by mass or less.

[0392] It should be noted that the solid components in the solid content concentration mentioned here mean the components other than the solvent contained in the charge transporting composition of the present invention.

[0393] The charge transport composition of the present invention can be produced by mixing the charge transport material of the present invention, an organic solvent, and a dopant material used as needed. There is no particular limitation on the mixing order.

[0394] When preparing the composition, heating can be appropriately carried out within the range where the components do not decompose or deteriorate.

[0395] In the present invention, regarding the charge transport composition, from the viewpoint of reproducibly obtaining a film with higher flatness, after dissolving the charge transport material, etc. in an organic solvent, it is preferably filtered using a submicron filter or the like.

[0396] By coating and firing the charge transport composition described above on a substrate, the charge transport film of the present invention can be formed on the substrate.

[0397] As the coating method of the composition, there is no particular limitation, and examples include dipping method, spin coating method, transfer printing method, roll coating method, brush coating, inkjet method, spraying method, slot coating method, etc. It is preferable to adjust the viscosity and surface tension of the composition according to the coating method.

[0398] When using the charge transport composition of the present invention, there is no particular limitation on the firing atmosphere either. Not only in an atmospheric atmosphere (under air), but also in an inert gas such as nitrogen or in a vacuum, a film with a uniform film formation surface and high charge transportability can be obtained, but usually it is under air.

[0399] In addition, there is no particular limitation on the firing conditions either. For example, heating and firing are carried out using a hot plate. Generally, also considering the desired charge transportability, etc., the firing temperature is appropriately determined within the range of 100 to 260 °C, and the firing time is appropriately determined within the range of 1 minute to 1 hour. Further, if necessary, multi-stage firing can be carried out at two or more different temperatures.

[0400] There is no particular limitation on the film thickness of the charge transport film. When used as a functional layer of an organic EL element, it is preferably 5 to 300 nm. As a method for changing the film thickness, there are methods such as changing the solid content concentration in the charge transport composition and changing the liquid amount during coating.

[0401] Since the fluorine-containing aniline derivative or polymer of the present invention contains fluorine atoms, it is mainly aimed at adjusting film physical properties such as improving coatability, improving the transparency of the obtained film, and adjusting the wettability of the film surface, and can also be used as an additive added to a charge transport composition containing other charge transport materials.

[0402] [6] Organic EL element

[0403] The organic EL element of the present invention has a pair of electrodes, and the charge transport film of the present invention is provided between these electrodes.

[0404] As representative configurations of the organic EL element, the following (a) to (f) can be cited, but are not limited thereto. It should be noted that 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 (hole) blocking layer or the like can be provided between the light-emitting layer and the cathode as needed. In addition, the hole injection layer, the hole transport layer, or the hole injection transport layer can also function as an electron blocking layer or the like, and the electron injection layer, the electron transport layer, or the electron injection transport layer can also function as a hole (hole) blocking layer or the like.

[0405] (a) Anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode

[0406] (b) Anode / hole injection layer / hole transport layer / light-emitting layer / electron injection transport layer / cathode

[0407] (c) Anode / hole injection transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode

[0408] (d) Anode / hole injection transport layer / light-emitting layer / electron injection transport layer / cathode

[0409] (e) Anode / hole injection layer / hole transport layer / light-emitting layer / cathode

[0410] (f) Anode / hole injection transport layer / light-emitting layer / cathode

[0411] The "hole injection layer", the "hole transport layer", and the "hole injection transport layer" are layers formed between the light-emitting layer and the anode, and have the function of transporting holes from the anode to the light-emitting layer. When only one layer of hole transport material is provided between the light-emitting layer and the anode, it is the "hole injection transport layer". When two or more layers of hole transport material are provided between the light-emitting layer and the anode, the layer close to the anode is the "hole injection layer", and the other layers are the "hole transport layer". In particular, the hole injection (transport) layer uses a film that is excellent not only in hole acceptability from the anode but also in hole injection property to the hole transport (light-emitting) layer.

[0412] The "electron injection layer", the "electron transport layer", and the "electron injection transport layer" are layers formed between the light-emitting layer and the cathode, and have the function of transporting electrons from the cathode to the light-emitting layer. When only one layer of electron transport 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 transport material are provided between the light-emitting layer and the cathode, the layer close to the cathode is the "electron injection layer", and the other layers are the "electron transport layer".

[0413] The "light-emitting layer" is an organic layer having a light-emitting function. In the case of an doping system, it contains a host material and a dopant material. At this time, the host material mainly has the functions of promoting the recombination of electrons and holes and confining excitons within the light-emitting layer, and the dopant material has the function of efficiently emitting light from the excitons obtained through recombination. In the case of a phosphorescent element, the host material mainly has the function of confining the excitons generated by the dopant within the light-emitting layer.

[0414] The charge-transporting thin film of the present invention can preferably be used as an organic functional film provided between the anode and the light-emitting layer in an organic EL element, can more preferably be used as a hole injection layer, a hole transport layer, a hole injection and transport layer, and can further preferably be used as a hole injection layer.

[0415] As the materials and manufacturing methods when manufacturing an organic EL element using the charge-transporting composition of the present invention, the following materials and manufacturing methods can be cited, but are not limited thereto.

[0416] An example of a manufacturing method of an OLED element having a hole injection layer composed of a thin film obtained from the charge-transporting composition of the present invention is as follows. Further, with respect to the electrodes, it is preferable to perform cleaning using alcohol, pure water, etc. and surface treatment such as UV ozone treatment and oxygen-plasma treatment in a range that does not cause adverse effects on the electrodes in advance.

[0417] On the anode substrate, using the above method, a hole injection layer is formed using the above charge-transporting composition. It is introduced into a vacuum evaporation 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 evaporated. Alternatively, in this method, instead of forming the hole transport layer and the light-emitting layer by evaporation, a hole transport layer forming composition containing a hole-transporting polymer and a light-emitting layer forming composition containing a light-emitting polymer are used, and these layers are formed by a wet method. Further, if necessary, an electron blocking layer can be provided between the light-emitting layer and the hole transport layer.

[0418] As anode materials, transparent electrodes represented by indium tin oxide (ITO) and indium zinc oxide (IZO), metal anodes composed of metals represented by aluminum, their alloys, etc. can be cited, and anode materials that have preferably been subjected to a planarization treatment are preferred. Poly(thiophene) derivatives and polyaniline derivatives having high charge transportability can also be used.

[0419] Further, as other metals constituting the metal anode, gold, silver, copper, indium, their alloys, etc. can be cited, but are not limited thereto.

[0420] Examples of materials for forming the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spiro dimers, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine (α-NPD), 4,4',4''-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4',4''-tris[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA) and other triarylamines, 5,5''-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2':5',2''-terthiophene (BMA-3T) and other oligothiophenes, etc.

[0421] Examples of materials for forming the light-emitting layer include 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 low molecular weight light-emitting materials such as silole derivatives; systems formed by mixing light-emitting materials and electron-transporting materials in high molecular weight compounds such as poly(p-phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly(3-alkylthiophene), polyvinylcarbazole, etc.

[0422] In addition, in the case of forming the light-emitting layer by vapor deposition, it can be co-vapor deposited with a light-emitting dopant. Examples of the light-emitting dopant include metal complexes such as tris(2-phenylpyridine)iridium(III) (Ir(ppy)3), pentacene derivatives such as rubrene, quinacridone derivatives, condensed polycyclic aromatic rings such as perylene, etc.

[0423] Examples of materials for forming the electron transport layer / hole blocking layer include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, pyrimidine derivatives, etc.

[0424] Examples of materials for forming the electron injection layer include metal oxides such as lithium oxide (Li2O), magnesium oxide (MgO), aluminum oxide (Al2O3), and metal fluorides such as lithium fluoride (LiF), sodium fluoride (NaF), but are not limited to these.

[0425] Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, etc.

[0426] Examples of materials for forming the electron blocking layer include tris(phenylpyrazole)iridium, etc.

[0427] Examples of hole-transporting polymers include poly[(9,9-dihexylfluorene-2,7-diyl)-co-(N,N'-bis{4-butylphenyl}-1,4-diaminophenylene)], poly[(9,9-dioctylfluorene-2,7-diyl)-co-(N,N'-bis{4-butylphenyl}-1,1'-biphenyl-4,4-diamine)], poly[(9,9-bis{1'-penten-5'-yl}fluorene-2,7-diyl)-co-(N,N'-bis{4-butylphenyl}-1,4-diaminophenylene)], poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine] capped with polysilsesquioxane, poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-butylphenyl))diphenylamine)], and the like.

[0428] Examples of light-emitting polymers include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), poly(phenylene vinylene) derivatives such as poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene) (MEH-PPV), poly(thiophene) derivatives such as poly(3-alkylthiophene) (PAT), polyvinylcarbazole (PVCz), and the like.

[0429] Regarding the organic EL element of the present invention, in order to prevent deterioration of characteristics, it can be sealed together with a water scavenger or the like according to a conventional method as needed.

[0430] Examples

[0431] Examples and comparative examples are listed below to illustrate the present invention more specifically, but the present invention is not limited to the following examples.

[0432] [Apparatus]

[0433] The physical properties of the samples were measured based on the following conditions using the following apparatus.

[0434] (1) Liquid chromatography (tracking of reaction)

[0435] Apparatus: Manufactured by Shimadzu Corporation

[0436] UV-VIS detector: SPD-20A

[0437] Column oven: CTO-20A

[0438] Degassing unit: DGU-20A

[0439] Liquid delivery unit: LC-20AB

[0440] Autosampler: SIL-20A

[0441] Column: Poroshell 120EC-C18 (2.7 μm, 3.0 × 50 mm, Agilent)

[0442] Column temperature: 40 °C

[0443] Solvent: Acetonitrile / water Acetonitrile concentration: 40% (0 - 0.01 min) → 40% - 100% (0.01 - 5 min) → 100% (5 - 15 min) (volume ratio)

[0444] Detector: UV

[0445] (2) Gel permeation chromatography (molecular weight determination of polymers)

[0446] Equipment: Manufactured by Shimadzu Corporation

[0447] UV-VIS detector: SPD-20A

[0448] Differential refractometer detector: RID-20A

[0449] Column oven: CTO-20A

[0450] Degassing unit: DGU-20A

[0451] Liquid delivery unit: LC-20AD

[0452] Autosampler: SIL-20A

[0453] Column: Shodex KF-G + KF-804L

[0454] Column temperature: 40 °C

[0455] Solvent: Tetrahydrofuran

[0456] Detector: UV

[0457] (3) Coating of the composition: Manufactured by Mikasa Co., Ltd., spin coater MS-A100

[0458] (4) Fabrication of components: Manufactured by Choshu Sangyo Co., Ltd., multifunctional evaporation device system C-E2L1G1-N

[0459] (5) Measurement of the current density of components: I-V-L measurement system manufactured by Tech World Co., Ltd.

[0460] (6) Glass transition temperature (Tg) measurement device: Diamond DSC manufactured by Perkin elmer

[0461] Measurement conditions: Under nitrogen atmosphere

[0462] Heating rate: 5 °C / min (40 - 300 °C)

[0463] (7) Measurement of 5% weight loss temperature (Td5%)

[0464] Apparatus: TG8120 manufactured by Rigaku Corporation

[0465] Measurement conditions: In an air atmosphere

[0466] Heating rate: 10 °C / min (40 - 500 °C)

[0467] (8) Automatic column chromatography apparatus (fractionation of target substance): 2CH parallel purification apparatus Purif-espoir2 manufactured by Shoko Scientific Co., Ltd.

[0468] (9) NMR: Avance III 500 MHz manufactured by Bruker

[0469] Internal standard

[0470] 19 F-NMR chemical shift correction

[0471] Trifluorotoluene = -64 ppm

[0472] 13 C-NMR chemical shift correction

[0473] Acetone-d6 = 206.68 ppm

[0474] Chloroform-d1 = 77.23 ppm

[0475] N,N-Dimethylformamide-d7 = 163.15 ppm

[0476] Tetrahydrofuran-d8 = 67.57 ppm

[0477] [Reagents]

[0478] The reagents used in the following examples and comparative examples are as described below.

[0479] Pd(PPh3)4 [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0480] Pd(DBA)2 [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0481] Pd(dppf)Cl2 [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0482] t-BuONa [manufactured by Kishida Chemical Co., Ltd.]

[0483] BINAP [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0484] Cesium carbonate [manufactured by Junsei Chemical Co., Ltd.]

[0485] Magnesium sulfate [manufactured by Kishida Chemical Co., Ltd.]

[0486] Potassium acetate [manufactured by Junsei Chemical Co., Ltd.]

[0487] Lithium hexamethyldisilazide (LHMDS) 1.3 mol / L solution in tetrahydrofuran [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0488] Lithium hexamethyldisilazide (LHMDS) 1 mol / L solution in toluene [manufactured by Aldrich]

[0489] RuPhos [manufactured by Aldrich]

[0490] t-BuXPhos [manufactured by Aldrich]

[0491] SPhos [manufactured by Aldrich]

[0492] t-BuMePhos [manufactured by Aldrich]

[0493] JhonPhos [manufactured by Aldrich]

[0494] CyJhonPhos [manufactured by Aldrich]

[0495] N,N-Dimethylformamide [manufactured by Junsei Chemical Co., Ltd.]

[0496] Ethyl acetate [manufactured by Tokyo Chemical Industry Co., Ltd. or Junsei Chemical Co., Ltd.]

[0497] Toluene [manufactured by Junsei Chemical Co., Ltd. or Kanto Chemical Co., Inc.]

[0498] Dioxane [manufactured by Kanto Chemical Co., Inc.]

[0499] Hexane [manufactured by Junsei Chemical Co., Ltd.]

[0500] Tetrahydrofuran [manufactured by Junsei Chemical Co., Ltd.]

[0501] Tetrahydrofurfuryl alcohol [manufactured by Kanto Chemical Co., Inc.]

[0502] Pentafluoroaniline [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0503] Fluorobenzene [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0504] Chlorobenzene [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0505] Bromobenzene [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0506] Iodobenzene [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0507] Bromopentafluorobenzene [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0508] 2-Fluoroaniline [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0509] 4-Bromoanisole [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0510] 4,4′-Diaminooctafluorobiphenyl [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0511] 1-Bromo-4-tert-butylbenzene [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0512] 1-Bromonaphthalene [manufactured by Junsei Chemical Co., Ltd.]

[0513] 2-Bromonaphthalene [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0514] 4-Bromotriphenylamine [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0515] 4-Iodotriphenylamine [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0516] 4-Bromo-4′-(diphenylamino)biphenyl [manufactured by FUJIFILM Wako Pure Chemical Corporation]

[0517] 2-Bromo-9,9′-spirobi[9H-fluorene] [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0518] 4,4′-Dibromobiphenyl [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0519] 1,4-Dibromobenzene [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0520] 3,6-Dibromo-9-phenylcarbazole [manufactured by FUJIFILM Wako Pure Chemical Corporation]

[0521] 2,7-Dibromo-9,9-dimethylfluorene [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0522] 4-Fluorobromobenzene [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0523] [1] Synthesis of fluorinated aromatic secondary amine compounds

[0524] (1) Reaction of pentafluoroaniline with 4-bromoanisole

[0525] [Chemical formula 49]

[0526]

[0527] [Comparative Example 1-1]

[0528] In a 30 mL reaction flask equipped with a reflux condenser, 0.05 mmol (57.8 mg) of Pd(PPh3)4, 1.2 mmol (115.3 mg) of t-BuONa, and 1.2 mmol (219.7 mg) of pentafluoroaniline were measured. The system was purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added thereto. After stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). In the liquid chromatography using a trace amount of the solution taken from the flask, peaks attributable to the starting materials could be confirmed, but peaks attributable to the target compound could not be confirmed.

[0529] [Comparative Example 1-2]

[0530] In a 30 mL reaction flask equipped with a reflux condenser, 0.05 mmol (57.8 mg) of Pd(PPh3)4, 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 were measured. The system was purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added thereto. After stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). In the liquid chromatography using a trace amount of the solution taken from the flask, peaks attributable to the starting materials could be confirmed, but peaks attributable to the target compound could not be confirmed.

[0531] [Comparative Example 1-3]

[0532] In a 30 mL reaction flask equipped with a reflux condenser, 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 were measured. The system was purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added thereto. Further, 0.923 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was added. After stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). In the liquid chromatography using a trace amount of the solution taken from the flask, peaks attributable to the starting materials could be confirmed, but peaks attributable to the target compound could not be confirmed.

[0533] [Comparative Example 1-4]

[0534] Except that RuPhos 0.075 mmol (35.0 mg) represented by the following formula (L2) was used instead of (±)BINAP, the operation was carried out in the same manner as in Comparative Examples 1-3. In the liquid chromatography using a trace amount of the solution taken from the flask, a peak attributable to the raw material could be confirmed, but a peak attributable to the target substance could not be confirmed.

[0535] [Chemical Formula 50]

[0536]

[0537] (In the formula, i-Pr represents isopropyl and Cy represents cyclohexyl.)

[0538] [Comparative Example 1-5]

[0539] 0.05 mmol (28.8 mg) of Pd(DBA)2 and 1.2 mmol (219.7 mg) of pentafluoroaniline were measured into a 30 mL reaction flask equipped with a reflux column, and the system was purged with nitrogen. 4 mL of dioxane, 1 mmol (187.0 mg) of 4-bromoanisole were added thereto, and further 0.923 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was added. After stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). In the liquid chromatography using a trace amount of the solution taken from the flask, a peak attributable to the raw material could be confirmed, but a peak attributable to the target substance could not be confirmed.

[0540] [Comparative Example 1-6]

[0541] 0.05 mmol (28.8 mg) of Pd(DBA)2, 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 were measured into a 30 mL reaction flask equipped with a reflux column, and the system was purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added thereto. After stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). In the liquid chromatography using a trace amount of the solution taken from the flask, a peak attributable to the raw material could be confirmed, but a peak attributable to the target substance could not be confirmed.

[0542] [Comparative Example 1-7]

[0543] In a 30 mL reaction flask equipped with a reflux column, 0.05 mmol (28.8 mg) of Pd(DBA)₂, 0.075 mmol (46.7 mg) of (±)-BINAP, and 1.2 mmol (219.7 mg) of pentafluoroaniline were measured. The system was purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added thereto. Further, 0.923 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was added. After stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). In the liquid chromatography using a trace amount of the solution taken from inside the flask, a peak attributable to the starting material could be confirmed, but a peak attributable to the target compound could not be confirmed.

[0544] [Example 1-1]

[0545] In a 30 mL reaction flask equipped with a reflux column, 0.05 mmol (28.8 mg) of Pd(DBA)₂, 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 were measured. The system was purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added thereto. After stirring at room temperature for 5 minutes, 0.923 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (1.2 mmol of LHMDS) was added. After stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). Incidentally, during the process, a trace amount of the solution inside the flask was taken, and the reaction was monitored by liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target compound increased. At this time, no distinct peak corresponding to the by-product was confirmed.

[0546] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated aqueous ammonium chloride solution and 30 mL of ethyl acetate, and extraction was carried out, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto, and extraction was carried out, and the organic layer was recovered. All the recovered organic layers were combined and dried over magnesium sulfate.

[0547] The magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The resulting residue was dissolved in 3 mL of toluene, and column chromatography was carried out using the resulting solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3), and the fraction containing the target compound was collected.

[0548] Finally, the solvent was removed from the fraction collected at 80 °C under reduced pressure to obtain 67.2 mg of the target product (yield 26%).

[0549] 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, 2H)

[0550] 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

[0551] 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)

[0552] 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)

[0553] HRMS (ESI): C 13 H8F5NO (M + H) + Calculated value for 289.0526, measured value 290.0589.

[0554] [Example 1 - 2]

[0555] 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 product (yield > 99%).

[0556] [Example 1 - 3]

[0557] In a 30 mL reaction flask equipped with a reflux column, 0.05 mmol (28.8 mg) of Pd(DBA)₂, 0.075 mmol (35.0 mg) of RuPhos, and 1.2 mmol (219.7 mg) of pentafluoroaniline were measured. The system was purged with nitrogen. 4 mL of dioxane and 1 mmol (187.0 mg) of 4-bromoanisole were added thereto, and the mixture was stirred at room temperature for 5 minutes. Next, 0.923 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was added, and after stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 °C for 3 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was monitored by liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target compound increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0558] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated aqueous ammonium chloride solution and 30 mL of ethyl acetate, and extraction was carried out, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto, and extraction was carried out, and the organic layer was recovered. All the recovered organic layers were combined and dried over magnesium sulfate.

[0559] Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate using a rotary evaporator. The obtained residue was dissolved in 3 mL of toluene, and column chromatography was carried out using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3), and the fraction containing the target compound was fractionated.

[0560] Finally, the solvent was removed from the fraction fractionated at 80 °C under reduced pressure to obtain 287.3 mg of the target compound (yield > 99%).

[0561] [Example 1-4]

[0562] Except for using 0.2 mmol (93.3 mg) of RuPhos and setting the reaction time to 5 hours, the reaction and post-treatment were carried out in the same manner as in Examples 1-3 to obtain 286.0 mg of the target compound (yield > 99%).

[0563] [Example 1-5]

[0564] Except for using 0.075 mmol (31.8 mg) of t-BuXPhos represented by the following formula (L4) instead of RuPhos and setting the reaction time to 5 hours, the reaction and post-treatment were carried out in the same manner as in Examples 1-3 to obtain 243.9 mg of the target product (yield 84%).

[0565] [Chemical Formula 51]

[0566]

[0567] (In the formula, i-Pr represents isopropyl and t-Bu represents tert-butyl.)

[0568] [Example 1-6]

[0569] Except for using 0.075 mmol (30.8 mg) of SPhos represented by the following formula (L1) instead of RuPhos and setting the reaction time to 5 hours, the reaction and post-treatment were carried out in the same manner as in Examples 1-3 to obtain 246.0 mg of the target product (yield 85%).

[0570] [Chemical Formula 52]

[0571]

[0572] (In the formula, Me represents methyl and Cy represents cyclohexyl.)

[0573] [Example 1-7]

[0574] Except for using 0.075 mmol (23.4 mg) of t-BuMePhos represented by the following formula (L5) instead of RuPhos and setting the reaction time to 5 hours, the reaction and post-treatment were carried out in the same manner as in Examples 1-3 to obtain 246.3 mg of the target product (yield 85%).

[0575] [Chemical Formula 53]

[0576]

[0577] (In the formula, Me represents methyl and t-Bu represents tert-butyl.)

[0578] [Example 1-8]

[0579] Except for using 0.075 mmol (22.4 mg) of JhonPhos represented by the following formula (L6) instead of RuPhos and setting the reaction time to 5 hours, the reaction and post-treatment were carried out in the same manner as in Examples 1-3 to obtain 268.2 mg of the target product (yield 95%).

[0580] [Chemical Formula 54]

[0581]

[0582] (In the formula, t-Bu represents tert-butyl.)

[0583] [Example 1-9]

[0584] Except for using 0.075 mmol (26.3 mg) of CyJhonPhos represented by the following formula (L7) instead of RuPhos and setting the reaction time to 5 hours, the reaction and post-treatment were carried out in the same manner as in Examples 1-3 to obtain 208.9 mg of the target product (yield 73%).

[0585] [Chemical Formula 55]

[0586]

[0587] (In the formula, Cy represents cyclohexyl.)

[0588] The summaries of the above Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-7 are shown in Table 1.

[0589] [Table 1]

[0590]

[0591] (Example 1-4: Amount of RuPhos used: 0.2 mmol)

[0592] (2) Reaction of pentafluoroaniline with aryl halide

[0593] [Chemical Formula 56]

[0594]

[0595] [Comparative Example 1-8]

[0596] 0.05 mmol (28.8 mg) of Pd(DBA)2, 0.075 mmol (35.0 mg) of RuPhos, and 1.2 mmol (219.7 mg) of pentafluoroaniline were measured into a 30 mL reaction flask equipped with a reflux column, and the system was purged with nitrogen. 4 mL of dioxane and 1 mmol (96.1 mg) of fluorobenzene were added thereto, and the mixture was stirred at room temperature for 5 minutes. Next, 0.923 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was added, and the mixture was stirred at room temperature for 5 minutes and then heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during the process, a trace amount of the solution taken from the flask was used, and the reaction was traced by liquid chromatography. Except for the peaks attributable to the raw materials, a large number of obvious peaks not attributable to the target product could be confirmed.

[0597] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated ammonium chloride aqueous solution and 30 mL of ethyl acetate for extraction, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto for extraction, the organic layer was recovered, all the recovered organic layers were combined, and it was dried over magnesium sulfate.

[0598] The magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate using a rotary evaporator. The obtained residue was dissolved in 3 mL of toluene, and column chromatography (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3) was carried out using the obtained solution, and the fraction other than the fraction mainly containing the raw material was fractionated.

[0599] Finally, the solvent was removed from the fraction fractionated at 80 °C under reduced pressure to obtain a solid. However, in the 1 1H-NMR spectrum of the obtained solid, a large number of peaks that could not be attributed to the raw material or the target compound were found. This mixture was a mixture containing multiple by-products, and it was judged that it was difficult to separate the target compound therefrom, and no further purification was attempted.

[0600] [Example 1-10]

[0601] 0.05 mmol (28.8 mg) of Pd(DBA)2, 0.075 mmol (35.0 mg) of RuPhos, and 1.2 mmol (219.7 mg) of pentafluoroaniline were measured in a 30 mL reaction flask equipped with a reflux column, and the system was purged with nitrogen. 4 mL of dioxane and 1 mmol (112.6 mg) of chlorobenzene were added thereto, and the mixture was stirred at room temperature for 5 minutes. Next, 0.923 mL of 1.3 mol / L LHMDS in tetrahydrofuran solution (equivalent to 1.2 mmol of LHMDS) was added, and after stirring at room temperature for 5 minutes, it was heated and stirred in a bath at 110 °C for 3 hours (internal temperature 92 °C). It should be noted that during this process, a small amount of the solution in the flask was taken, and the reaction was traced using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target compound increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0602] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated aqueous ammonium chloride solution 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 placed in the separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto for extraction, the organic layer was recovered, all the recovered organic layers were combined, and it was dried over magnesium sulfate.

[0603] The magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate using a rotary evaporator. The obtained residue was dissolved in 3 mL of toluene, and column chromatography was carried out using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3), and the fraction containing the target compound was collected.

[0604] Finally, the solvent was removed from the fraction collected at 80 °C under reduced pressure to obtain 195.7 mg of the target compound (yield 81%).

[0605] [Example 1-11]

[0606] 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 5 hours, to obtain 256.6 mg of the target compound (yield > 99%).

[0607] [Example 1-12]

[0608] 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 1 mol / L LHMDS toluene solution (equivalent to 1.2 mmol of LHMDS) was used instead of 1.3 mol / L LHMDS tetrahydrofuran solution, and the reaction time was 5 hours, to obtain 243.5 mg of the target compound (yield 94%).

[0609] [Example 1-13]

[0610] 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%).

[0611] [Example 1-14]

[0612] [Chemical formula 57]

[0613]

[0614] In a 30 mL reaction flask equipped with a reflux condenser, 0.05 mmol (28.8 mg) of Pd(DBA)₂, 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 were measured. The system was purged with nitrogen. 4 mL of dioxane was added thereto, and the mixture was stirred for 5 minutes. Next, 0.923 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was added, and after stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was monitored by liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0615] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated aqueous ammonium chloride solution and 30 mL of ethyl acetate, and extraction was carried out, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto, and extraction was carried out, and the organic layer was recovered. All the recovered organic layers were combined and dried over magnesium sulfate.

[0616] The magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The resulting residue was dissolved in 3 mL of toluene, and column chromatography was carried out using the resulting solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3), and the fraction containing the target product was collected.

[0617] Finally, the solvent was removed from the fraction collected at 50 °C under reduced pressure to obtain 242.9 mg of the target product (yield 88%).

[0618] 1 H NMR (500.13 MHz, CDCl₃): δ = 5.39 (brs, 1H), 6.84 (m, 2H), 7.00 (brt, 2H)

[0619] 13 C NMR (125.77 MHz, CDCl₃): δ = 116.0, 116.2, 118.9, 119.0, 138.3, 157.8, 159.7

[0620] 1919F NMR (470.53 MHz, CDCl3): δ -165.6 (brt, 1F), -164.0 (brdt, 1F), 151.8 (brd, 2F), 122.6 (brs, 1F);

[0621] 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)

[0622] The summaries of the above Examples 1-10 to 1-14 and Comparative Examples 1-8 are shown in Table 2.

[0623] [Table 2]

[0624]

[0625] (3) Reaction of mono- to tetrafluoroaniline with 4-bromoanisole

[0626] [Chemical Formula 58]

[0627]

[0628] [Example 1-15]

[0629] Weigh 0.05 mmol (28.8 mg) of Pd(DBA)2 and 0.075 mmol (35.0 mg) of RuPhos in a 30 mL reaction flask equipped with a reflux column, and displace the nitrogen in the system. Add 4 mL of dioxane thereto, and then add 1.2 mmol (133.3 mg) of 2-fluoroaniline and 1 mmol (187.0 mg) of 4-bromoanisole. Stir at room temperature for 5 minutes. Next, add 0.923 mL of 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS). After stirring at room temperature for 5 minutes, heat and stir in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was traced using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0630] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together 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 placed in the separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto for extraction, the organic layer was recovered, all the recovered organic layers were combined, and it was dried over magnesium sulfate.

[0631] The magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The resulting residue was dissolved in 3 mL of toluene, and column chromatography (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3) was carried out using the resulting solution, and the fraction containing the target compound was collected.

[0632] Finally, the solvent was removed from the fraction collected at 80 °C under reduced pressure to obtain 217.6 mg of the target compound (yield 98%).

[0633] 1 H 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)

[0634] 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

[0635] 19 F NMR (470.53 MHz, CDCl3): δ - 136.1 (brs); IR (pure substance)

[0636] 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)

[0637] HRMS(ESI):C 13 H 12 FNO(M+H) + Calculated value for 217.0903, measured value 218.0963.

[0638] [Example 1-16]

[0639] 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, and 210.6 mg (yield 97%) of the target product was obtained.

[0640] 1 H NMR(500.13MHz,CDCl3):δ=3.79(s,3H),5.57(brs,1H),6.47(ddd,J=8.3,2.3,0.9Hz,1H),6.56(dt,J=11.4,2.3Hz,1H),6.59(ddd,J=8.3,2.2,0.9Hz,1H),6.87(d,J=8.9,6.7Hz,2H),7.07(dd,J=8.9,6.7Hz,2H),7.11(td,J=8.3,6.7Hz,2H)

[0641] 13 C NMR(125.77MHz,CDCl3):δ=55.7,101.9,105.9,111.0,1145.0,123.6,130.6,134.8,147.7,156.2,164.2

[0642] 19 F NMR (470.53 MHz, CDCl3): δ = -113.7 (ms)

[0643] IR (pure substance): 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)

[0644] HRMS(ESI): C 13 H 12 FNO(M + H) + Calculated value: 217.0903, Measured value: 218.0969.

[0645] [Example 1 - 17]

[0646] Except for using 1.2 mmol (133.3 mg) of 4 - fluoroaniline instead of 2 - fluoroaniline, the reaction and post - treatment were carried out in the same manner as in Example 1 - 15, and 161.7 mg (yield 74%) of the target product was obtained.

[0647] 1 H NMR(500.13 MHz, CDCl3): δ = 3.79(s, 3H), 5.36(brs, 1H), 6.84 - 7.25(m, 8H)

[0648] 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

[0649] 19 F NMR(470.45 MHz, CDCl3): δ = - 125.6(s)

[0650] IR (pure substance): 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)

[0651] HRMS(ESI): C 13 H12 FNO(M+H) + Calculated value: 217.0903, Measured value: 218.0965

[0652] [Example 1-18]

[0653] 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, and 216.2 mg (yield 92%) of the target product was obtained.

[0654] 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)

[0655] 13 C NMR (125.77 MHz, CDCl3): δ = 55.8, 112.0, 114.6, 118.8, 121.0, 121.9, 137.1, 154.9, 156.1

[0656] 19 F NMR (470.45 MHz, CDCl3): δ = -123.4 (m)

[0657] 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)

[0658] HRMS (ESI): C 13 H 11 F2NO(M+H) + Calculated value: 235.0809, Measured value: 236.0867

[0659] [Example 1-19]

[0660] In a 30 mL reaction flask equipped with a reflux column, 0.05 mmol (28.8 mg) of Pd(DBA)₂, 0.075 mmol (35.0 mg) of RuPhos, and 1.2 mmol (176.5 mg) of 2,4,6-trifluoroaniline were measured. The system was purged with nitrogen. 4 mL of dioxane was added thereto, and then 1 mmol (187.0 mg) of 4-bromoanisole was added. After stirring for 5 minutes, 0.923 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was added, and the mixture was heated and stirred in a bath at 110 °C for 4 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was monitored by liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0661] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated ammonium chloride aqueous solution and 30 mL of ethyl acetate, and extraction was carried out, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto, and extraction was carried out, and the organic layer was recovered. All the recovered organic layers were combined and dried over magnesium sulfate.

[0662] The magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate using a rotary evaporator. The obtained residue was dissolved in 3 mL of toluene, and column chromatography was carried out using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3), and the fraction containing the target product was fractionated.

[0663] Finally, the solvent was removed from the fraction fractionated at 80 °C under reduced pressure to obtain 237.4 mg of the target product (yield 91%).

[0664] 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)

[0665] 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

[0666] 1919F NMR (470.45 MHz, CDCl3): δ = -119.8 (brs), -116.9 (brs)

[0667] 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)

[0668] HRMS (ESI): C 13 H 10 F3NO (M + H) + Calcd for 253.0714, found 254.0772.

[0669] [Example 1 - 20]

[0670] 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, and 243.9 mg (yield 90%) of the target product was obtained.

[0671] 1 1H NMR (500.13 MHz, CDCl3): δ = 3.79 (s, 3H), 5.56 (brs, 1H), 6.63 (tt, J = 10.0, 7.1 Hz, 1H), 6.84 (d, J = 8.9 Hz, 2H), 6.92 (brd, J = 8.9 Hz, 2H)

[0672] 13 13C NMR (125.77 MHz, CDCl3): δ = 55.8, 96.8, 114.6, 121.1, 124.6, 134.9, 139.4, 146.8, 156.2

[0673] 1919F 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)

[0674] HRMS (ESI): C 13 H9F4NO (M + H) + Calculated value for 271.0620, found value 272.0694.

[0675] The summary of Examples 1-15 to 1-20 above is shown in Table 3. Further, the results of Example 1-3 are also shown together.

[0676] [Table 3]

[0677]

[0678] [Example 1-21]

[0679] 2.0 mmol (115.0 mg) of Pd(DBA)2, 0.3 mmol (140.0 mg) of RuPhos, and 2.5 mmol (656.3 mg) of 4,4'-diaminooctafluorobiphenyl were weighed into a 30 mL reaction flask equipped with a reflux column, and the system was purged with nitrogen. 8 mL of dioxane was added thereto, and then 4.8 mmol (753.6 mg) of bromobenzene was added. After stirring for 5 minutes, 3.7 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 4.8 mmol of LHMDS) was added, and the mixture was heated and stirred in an oil bath at 110 °C for 5 hours (internal temperature 92 °C). Incidentally, during the reaction, a small amount of the solution in the flask was taken, and the reaction was monitored by liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target compound increased. At this time, no distinct peak corresponding to the by-product was confirmed.

[0680] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated ammonium chloride aqueous solution and 30 mL of ethyl acetate for extraction, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto for extraction, the organic layer was recovered, all the recovered organic layers were combined, and it was dried over magnesium sulfate.

[0681] The magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate using a rotary evaporator. The obtained residue was dissolved in 3 mL of toluene, and column chromatography (elution solvent: hexane / ethyl acetate = 100 / 0 → 90 / 10) was carried out using the obtained solution, and the fraction containing the target substance was collected.

[0682] Finally, the solvent was removed from the fraction collected at 80 °C under reduced pressure to obtain 0.88 g of the target substance (yield 92%).

[0683] 1 H NMR (500.13 MHz, CDCl3): δ = 5.45 (brs, 1H), 6.85 (brd, 2H), 7.02 (brt, 1H), 7.30 (brt, 2H)

[0684] 13 C NMR (125.77 MHz, CDCl3): δ = 116.7, 122.2, 129.5, 142.3

[0685] 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 (pure substance): 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)

[0686] [Example 1-22]

[0687] Except that 4.8 mmol (1023.0 mg) of 1-bromo-4-tert-butylbenzene was used instead of bromobenzene, the reaction and post-treatment were carried out in the same manner as in Example 1-21 to obtain 1.07 g of the target substance (yield 91%).

[0688] 11H 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)

[0689] 13 13C NMR (125.77 MHz, acetone): δ = 31.9, 34.8, 98.5, 118.9, 125.9, 126.6, 140.4, 141.2, 146.0

[0690] 19 19F NMR (470.45 MHz, acetone): δ = -152.67 (brd, F), -143.45 - (-143.1) (m, 4F)

[0691] 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)

[0692] HRMS (ESI): C 32 H 28 F8N2 (M + H) + Calculated value for 592.2125, found value 593.2170.

[0693] [Example 1 - 23]

[0694] In a 30 mL reaction flask equipped with a reflux column, 0.2 mmol (115.0 mg) of Pd(DBA)₂, 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′-tert-butylbiphenyl were measured. The system was purged with nitrogen. 8 mL of dioxane was added thereto, and after stirring for 5 minutes, 3.7 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 4.8 mmol of LHMDS) was added, and the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was traced using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target compound increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0695] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated ammonium chloride aqueous solution and 30 mL of ethyl acetate, and extraction was carried out, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto, and extraction was carried out, and the organic layer was recovered. All the recovered organic layers were combined and dried over magnesium sulfate.

[0696] The magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The resulting residue was dissolved in 3 mL of toluene, and column chromatography was carried out using the resulting solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 90 / 10), and the fraction containing the target compound was collected.

[0697] Finally, the solvent was removed from the fraction collected at 80 °C under reduced pressure to obtain 892.6 mg of the target compound (yield 60%).

[0698] 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)

[0699] 13 C NMR (125.77 MHz, THF): δ = 31.9, 34.8, 98.5, 118.9, 125.9, 126.6, 140.4, 141.2, 146.0

[0700] 19¹⁹F NMR (470.45 MHz, THF): δ = -152.14 (brd, F), -143.24, -143.29 (m, 4F)

[0701] 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)

[0702] HRMS (ESI): C 44 H 36 F₈N₂ (M + H) + Calcd for 744.2751, found 745.2794.

[0703] [Example 1 - 24]

[0704] The reaction and workup were carried out in the same manner as in Example 1 - 23, except that 1 - bromonaphthalene 4.8 mmol (993.9 mg) was used instead of 4 - bromo - 4'-tert - butylbiphenyl, to give the title compound 617.0 mg (yield 68%).

[0705] 1 ¹H 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)

[0706] 13 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, 129 126.9, 127.4, 127.7, 128.6, 129, 135.6, 141.4, 146.1

[0707] 1919F NMR (470.45 MHz, DMF): δ = -153.18 (brd, J = 13.9 Hz, 4F), -143.45 - (-143.35) (m, 4F)

[0708] 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)

[0709] HRMS (ESI): C 32 H 16 F8N2 (M + H) + Calcd for 580.1186, found 581.1249.

[0710] [Example 1 - 25]

[0711] The reaction and work-up were carried out in the same manner as in Examples 1 - 23, except that 4.8 mmol (993.9 mg) of 2-bromonaphthalene was used instead of 4-bromo-4'-tert-butylbiphenyl, to give 770.2 mg (53% yield) of the target compound.

[0712] 1 1H 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)

[0713] 13 13C 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

[0714] 19 19F NMR (470.45 MHz, DMSO): δ = -148.08 (brd, 4F), -140.33 (brd, 4F)

[0715] IR (pure substance): 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)

[0716] HRMS (ESI): C 32 H 16 F8N2(M + H) + Calculated value 580.1186, measured value 581.1249.

[0717] [Example 1 - 26]

[0718] Except for using 4 - bromotriphenylamine 4.8 mmol (1556.2 mg) instead of 4 - bromo - 4′ - tert - butylbiphenyl, the reaction and post - treatment were carried out in the same manner as in Example 1 - 23, and 1417.3 mg of the target product was obtained (yield 87%).

[0719] 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)

[0720] 13 C 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

[0721] 19 F NMR (470.45 MHz, acetone): δ = - 152.72(brd, J = 13.9 Hz, 4F), - 143.27(m, 4F)

[0722] IR (pure substance): 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)

[0723] HRMS (ESI): C 48 H 30 F8N4(M + H) + Calculated value for 814.2343, measured value 814.2312.

[0724] [Example 1 - 27]

[0725] Except for using 4 - iodotriphenylamine 4.8 mmol (1781.9 mg) instead of 4 - bromo - 4′ - tert - butylbiphenyl, the reaction and post - treatment were carried out in the same manner as in Example 1 - 23, and the target product 1101.3 mg (yield 68%) was obtained.

[0726] [Example 1 - 28]

[0727] Except for using 4 - bromo - 4′ - (diphenylamino)biphenyl 4.8 mmol (1921.5 mg) instead of 4 - bromo - 4′ - tert - butylbiphenyl, the reaction and post - treatment were carried out in the same manner as in Example 1 - 23, and the target product 1903.1 mg (yield 99%) was obtained.

[0728] [Example 1 - 29]

[0729] Except for using 2 - bromo - 9,9′ - spirobi[9H - fluorene] 4.8 mmol (1897.4 mg) instead of 4 - bromo - 4′ - tert - butylbiphenyl, the reaction and post - treatment were carried out in the same manner as in Example 24, and the target product 1.88 g (yield 98%) was obtained.

[0730] 11H 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, 4H), 7.36 (td, J = 7.5, 1.0 Hz, 2H), 7.40 (td, J = 7.5, 1.0 Hz, 4H), 7.82 (s, 2H), 7.89 (brdd, 4H) 7.97 (brd, J = 7.5, 4H)

[0731] 13 13C 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

[0732] 19 19F NMR (470.45 MHz, acetone): δ = -152.3 (brd, 4F), -143.2 (m, 4F)

[0733] 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)

[0734] HRMS (ESI): C 62 H 32 F8N2 (M + H) + Calculated value for 956.2438, found value 812.4212.

[0735] [Example 1 - 30]

[0736] [Chemical Formula 59]

[0737]

[0738] In a 100 mL reaction flask equipped with a reflux column, 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 were measured, and the system was purged with nitrogen. 150 mL of N,N-dimethylformamide was added thereto, and after stirring for 5 minutes, the mixture was heated and stirred in a 90 °C bath for 3 hours. Furthermore, the reaction was monitored by chromatography (TLC) using a trace amount of the reaction mixture obtained from the system.

[0739] After cooling the reaction mixture to room temperature, the solvent was removed and concentrated under reduced pressure from the cooled reaction mixture. 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 for extraction. The organic layer was recovered from the separatory funnel. Then, the recovered organic layer was dried over magnesium sulfate.

[0740] The magnesium sulfate was removed by filtration, the obtained filtrate was concentrated, and column chromatography (elution solvent: hexane / ethyl acetate = 100 / 0 → 96 / 4) was performed using the obtained concentrate, and the fraction containing the target compound was collected.

[0741] Finally, the solvent was removed from the fraction collected under reduced pressure to obtain 4.21 g (yield 76%) of N-phenylcarbazol-3-ylboronic acid pinacol ester.

[0742] 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)

[0743] [Chemical formula 60]

[0744]

[0745] In a 50 mL reaction flask equipped with a reflux column, 0.09 mmol (104.1 mg) of Pd(PPh3)4, 9 mmol (359.9 mg) of sodium hydroxide, 3 mmol (1107.8 mg) of N-phenylcarbazol-3-yl-boronic acid pinacol ester, and 3.3 mmol (1184.7 mg) of 4-bromo-4′-iodobiphenyl were measured. The system was purged with nitrogen. 13.5 mL of a mixed solvent of tetrahydrofuran and water (2 / 1 (v / v)) was added thereto. After stirring for 5 minutes, it was heated and stirred in a 50 °C bath for 5 hours. Furthermore, the reaction was monitored by chromatography (TLC) using a small amount of the reaction mixture obtained from the system.

[0746] After cooling the reaction mixture to room temperature, the solvent was removed and concentrated under reduced pressure from the cooled reaction mixture. The concentrate was placed in a separatory funnel together with 50 mL of ion-exchanged water and washed. Next, 50 mL of tetrahydrofuran was added and extraction was performed. The organic layer was recovered from the separatory funnel. Then, the recovered organic layer was dried over magnesium sulfate.

[0747] Magnesium sulfate was removed by filtration, the obtained filtrate was concentrated, and column chromatography (elution solvent: hexane / ethyl acetate = 100 / 0 → 96 / 4) was performed using the obtained concentrate, and the fraction containing the target compound was collected.

[0748] Finally, the solvent was removed from the fraction collected under reduced pressure to obtain 810 mg (yield 57%) of 4-bromo-4′-(N-phenylcarbazol-3-yl)-biphenyl.

[0749] 1 1H 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 = 7.9 Hz, 1H), 8.39 (brs, 1H)

[0750] In a 30 mL reaction flask equipped with a reflux column, 0.5 mmol (28.8 mg) of Pd(DBA)₂, 0.75 mmol (35.0 mg) of RuPhos, and 0.5 mmol (164.1 mg) of 4,4′-diaminooctafluorobiphenyl were measured. The system was purged with nitrogen. 8 mL of dioxane was added thereto, and then 1.05 mmol (498.1 mg) of 4-bromo-4′-(N-phenylcarbazol-3-yl)-biphenyl was added. After stirring for 5 minutes, 0.923 mL (1.2 mmol) of a 1.3 mol / L solution of LHMDS in tetrahydrofuran was added, and the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was monitored by liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target compound increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0751] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated aqueous ammonium chloride solution and 30 mL of ethyl acetate, and extraction was carried out, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto, and extraction was carried out, and the organic layer was recovered. All the recovered organic layers were combined and dried over magnesium sulfate.

[0752] The magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The resulting residue was dissolved in 3 mL of toluene, and column chromatography was carried out using the resulting solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 90 / 10), and the fraction containing the target compound was collected.

[0753] Finally, the solvent was removed from the fraction collected at 80 °C under reduced pressure to obtain 457 mg of the target compound (yield 82%).

[0754] 1 ¹H 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)

[0755] [Example 1 - 31]

[0756] [Chemical Formula 61]

[0757]

[0758] In a 100 mL reaction flask equipped with a reflux condenser, 0.45 mmol (367.5 mg) of Pd(dppf)Cl₂, 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 were measured, and the system was purged with nitrogen. 150 mL of N,N-dimethylformamide was added thereto, and after stirring for 5 minutes, the mixture was heated and stirred in a 90 °C bath for 3 hours. Furthermore, the reaction was monitored by chromatography (TLC) using a small amount of the reaction mixture obtained from the system.

[0759] After cooling the reaction mixture to room temperature, the solvent was removed and concentrated under reduced pressure from the cooled reaction mixture. The concentrate was placed in a separatory funnel together with 50 mL of ionized water and washed, and then 50 mL of chloroform was added for extraction. The organic layer was recovered from the separatory funnel. Then, the recovered organic layer was dried over magnesium sulfate.

[0760] The magnesium sulfate was removed by filtration, the obtained filtrate was concentrated, and column chromatography (elution solvent: hexane / ethyl acetate = 100 / 0 → 96 / 4) was performed using the obtained concentrate, and the fraction containing the target compound was collected.

[0761] Finally, the solvent was removed from the fraction collected under reduced pressure to obtain 1.85 g (yield 28%) of 9,9′-spirobi[9H-fluorene]-2-ylboronic acid pinacol ester.

[0762] 1 ¹H 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)

[0763] [Chemical formula 62]

[0764]

[0765] In a 50 mL reaction flask equipped with a reflux condenser, 0.09 mmol (104.1 mg) of Pd(PPh3)4, 9 mmol (359.9 mg) of sodium hydroxide, 3 mmol (1327.1 mg) of 9,9′-spirobi[9H-fluorene]-2-ylboronic acid pinacol ester, and 3.3 mmol (1184.7 mg) of 4-bromo-4′-iodobiphenyl were measured. The system was purged with nitrogen. A mixed solvent of tetrahydrofuran and water (2 / 1 (v / v)) (13.5 mL) was added thereto, and after stirring for 5 minutes, the mixture was heated and stirred in a 50 °C bath for 5 hours. Further, the reaction was monitored by chromatography (TLC) using a small amount of the reaction mixture obtained from the system.

[0766] After cooling the reaction mixture to room temperature, the solvent was removed and concentrated under reduced pressure from the cooled reaction mixture. 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 for extraction. The organic layer was recovered from the separatory funnel. Then, the recovered organic layer was dried over magnesium sulfate.

[0767] Magnesium sulfate was removed by filtration, the obtained filtrate was concentrated, and column chromatography was performed using the obtained concentrate (elution solvent: hexane / ethyl acetate = 100 / 0 → 96 / 4), and the fraction containing the target compound was collected.

[0768] Finally, the solvent was removed from the fraction collected under reduced pressure to obtain 836.4 mg (yield 51%) of 2-(4′-biphenyl-4-yl)-9,9′-spirobi[9H-fluorene].

[0769] 1 1H 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, 5H), 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, 2H), 7.87 (d, J = 7.6 Hz, 1H), 7.92 (d, J = 7.9 Hz, 1H)

[0770] In a 30 mL reaction flask equipped with a reflux column, 0.5 mmol (28.8 mg) of Pd(DBA)₂, 0.75 mmol (35.0 mg) of RuPhos, and 0.5 mmol (164.1 mg) of 4,4′-diaminooctafluorobiphenyl were measured. The system was purged with nitrogen. 8 mL of dioxane was added thereto, and then 1.05 mmol (574.9 mg) of 2-(4′-bromobiphenyl-4-yl)-9,9′-spirobi[9H-fluorene] was added. After stirring for 5 minutes, 0.923 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 1.2 mmol of LHMDS) was added, and the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was traced using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0771] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated ammonium chloride aqueous solution and 30 mL of ethyl acetate, and extraction was carried out, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto, and extraction was carried out, and the organic layer was recovered. All the recovered organic layers were combined and dried over magnesium sulfate.

[0772] Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate using a rotary evaporator. The obtained residue was dissolved in 3 mL of toluene, and column chromatography was carried out using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 90 / 10), and the fraction containing the target product was fractionated.

[0773] Finally, the solvent was removed from the fraction fractionated at 80 °C under reduced pressure to obtain 532 mg of the target product (yield 86%).

[0774] 1 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),

[0775] 1313C 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

[0776] 19 19F NMR (470.45 MHz, CDCl3): δ = -151.41 (brd, 4F), -140.63 (m, 4F)

[0777] 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)

[0778] The summaries of the above Examples 1-21 to 1-31 are shown in Table 4.

[0779] [Table 4]

[0780]

[0781] (4) Reaction of pentafluoroaniline with 4,4'-dibromobiphenyl

[0782] [Chemical Formula 63]

[0783]

[0784] [Example 1-32]

[0785] In a 30 mL reaction flask equipped with a reflux column, 0.1 mmol (57.5 mg) of Pd(DBA)₂, 0.15 mmol (69.8 mg) of RuPhos, and 1 mmol (312.7 mg) of 4,4′-dibromobiphenyl were measured, and the system was purged with nitrogen. 8 mL of dioxane and 2.4 mmol (439.3 mg) of pentafluoroaniline were added thereto. After stirring for 5 minutes, 1.84 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 2.4 mmol of LHMDS) was added, and the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was traced using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0786] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated aqueous ammonium chloride solution and 30 mL of ethyl acetate, and extraction was carried out, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 20 mL of ethyl acetate was added thereto, and extraction was carried out, and the organic layer was recovered. All the recovered organic layers were combined and dried over magnesium sulfate.

[0787] Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The resulting residue was dissolved in 3 mL of toluene, and column chromatography was carried out using the resulting solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 90 / 10), and the fraction containing the target product was collected.

[0788] Finally, the solvent was removed from the fraction collected at 80 °C under reduced pressure to obtain 451.7 mg of the target product (yield 58%).

[0789] 1 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)

[0790] 13 ¹³C NMR (125.77 MHz, DMSO): δ = 116.1, 118.1, 126.9, 132.4, 137.0, 138.3, 142.3, 142.7

[0791] 1919F NMR (470.45 MHz, DMSO): δ = -165.04 (brt, 2F), -163.81 (brt, 4F), -148.47 (brd, 4H)

[0792] 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)

[0793] (5) Reaction of pentafluoroaniline with bromobenzene: Influence of base

[0794] [Chemical formula 64]

[0795]

[0796] [Examples 1 - 33]

[0797] Except for using pentafluoroaniline (1 mmol), bromobenzene (2.4 mmol), 1.85 mL of 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 2.4 mmol of LHMDS), the reaction and post - treatment were carried out in the same manner as in Examples 1 - 11, and 179.8 mg of the target product was obtained (yield 69%).

[0798] [Examples 1 - 34]

[0799] Except for using pentafluoroaniline (2.4 mmol), bromobenzene (1 mmol), 1.85 mL of 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 2.4 mmol of LHMDS), the reaction and post - treatment were carried out in the same manner as in Examples 1 - 11, and 193.6 mg of the target product was obtained (yield 75%).

[0800] The summaries of Examples 1 - 33 and Examples 1 - 34 are shown in Table 5. From their results, it can be seen that if there is an excess of base in the system, there is a tendency for the yield to decrease.

[0801] [Table 5]

[0802]

[0803] (6) Synthesis of polymers

[0804] [Chemical formula 65]

[0805]

[0806] [Example 2-1]

[0807] Weigh 0.08 mmol (46.0 mg) of Pd(DBA)₂, 0.12 mmol (56.0 mg) of RuPhos, and 4.2 mmol (1378.3 mg) of 4,4′-diaminooctafluorobiphenyl in a 30 mL reaction flask equipped with a reflux column, and displace the nitrogen in the system. Add 8 mL of dioxane and 10 mmol (943.6 mg) of 1,4-dibromobenzene thereto. After stirring for 5 minutes, add 7.1 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 9.2 mmol of LHMDS), and heat and stir in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was traced using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0808] After cooling the reaction mixture to room temperature, put the cooled reaction mixture together with 100 mL of saturated ammonium chloride aqueous solution and 50 mL of ethyl acetate into a separatory funnel for extraction, leaving the organic layer in the separatory funnel and recovering the aqueous layer. Put 50 mL of saturated brine into the separatory funnel, wash the remaining organic layer, and recover the aqueous layer and the organic layer separately. Then, combine all the recovered aqueous layers, put them into a separatory funnel, add 30 mL of ethyl acetate thereto for extraction, recover the organic layer, combine all the recovered organic layers, and dry them with magnesium sulfate.

[0809] Remove the magnesium sulfate by filtration, and distill off the solvent from the obtained filtrate using a rotary evaporator. Dissolve the obtained residue in 10 mL of tetrahydrofuran, drop the obtained solution into 500 mL of a mixed solvent of hexane and toluene (2 / 1 (v / v)), recover the generated solid by filtration, and dry the obtained filtrate at 80 °C under reduced pressure to obtain 0.47 g of the target product.

[0810] 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)

[0811] 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

[0812] 1919F NMR (470.45 MHz, DMSO): δ = -148.76 (d, J = 17.3 Hz, 4F), -140.67 (s, 4F)

[0813] 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)

[0814] [Example 2-2]

[0815] Except for using 0.4 mmol (230.0 mg) of Pd(DBA)2 and 0.6 mmol (280.0 mg) of RuPhos, the reaction and post-treatment were carried out in the same manner as in Example 2-1, and 1.60 g of the target product was obtained.

[0816] The summaries of Example 2-1 and Example 2-2 are shown in Table 6. As shown in Table 6, it can be seen that the molecular weight of the obtained polymer can be controlled by changing the amount of catalyst.

[0817] [Table 6]

[0818]

[0819] [Chemical Formula 66]

[0820]

[0821] [Example 2-3]

[0822] [Chemical Formula 67]

[0823]

[0824] In a 30 mL reaction flask equipped with a reflux column, 0.5 mmol (287.5 mg) of Pd(DBA)₂, 0.75 mmol (350.0 mg), 2.5 mmol (820.4 mg) of 4,4′-diaminooctafluorobiphenyl, and 2.38 mmol (742.9 mg) of 4,4′-dibromobiphenyl were measured, and the system was purged with nitrogen. 8 mL of dioxane was added thereto, and after stirring for 5 minutes, 7.1 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 9.2 mmol of LHMDS) was added, and the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during this process, a small amount of the solution in the flask was taken, and the reaction was traced using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target substance increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0825] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 100 mL of saturated aqueous ammonium chloride solution and 50 mL of ethyl acetate for extraction, and the organic layer was left in the separatory funnel while the aqueous layer was recovered. 50 mL of saturated brine was placed in the separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 30 mL of ethyl acetate was added thereto for extraction, the organic layer was recovered, all the recovered organic layers were combined, and it was dried over magnesium sulfate.

[0826] The magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The resulting residue was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was dropped into 500 mL of a mixed solvent of hexane and toluene (2 / 1 (v / v)), and the resulting solid was recovered by filtration. The obtained filtrate was dried at 80 °C under reduced pressure to obtain 1.01 g of the target substance. The obtained polymer had Mw = 32000, Mn = 15000, Mw / Mn = 2.13, and in addition, ΔT5 was 321.6 °C, and no Tg was observed.

[0827] [Example 2-4]

[0828] [Chemical formula 68]

[0829]

[0830] In a 30 mL reaction flask equipped with a reflux condenser, 0.3 mmol (172.5 mg) of Pd(DBA)₂, 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 were measured. The system was purged with nitrogen. 8 mL of dioxane was added thereto, and after stirring for 5 minutes, 2.54 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 3.3 mmol of LHMDS) was added, and the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was monitored by liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target compound increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0831] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 100 mL of saturated aqueous ammonium chloride solution and 50 mL of ethyl acetate, and extraction was carried out, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 30 mL of ethyl acetate was added thereto, and extraction was carried out, and the organic layer was recovered. All the recovered organic layers were combined and dried over magnesium sulfate.

[0832] Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate using a rotary evaporator. The obtained residue was dissolved in 10 mL of tetrahydrofuran, and the obtained solution was dropped into 500 mL of a mixed solvent of hexane and toluene (2 / 1 (v / v)), and the formed solid was recovered by filtration. The obtained filtrate was dried at 80 °C under reduced pressure to obtain 928 mg of the target compound. The obtained polymer had Mw = 12000, Mn = 7000, Mw / Mn = 1.71, and in addition, ΔT5 was 340.1 °C, and no Tg was observed.

[0833] 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 = 8.0 Hz, 2H), 8.06 (brs, 2H)

[0834] 1313C 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

[0835] 19 19F NMR (470.45 MHz, THF): δ = -151.34 (brd, 4F), -145.89 (brd, 4F)

[0836] 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)

[0837] [Example 2-5]

[0838] [Chemical Formula 69]

[0839]

[0840] In a 30 mL reaction flask equipped with a reflux column, 0.4 mmol (230.0 mg) of Pd(DBA)2, 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 were measured, and the system was purged with nitrogen. 8 mL of dioxane was added thereto, and after stirring for 5 minutes, 3.2 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 4.2 mmol of LHMDS) was added, and the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was monitored by liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0841] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 100 mL of saturated ammonium chloride aqueous solution and 50 mL of ethyl acetate for extraction, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 30 mL of ethyl acetate was added thereto for extraction, the organic layer was recovered, all the recovered organic layers were combined, and it was dried over magnesium sulfate.

[0842] The magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate using a rotary evaporator. The obtained residue was dissolved in 10 mL of tetrahydrofuran, the obtained solution was dropped into 500 mL of a mixed solvent of hexane and toluene (2 / 1 (v / v)), the formed solid was recovered by filtration, and it was dried at 80 °C under reduced pressure to obtain 926 mg of the target product. The obtained polymer had Mw = 20000, Mn = 11000, Mw / Mn = 1.82, and in addition, ΔT5 was 340.1 °C and no Tg was observed.

[0843] 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)

[0844] 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

[0845] 19 F NMR (470.45 MHz, THF): δ = -151.76 (brd, 4F), -142.20 (brd, 4F)

[0846] 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)

[0847] [Example 2-6]

[0848] [Chemical Formula 70]

[0849]

[0850] In a 30 mL reaction flask equipped with a reflux column, 0.3 mmol (172.5 mg) of Pd(DBA)₂, 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 were measured, and the system was purged with nitrogen. 8 mL of dioxane was added thereto, and after stirring for 5 minutes, 2.54 mL of a 1.3 mol / L solution of LHMDS in tetrahydrofuran (equivalent to 3.3 mmol of LHMDS) was added, and the mixture was heated and stirred in a bath at 110 °C for 5 hours (internal temperature 92 °C). It should be noted that during the process, a small amount of the solution in the flask was taken, and the reaction was traced using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At this time, no obvious peak corresponding to the by-product was confirmed.

[0851] After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 100 mL of saturated aqueous ammonium chloride solution and 50 mL of ethyl acetate, and extraction was carried out, leaving the organic layer in the separatory funnel and recovering the aqueous layer. 50 mL of saturated brine was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered separately. Then, all the recovered aqueous layers were combined, placed in a separatory funnel, 30 mL of ethyl acetate was added thereto, and extraction was carried out, and the organic layer was recovered. All the recovered organic layers were combined and dried over magnesium sulfate.

[0852] Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The resulting residue was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was dropped into 500 mL of a mixed solvent of hexane and toluene (2 / 1 (v / v)), and the generated solid was recovered by filtration, and the filtrate was dried at 80 °C under reduced pressure to obtain 928 mg of the target product. The obtained polymer had Mw = 18000, Mn = 8100, and Mw / Mn = 2.22.

[0853] 1 H NMR (500.13 MHz, DMSO): δ = 7.60 (brs, 2H), 8.31 (brs, 2H), 9.30 (brs, 1H)

[0854] 1313C NMR (125.77 MHz, CDCl3): δ = 123.9, 126.4, 128.7, 129.3, 131.3, 135.8, 137.7, 143.5, 145.5

[0855] 19 19F NMR (470.53 MHz, CDCl3): δ = -160.0 (brs, 4F), -143.2 (brs, 4F)

[0856] 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)

[0857] [2] Preparation of Charge Transport Composition and Charge Transport Film

[0858] [Example 3-1]

[0859] Weighed 35.9 mg of the fluorinated arylamine compound having a naphthyl group represented by the following formula (H1) and 56.2 mg of the arylsulfonic acid compound represented by the following formula (D2) synthesized in Example 1-24 in a sample bottle (10 mL), added 3 g of tetrahydrofurfuryl alcohol, and stirred at room temperature until it became uniform to obtain a solution with a solid content of 3% by mass. After coating this solution on an ITO substrate using a spin coater, it was dried at 80 °C for 1 minute in the atmosphere, and then fired at 230 °C for 15 minutes to fabricate a film with a thickness of 50 nm. As the ITO substrate, a glass substrate with indium tin oxide (ITO) formed on the surface with a film thickness of 50 nm was used. On this film, an aluminum film was formed using an evaporation device (vacuum degree 4.0×10 -5 Pa) to obtain a single-layer device. The evaporation was carried out under the condition of an evaporation rate of 0.2 nm / second. The film thickness of the aluminum film was set to 80 nm. It should be noted that the arylsulfonic acid compound represented by the following formula (D2) was synthesized according to the method described in International Publication No. 2006 / 025342.

[0860] [Chemical Formula 71]

[0861]

[0862] [Example 3-2]

[0863] In a sample bottle (10 mL), 44 mg of the fluorinated arylamine compound having a triphenylamino group represented by the following formula (H2) synthesized in Examples 1-26 and 49 mg of the arylsulfonic acid compound represented by the above formula (D2) were measured, 3 g of tetrahydrofurfuryl alcohol was added, and the mixture was stirred at room temperature until it became homogeneous, obtaining a solution with a solid content of 3% by mass. Except for using this solution, a single-layer element was produced in the same manner as in Example 3-1.

[0864] [Chemical formula 72]

[0865]

[0866] [Example 3-3]

[0867] In a sample bottle (10 mL), 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 measured, 3 g of tetrahydrofurfuryl alcohol was added, and the mixture was stirred at room temperature until it became homogeneous, obtaining a solution with a solid content of 2% by mass. Except for using this solution, a single-layer element was produced in the same manner as in Example 3-1.

[0868] [Chemical formula 73]

[0869]

[0870] [Example 3-4]

[0871] In a sample bottle (10 mL), 36 mg of the fluorinated arylamine copolymer having a phenylcarbazolyl 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 measured, 3 g of tetrahydrofurfuryl alcohol was added, and the mixture was stirred at room temperature until it became homogeneous, obtaining a solution with a solid content of 3% by mass. Except for using this solution, a single-layer element was produced in the same manner as in Example 3-1.

[0872] [Chemical formula 74]

[0873]

[0874] [Example 3-5]

[0875] In a sample bottle (10 mL), 34 mg of the fluorinated arylamine copolymer having a 9,9-dimethylfluorenyl 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 measured, 3 g of tetrahydrofurfuryl alcohol was added, and the mixture was stirred at room temperature until it became homogeneous, obtaining a solution with a solid content of 3% by mass. Except for using this solution, a single-layer element was produced in the same manner as in Example 3-1.

[0876] [Chemical 75]

[0877]

[0878] For each of the obtained single-layer elements, the current density at a driving voltage of 5 V was measured. The results are shown in Table 7.

[0879] [Table 7]

[0880]

[0881] As shown in Table 7, it can be seen that the thin film containing the fluorinated arylamine compound or polymer of the present invention as a charge transporting material exhibits good conductivity.

Claims

1. A fluoroaniline derivative represented by formula (T1) or (T2), wherein, excluding compounds represented by the following formulas [1], [2] and [7], In the formula, X 211 represents a divalent group represented by the following formula (A02-1-1), Y 211 and Y 212 are the same and represent a monovalent group represented by any one of formulas (B01), (B02), (B04), (B08) and (B18). In the formula, Z 101 , Z 102 , Z 104 and Z 118 each independently represents a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group or a n-pentyl group. Z 108 each independently represents a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or n-pentyl, and Z present on different benzene rings 108 may combine with each other to form a ring Ar 2 represents a single bond, 1,4-phenylene or biphenyl-4,4'-diyl, X 221 and X 222 are the same and represent a monovalent group represented by formula (C01). wherein, b 11 represents the number of fluorine atoms substituted on the aromatic ring, b 12 represents the number of Z 01 substituted on the aromatic ring, being 0, b 11 is an integer of 2 to 5 Y 221 represents a divalent group represented by formula (D02-1), wherein, Z 102’ represents a hydrogen atom, 2. The fluoroaniline derivative according to claim 1, wherein, In the formula (B08), the groups in which Zs present on different benzene rings combine to form a ring are represented by the following formula (B08') 108 ​ In the formula, Z 108 represents a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group or a n-pentyl group, and Ar 2 represents a single bond, 1,4-phenylene or biphenyl-4,4'-diyl.

3. The fluoroaniline derivative according to claim 1, wherein, The said Z 101 , Z 102 , Z 104 and Z 118 are each independently a hydrogen atom or a tert-butyl group.

4. The fluoroaniline derivative according to claim 1, wherein, Said Z 108 is a hydrogen atom or at least one group of Z that exists at the ortho position of the nitrogen atom on different benzene rings 108 and is a single bond formed therebetween.

5. The fluoroaniline derivative according to claim 2, wherein, The said Z 108 is a hydrogen atom.

6. The fluoroaniline derivative according to claim 1, represented by any one of the following formulas, In the formula, t-Bu represents tert-butyl.

7. The fluoroaniline derivative according to claim 1, represented by any one of the following formulas, 8. A charge transporting material composed of the aniline derivative according to any one of claims 1 to 7.

9. A composition for forming a charge transporting thin film, comprising the charge transporting material according to claim 8 and an organic solvent.

10. The composition for forming a charge transporting thin film according to claim 9, which comprises a dopant material.

11. A charge-transporting thin film obtained from the composition for forming a charge-transporting thin film according to claim 9 or 10.

12. An electronic component comprising the charge-transporting thin film according to claim 11.

13. An organic electroluminescent element comprising the charge-transporting thin film according to claim 11.

14. The organic electroluminescent element according to claim 13, wherein the charge transport thin film is a hole injection layer or a hole transport layer.

Images