Process for producing fluorinated secondary aromatic amine compounds

Abstract

A method for producing a fluorinated aromatic secondary amine compound by reacting a fluorinated aromatic primary amine compound with a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon in the presence of a catalyst comprising a palladium 0-valence complex of dibenzylideneacetone, a ligand represented by the following formula (L) and a base, enables the coupling reaction of a fluorinated aromatic amine compound with a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon to be carried out simply and efficiently without the use of a special catalyst.(R 1 each independently represents an alkyl group having 1 to 20 carbons or the like, R 2 ~R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbons or the like, R 6 ~R 8 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbons or the like.)

Description

[0001] This application is a divisional application of the patent application with the application date of "2019.08.01", the application number of "201980050340.6", and the invention name of "Method for producing fluorinated aromatic secondary amine compound". TECHNICAL FIELD

[0002] The present application relates to a method for producing a fluorinated aromatic secondary amine compound. BACKGROUND

[0003] The reaction of cross-coupling of amine with halide, pseudohalide using a palladium catalyst to form C-N bond is used for the synthesis of aromatic amine, the formation of heterocycle. The cross-coupling has become an important technology in many fields such as pharmaceutical field, material field (non-patent literature 1), and the research on the catalyst used in the reaction, the reaction process is also widely carried out.

[0004] On the other hand, the electronegativity of fluorine is the largest among all elements, so by introducing it into the molecule, the electronic state of the whole molecule can be greatly changed, and fluorine not only has the above characteristics, but also has the following characteristics: because its atomic radius is the same as that of hydrogen atom, even if the fluorine atom is introduced into the molecule instead of hydrogen atom, compared with the case of introducing other atoms, substituents, the change of molecular size is inhibited.

[0005] Therefore, the research on fluorides is actively carried out, and a large number of reports on fluorides for medicine, electronic materials are carried out. For example, in the field of electronic materials, it is reported that amine compounds with fluorine atoms in the molecule are suitable as charge transport substances (patent literature 1).

[0006] Under such circumstances, as a synthesis method of fluorine aryl compound with amino group, the reaction of aromatic amine with perfluoro aryl boronic acid using copper acetate as catalyst (non-patent literature 2), the reaction of N-formanilide with perfluorobenzene in the presence of lithium hydroxide (non-patent literature 3), the reaction of aniline with perfluorobenzene in the presence of t-BuONa (non-patent literature 4) and the like are reported, in these reactions, the amino group as the reaction site exists in the aromatic compound side which does not have fluorine atom among the two raw materials for coupling reaction.

[0007] The reported examples of coupling reaction of fluorine aryl amine compound with halogenated aryl compound which has fluorine atom and amino group are few, for example, although the method of coupling fluorinated aryl amine compound with halogenated aryl compound using special palladium carbene complex as catalyst is reported in non-patent literature 5, but it has the problems of high price of catalyst and low yield of target product.

[0008] PRIOR ART DOCUMENTS

[0009] PATENT LITERATURE

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

[0011] Non-Patent Literature

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

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

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

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

[0016] Non-Patent Literature 5: Angew. Chem. Int. Ed. 2014, 53, 3223 SUMMARY

[0017] PROBLEMS TO BE SOLVED BY THE INVENTION

[0018] The present application has been achieved in view of the above-described actual circumstances, and aims to provide a method for producing a secondary amine compound having a fluoroaryl moiety in the molecule, by coupling a fluorinated aromatic amine compound with a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon without using a special catalyst, simply and efficiently.

[0019] MEANS FOR SOLVING THE PROBLEMS

[0020] The present inventors have intensively studied in order to achieve the above-described object, and as a result, have found that, in the presence of a prescribed palladium catalyst, a prescribed ligand and a base, coupling of an amino group of a fluorinated aromatic amine compound with a chlorine atom, a bromine atom or an iodine atom or a pseudohalogen group of a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon proceeds efficiently, and a secondary amine compound having a fluoroaryl moiety in the molecule is obtained selectively at a high yield, thereby completing the present application.

[0021] That is, the present application provides:

[0022] 1. A method for producing a fluorinated aromatic secondary amine compound, the method comprising a step of reacting a fluorinated aromatic primary amine compound with a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon in the presence of a catalyst, a ligand and a base, characterized in that the catalyst comprises a palladium 0-valence complex of dibenzylideneacetone, and the ligand comprises a biphenyl phosphine 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 carbons or an aryl group having 6 to 20 carbons, R 2 ~R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbons, or an alkoxy group having 1 to 20 carbons, R 6 ~R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbons, an alkoxy group having 1 to 20 carbons, or NR 9 2group, R 9 each independently represents an alkyl group having 1 to 20 carbons.)

[0026] 2. A method for producing a fluorinated aromatic secondary amine compound of 1, wherein the catalyst is a palladium 0-valence complex of dibenzylideneacetone, and the ligand is a biphenyl phosphine compound represented by the formula (L),

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

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

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

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

[0031] [Chemical Formula 2]

[0032]

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

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

[0035] 8. The method 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 2 or more fluorine atoms in the molecule.

[0036] 9. The method 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 monochloro or dichloro aromatic hydrocarbon, a monobromo or dibromo aromatic hydrocarbon, or a monoiodo or diiodo aromatic hydrocarbon.

[0037] 10. A fluorine-containing aniline derivative represented by formula (Tl) or (T2) (however, excluding compounds represented by the following formulas [1] to

[13] ).

[0038] [Chemical Formula 3]

[0039]

[0040] [In the formula, X 211 represents a divalent group represented by any one of 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-, fluorene-9,9-diyl, -NH- or -NZ 10

[0044] L 02 and L 03 each independently represent a hydrogen atom, a carbon number 1 to 20 alkyl group which can be substituted with Z 11 , a carbon number 2 to 20 alkenyl group which can be substituted with Z 11 , or a carbon number 6 to 20 aryl group which can be substituted with Z 12 ,

[0045] L 04 represents a hydrogen atom, a carbon number 1 to 20 alkyl group which can be substituted with Z 11 , or a carbon number 6 to 20 aryl group which can be substituted with Z 11 ​substituted C2-20 alkenyl group or a group which can be substituted by Z 12 substituted C6-20 aryl group,

[0046] Z' represents a substituent of an aromatic ring, each independently represents a chlorine atom, a bromine atom, a nitro group, a cyano group, a group which can be substituted by Z 11 substituted C1-20 alkyl group, a group which can be substituted by Z 11 substituted C2-20 alkenyl group or a group which can be substituted by Z 12 substituted C6-20 aryl group,

[0047] Z 01 ~Z 09 represents a substituent of an aromatic ring, each independently represents a chlorine atom, a bromine atom, a nitro group, a cyano group, a group which can be substituted by Z 11 substituted C1-20 alkyl group, a group which can be substituted by Z 11 substituted C2-20 alkenyl group or a group which can be substituted by Z 12 substituted C6-20 aryl group,

[0048] Z 10 represents a group which can be substituted by Z 11 substituted C1-20 alkyl group, a group which can be substituted by Z 11 substituted C2-20 alkenyl group or a group which can be substituted by Z 12 substituted C6-20 aryl group,

[0049] Z 11 each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group or a group which can be substituted by Z 13 substituted C6-20 aryl group,

[0050] Z 12 each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a group which can be substituted by Z 13 substituted C1-20 alkyl group or a group which can be substituted by Z 13 substituted C2-20 alkenyl group,

[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 a93 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's substituted on the aromatic ring, 01 ~ Z 09 the number of,

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

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

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

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

[0058] a 31 and a 33 are each independently an integer of 1 to 4, a 32 and a 34 are each independently an integer of 0 to 3, and a 31 + a 32 ≤ 4 and a 33 + a 34 ≤ 4,

[0059] a 41 is an integer of 1 to 6, a42 is an integer of 0 to 5, and satisfies a 41 + a 42 ≤ 6,

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

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

[0062] a 71 and a 73 each independently is an integer of 1 to 3, a 72 and a 74 each independently is an integer of 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 of 0 to 4,

[0063] a 81 and a 83 each independently is an integer of 1 to 3, a 82 and a 84 each independently is an integer of 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 of 1 to 3, a 92 and a 94 each independently is an integer of 0 to 2, and satisfies a 91 + a 92 ≤ 3 and a 93 + a 94 ≤ 3.

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

[0066] [Chemical Formula 5]

[0067]

[0068] [Chemistry 6]

[0069]

[0070] [Chemistry 7]

[0071]

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

[0073] L 12 Represents hydrogen atoms, which can be Z 130 Alkyl groups with 1 to 20 carbon atoms, which may be substituted by Z 130 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 131 a substituted aryl group having 6 to 20 carbon atoms,

[0074] L 13 and L 14 Each independently represents a hydrogen atom, which may be replaced by Z 130 Alkyl groups with 1 to 20 carbon atoms, which may be substituted by Z 130 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 131 a substituted aryl group having 6 to 20 carbon atoms,

[0075] Z 100 Indicates that it can be Z 130 Alkyl groups with 1 to 20 carbon atoms, which may be substituted by Z 130 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 131 a substituted aryl group having 6 to 20 carbon atoms,

[0076] Z 101 ~Z 107 and Z 109 ~Z 121 Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a Z 130 Alkyl groups with 1 to 20 carbon atoms, which may be substituted by Z 130 The substituted alkenyl group having 2 to 20 carbon atoms may be 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 Z 130 Alkyl groups with 1 to 20 carbon atoms, which may be substituted by Z130 substituted C2-20 alkenyl group or a C2-20 alkenyl group which can be substituted by Z 131 substituted C6-20 aryl group, Z 108 may combine to form a ring,

[0078] Z 130 each independently represents a fluorine atom, a chlorine atom, a bromine atom or a C1-20 alkyl group which can be substituted by Z 132 substituted C6-20 aryl group,

[0079] Z 131 each independently represents a fluorine atom, a chlorine atom, a bromine atom, a C1-20 alkyl group which can be substituted by Z 132 substituted C1-20 alkyl group or a C1-20 alkyl group which can be substituted by Z 132 substituted C2-20 alkenyl group,

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

[0081] Ar 1 each independently represents a C6-20 aryl group,

[0082] Ar 2 represents a single bond or a C6-20 arylene group.

[0083] X 221 and X 222 each independently represents a monovalent group represented by any one of formulae (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 , b 91 and b 93 represent the number of fluorine atoms substituted on the aromatic ring,

[0087] b 12 , b 22 , b 24 , b 32 , b 34 , b 42 , b52 , b 62 , b 72 , b 74 , b 82 , b 84 , b 92 and b 94 represents the number of Z 01 ~Z 09 , the number of b

[0088] b 75 and b 76 represents the number of Z' substituted on the aromatic ring,

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

[0090] b 21 is an integer of 1 to 4, b 23 is an integer of 1 to 5, b 22 is an integer of 0 to 3, b 24 is an integer of 0 to 4, and b 21 +b 22 ≤ 4 and b 23 +b 24 ≤ 5,

[0091] b 31 is an integer of 1 to 4, b 33 is an integer of 1 to 5, b 32 is an integer of 0 to 3, b 34 is an integer of 0 to 4, and b 31 +b 32 ≤ 4 and b 33 +b 34 ≤ 5,

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

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

[0094] b 61 is an integer of 1 to 9, b 62 is an integer of 0 to 8, and b 61 +b62 ≤ 9,

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

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

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

[0098] L 01 to L 04 , Z' and Z 01 to Z 07 represent the same meanings as described above.

[0099] Y 221 represents a divalent group represented by any one of formulae (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 ~L 14 , Z 101 ~Z 121 and Ar 1 represent the same meanings as described above.)

[0109] [Chemical Formula 13]

[0110]

[0111] 11. The fluoroaniline derivative according to 10, wherein the X 211 is a divalent group represented by the formula (A02),

[0112] 12. The fluoroaniline derivative according to 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 ~a 24 and Z 02 represent the same meanings as described above.)

[0116] 13. The fluoroaniline derivative according to any one of 10 to 12, wherein the Y 211 and Y 212 are the same monovalent group,

[0117] 14. The fluoroaniline derivative according to 13, wherein the Y 211 and Y 212 are each a monovalent group represented by any one of the formulae (B01), (B02), (B04), (B08) and (B18),

[0118] 15. The fluoroaniline derivative according to 10, wherein the Y 221 is a divalent group represented by the formula (D02),

[0119] 16. The fluoroaniline derivative according to 15, wherein the Y 221 is a divalent group represented by the following formula (D02-1):

[0120] [Chemical Formula 15]

[0121]

[0122] 17. The fluoroaniline derivative of 10, 15 or 16, wherein X 221 and X 222 are the same monovalent group,

[0123] 18. The fluoroaniline derivative of 17, wherein X 221 and X 222 are each a monovalent group represented by the above formula (C01),

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

[0125] [Chem. 16]

[0126]

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

[0128] [Chem. 17]

[0129]

[0130] (In the formula, L 01 represents -S-, -0-, -CO-, -CH2-, -(CH2)2-, -C(CH3)2-, -CF2-, -(CF2)2-, -C(CF3)2-, fluorene-9,9-diyl, -NH- or -NZ 10 -,

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

[0132] L 04 represents a hydrogen atom, an alkyl group having a carbon number of 1 to 20 which can be substituted with Z 11 , an alkenyl group having a carbon number of 2 to 20 which can be substituted with Z 11 , or an aryl group having a carbon number of 6 to 20 which can be substituted with Z 12 ,

[0133] Z' represents an aromatic ring substituent, each independently represents an alkyl group having a carbon number of 1 to 20 which can be substituted with Z 11 , an alkenyl group having a carbon number of 2 to 20 which can be substituted with Z11 substituted C2-20 alkenyl group or a group represented by Z 12 substituted C6-20 aryl group,

[0134] Z 01 ~Z 09 substituted C6-20 aryl group, 11 substituted C1-20 alkyl group, a group represented by Z 11 substituted C2-20 alkenyl group or a group represented by Z 12 substituted C6-20 aryl group,

[0135] Z 10 substituted C6-20 aryl group, 11 substituted C1-20 alkyl group, a group represented by Z 11 substituted C2-20 alkenyl group or a group represented by Z 12 substituted C6-20 aryl group,

[0136] Z 11 substituted C6-20 aryl group, 13 substituted C6-20 aryl group,

[0137] Z 12 substituted C6-20 aryl group, 13 substituted C1-20 alkyl group or a group represented by Z 13 substituted C2-20 alkenyl group,

[0138] Z 13 substituted C6-20 aryl 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 substituted C6-20 aryl group,

[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 , the number of a

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

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

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

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

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

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

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

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

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

[0150] a 81 and a 83 are each independently an integer of 1 to 3, a 82 and a 84 are each independently an integer of 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 of 1 to 3, a 92 and a 94 are each independently an integer of 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 formulae (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-, fluorene-9,9-diyl, -NH- or -NZ 02

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

[0163] L 13 and L 14 each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 20 which can be substituted with Z 130 , an alkenyl group having a carbon number of 2 to 20 which can be substituted with Z 130 , or an aryl group having a carbon number of 6 to 20 which can be substituted with 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 a carbon number of 1 to 20 which can be substituted with Z 130 , an alkenyl group having a carbon number of 2 to 20 which can be substituted with Z 130 , or an aryl group having a carbon number of 6 to 20 which can be substituted with 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 a carbon number of 1 to 20 which can be substituted with Z 130 , an alkenyl group having a carbon number of 2 to 20 which can be substituted with Z 130 , or an aryl group having a carbon number of 6 to 20 which can be substituted with Z 131 , and Z 108 on different benzene rings can combine to form a ring,

[0166] Z 130 each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an aryl group having a carbon number of 6 to 20 which can be substituted with Z 132 ,​

[0167] Z 131 each independently represents a fluorine atom, a chlorine atom, a bromine atom, a carbon number 1 to 20 alkyl group which can be substituted with Z 132 or a carbon number 2 to 20 alkenyl group which can be substituted with Z 132

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

[0169] Ar 1 each independently represents a carbon number 6 to 20 aryl group,

[0170] Ar 3 each independently represents a carbon number 6 to 20 arylene group.

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

[0172] 21. The polymer according to claim 20, wherein said 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 claims 19 to 21, wherein said Y 221 is a divalent group represented by any one of the above formulae (D02), (D17) and (D19),

[0177] 23. A charge transportable substance composed of the aniline derivative according to any one of claims 10 to 18,

[0178] 24. A charge transportable substance composed of the polymer according to any one of claims 19 to 22,

[0179] 25. A charge transportable composition comprising the charge transportable substance according to claim 23 or 24, and an organic solvent,

[0180] 26. The charge transportable composition according to claim 25, comprising a dopant substance,

[0181] 27. A charge transportable thin film obtained from the charge transportable composition according to claim 25 or 26,

[0182] ​28. An electronic element comprising the charge transportable thin film of 27,

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

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

[0185] Effects of the Invention

[0186] The production method of the fluorinated aromatic secondary amine compound according to the present application, using a commercially available palladium catalyst and a ligand having a biphenyl skeleton, can efficiently and at a high yield and at a low cost produce a secondary amine compound (fluorine-containing aniline derivative) having a fluorine aryl site within the molecule from a fluorinated aromatic amine compound and a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon.

[0187] In addition, in this reaction, by using a 2-functional compound for both the fluorinated aromatic amine compound and the chlorinated, brominated or iodinated aromatic hydrocarbon or the pseudohalogenated aromatic hydrocarbon, a polymer such as an oligomeric aniline derivative or a polyaniline derivative having a fluorine aryl site within the molecule can be efficiently produced.

[0188] The fluorine-containing aniline derivative, polymer and the like fluorine-containing amine compound obtained by the production method of the present application are excellent in transparency because of having a fluorine atom within the molecule, and exhibit charge transportability, and thus can be suitably used as a charge transportable thin film forming material for electronic elements including organic EL elements. DETAILED DESCRIPTION

[0189] The present application is described in more detail below.

[0190] [1] Production method of fluorinated aromatic secondary amine compound

[0191] The production method of the fluorinated aromatic secondary amine compound according to the present application comprises a step of reacting a fluorinated aromatic primary amine compound with a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon in the presence of a catalyst, a ligand and a base.

[0192] (1) Catalyst

[0193] The catalyst used in the present application comprises a palladium 0-valence complex of dibenzylideneacetone.

[0194] Specific examples of the palladium 0-valence complex of dibenzylideneacetone include bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), tris(dibenzylideneacetone)(chloroform)dipalladium(0), and the like, among which bis(dibenzylideneacetone)palladium(0) is preferred.

[0195] The amount of the palladium 0-valence complex of dibenzylideneacetone used is not particularly limited as long as the amount in which the intended coupling reaction proceeds, and is preferably 0.0001 to 0.2 mol, more preferably 0.005 to 0.15 mol, further preferably 0.01 to 0.12 mol, and more further preferably 0.02 to 0.1 mol, in terms of palladium metal, relative to 1 mol of the NH of the amine site of the fluorinated primary aromatic amine compound.

[0196] In addition, in the present application, other metal catalysts can be used together with the palladium 0-valence complex of dibenzylideneacetone, within a range not impairing the effects of the present application.

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

[0198] In the case where these other metal catalysts are used, the amount thereof cannot be generally prescribed, and is usually less than 100 mol% relative to the palladium 0-valence complex of dibenzylideneacetone.

[0199] (2) Ligand

[0200] The ligand used in the present application includes 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 carbons or an aryl group having 6 to 20 carbons, R 2 to R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbons, or an alkoxy group having 1 to 20 carbons, R 6 to R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbons, an alkoxy group having 1 to 20 carbons, or NR 9 2group, R 9 each independently represents an alkyl group having 1 to 20 carbons.

[0204] As the alkyl group having 1 to 20 carbons, straight-chain, branched-chain, cyclic ones can be mentioned, for example, straight-chain or branched-chain alkyl groups having 1 to 20 carbons such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, icosyl, and the like; cyclic alkyl groups having 3 to 20 carbons such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, cyclononyl, cyclodecyl, adamantyl, and the like.

[0205] As the aryl group having 6 to 20 carbons, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, and the like can be mentioned.

[0206] As the alkoxy group having 1 to 20 carbons, methoxy, ethoxy, n-propoxy, isopropoxy, c-propoxy (cyclopropoxy), n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, and the like can be mentioned.

[0207] Of these, from the viewpoint of obtaining the target compound with good reproducibility, R 1 Each of R1to R4is preferably a bulky group, and is preferably a branched alkyl group having 3 to 20 carbons, a cyclic alkyl group having 3 to 20 carbons, or an aryl group having 6 to 20 carbons, in which the carbon atom at the binding end is a secondary carbon atom or a tertiary carbon atom. Further, from the viewpoints of solubility in a solvent and stability, a branched alkyl group having 3 to 5 carbons or a cyclic alkyl group having 5 to 7 carbons is more preferable, and a t-butyl group or a cyclohexyl group is further preferable.

[0208] Further, from the viewpoint of ease of synthesis, a combination in which two of R1to R4are hydrogen atoms and the other two are the same is preferable. 1 The same applies to R1to R4.

[0209] In addition, from the viewpoint of stability of the compound and the viewpoint of obtaining the target compound with good reproducibility, R 2 R1to R4are each independently hydrogen atoms or alkoxy groups having 1 to 5 carbons, and R 5 R1to R4are each independently hydrogen atoms or alkoxy groups having 1 to 5 carbons, and R 2 R1to R4are each independently hydrogen atoms or alkoxy groups having 1 to 5 carbons, and R 5 R1to R4are each independently hydrogen atoms or alkoxy groups having 1 to 5 carbons, and R 3 R1to R4are each independently hydrogen atoms or alkoxy groups having 1 to 5 carbons, and R 4 R1to R4are each independently hydrogen atoms or alkoxy groups having 1 to 5 carbons, and R 2 R1to R4are each independently hydrogen atoms or alkoxy groups having 1 to 5 carbons, and R 5 R1to R4are each independently hydrogen atoms or alkoxy groups having 1 to 5 carbons, and R

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

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

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

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

[0214] [Chemical Formula 24]

[0215]

[0216] (In the formulae, 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 commercial product, and for example, there can be mentioned 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, and the like, which are commercially available as Buchwald ligands and the like from Aldrich Corporation.

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

[0219] As for the amount of the ligand represented by formula (L) to be used, 1 to 2 equivalents relative to the catalyst to be used are preferred. In particular, in the case of less than 1 equivalent, palladium black can be produced.

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

[0221] As specific examples of the other ligands, mention can be made of 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, tertiary phosphines such as 1,1'-bis(diphenylphosphino)ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, and the like.

[0222] In the case where the other ligand is used, the amount thereof cannot be prescribed in general, and usually, it is less than 100 mol% relative to the ligand represented by formula (L).

[0223] (3) Fluorinated aromatic primary amine compound

[0224] In the production method of the present application, since the catalyst and the ligand described above have the characteristics, the fluorinated aromatic primary amine compound which is a raw material for the coupling reaction is not particularly limited.

[0225] The fluorinated aromatic primary amine compound can be a monoamine compound or a diamine compound, and for example, mention can be made of the compounds represented by the following formulae (Xl) and (X2).

[0226] [Chemical Formula 25]

[0227] Ar F1 -NH2(Xl) 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 can be one in which at least one hydrogen atom of the aryl group is substituted with a fluorine atom, and preferably, two or more hydrogen atoms are substituted with fluorine atoms.

[0230] The fluorinated arylene group can be one in which at least one hydrogen atom of the arylene group is substituted with a fluorine atom, and preferably, two or more hydrogen atoms are substituted with fluorine atoms.

[0231] That is, the fluorinated primary aromatic amine compound used in the present application is preferably a fluorinated primary aromatic 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 carbons is preferred, and as specific examples thereof, there can be mentioned a phenyl group; a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a 1-chrysenyl group, a 2-chrysenyl group, a 5-chrysenyl group, a 2-tryphenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a pentaphenyl group, a benzopyrenyl group, a benzo[9,10]phenanthryl group, and the like, which are derived from a condensed ring aromatic hydrocarbon compound by removing one hydrogen atom from the aromatic ring thereof; a biphenyl-2-yl group, a biphenyl-3-yl group, a biphenyl-4-yl group, a p-terphenyl-4-yl group, an m-terphenyl-4-yl group, an o-terphenyl-4-yl group, a 1,1'-binaphthyl-2-yl group, a 2,2'-binaphthyl-1-yl group, and the like, which are derived from a ring- linked hydrocarbon compound by removing one hydrogen atom from the aromatic ring thereof, and the like.

[0233] As the arylene group, an arylene group having 6 to 20 carbons is preferred, and as specific examples thereof, there can be mentioned a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group; a 1,5-naphthylene group, a 1,8-naphthylene group, a 2,6-naphthylene group, a 2,7-naphthylene group, a 1,2-anthrylene group, a 1,3-anthrylene group, a 1,4-anthrylene group, a 1,5-anthrylene group, a 1,6-anthrylene group, a 1,7-anthrylene group, a 1,8-anthrylene group, a 2,3-anthrylene group, a 2,6-anthrylene group, a 2,7-anthrylene group, a 2,9-anthrylene group, a 2,10-anthrylene group, a 9,10-anthrylene group, and the like, which are derived from a condensed ring aromatic hydrocarbon compound by removing two hydrogen atoms from the aromatic ring thereof; a biphenyl-4,4'-diyl group, a p-terphenyl-4,4"-diyl group, and the like, which are derived from a ring-linked hydrocarbon compound by removing two hydrogen atoms from the aromatic ring thereof, and the like.

[0234] (4) Chlorinated, brominated or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon

[0235] As the chlorinated, brominated or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon, there can be mentioned a monochloro, monobromo or monoiodo or monopseudohalogen compound having one reactive site with the amino group of the fluorinated primary aromatic amine, and a dichloro, dibromo or diiodo or dipseudohalogen compound having two or more reactive sites with the amino group of the fluorinated primary aromatic amine, for example, compounds represented by the following formulae (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 described above can be exemplified.

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

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

[0242] In particular, the chlorinated, brominated, or iodinated aromatic hydrocarbon or the pseudohalogenated aromatic hydrocarbon used in the present application is preferably a monochloro aromatic hydrocarbon or a dichloro aromatic hydrocarbon, a monobromo aromatic hydrocarbon or a dibromo aromatic hydrocarbon, or a monoiodo aromatic hydrocarbon or a diiodo aromatic hydrocarbon, and more preferably a monobromo aromatic hydrocarbon or a dibromo aromatic hydrocarbon, or a monoiodo aromatic hydrocarbon or a diiodo aromatic hydrocarbon.

[0243] (5) Base

[0244] As the base, there is also no particular limitation, and 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, and the like; alkali metal hydrides, alkali metal hydroxides, alkali metal alkoxides, alkali metal carbonates, alkali metal bicarbonates; alkaline earth metal carbonates such as calcium carbonate; organolithiums such as n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide (LDA), lithium 2,2,6,6-tetramethylpiperidide (LiTMP), lithium hexamethyldisilazane (LHMDS); amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, pyridine, and the like; and the like can be exemplified, but lithium amide reagents that lithiate secondary amines such as LDA, LiTMP, LHMDS, and the like, and alkali metal alkoxides such as lithium tert-butoxide are preferred.

[0245] (6) Coupling reaction

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

[0247] For example, in the reaction of formula (Xl) with formula (Yl), (Yl) is preferably about 1 to 1.2 relative to 1 of (Xl), in the reaction of formula (Xl) with (Y2), (Yl) is preferably about 0.5 to 0.6 relative to 1 of (Xl), in the reaction of formula (X2) with formula (Yl), (Yl) is preferably about 2 to 2.4 relative to 1 of (X2), and in the reaction of formula (X2) with (Y2), (Yl) is preferably about 1 to 1.2 relative to 1 of (X2).

[0248] In the case where all of the starting compounds are solids or from the viewpoint of obtaining the fluorinated aromatic secondary amine compound as a target with high efficiency, the coupling reaction of the present application is performed in a solvent.

[0249] In the case where a solvent is used, the kind thereof is not particularly limited as long as it does not adversely affect the reaction. As specific examples, aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, 1,2-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.), and the like can be used, either singly or in a mixture of two or more kinds.

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

[0251] The lower limit of the reaction temperature varies depending on the reactivity of the reaction substrate, etc., and thus cannot be generally defined, but if it is 45°C or higher, the coupling reaction generally proceeds well. In particular, if further improvement of the reactivity is taken into consideration, the reaction temperature is preferably 60°C or higher, more preferably 75°C or higher, further preferably 90°C or higher, and in particular, it is preferable to perform the reaction 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, and thus cannot be generally defined, but it is generally about 200°C or lower.

[0252] After the completion of the reaction, the aftertreatment is performed according to the conventional method, and the fluorinated aromatic secondary amine compound as a target can be obtained.

[0253] [2] Fluoroaniline derivatives

[0254] One of the fluoroaniline derivatives according to the present application is represented by the following formula (Tl).

[0255] [Chem. 27]

[0256]

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

[0258] [Chem. 28]

[0259]

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

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

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

[0263] As specific examples of the alkenyl group having a carbon number of 2 to 20, ethenyl, n-1- propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1- propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1- pentenyl, n-1-decenyl, n-1-icosenyl, and the like can be mentioned.

[0264] L 04 represents a hydrogen atom, an alkyl group having a carbon number of 1 to 20 which can be substituted with Z 11 , an alkenyl group having a carbon number of 2 to 20 which can be substituted with Z 11 , or an aryl group having a carbon number of 6 to 20 which can be substituted with Z 12Specific examples of the substituted aryl group having 6 to 20 carbon atoms include the same groups as those mentioned above. 04 Preferred are a hydrogen atom and a phenyl group.

[0265] Z' represents a substituent of the aromatic ring, each independently represents a substituent that can be replaced by Z 11 Alkyl groups with 1 to 20 carbon atoms, which may be substituted by Z 11 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 12 Specific examples of the substituted aryl group having 6 to 20 carbon atoms include the same groups as those mentioned above as specific examples of the alkyl group, alkenyl group, and aryl group.

[0266] 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 Z 11 Alkyl groups with 1 to 20 carbon atoms, which may be substituted by Z 11 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 12 Substituted aryl group having 6 to 20 carbon atoms, Z 10 Indicates that it can be Z 11 Alkyl groups with 1 to 20 carbon atoms, which may be substituted by Z 11 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 12 Substituted aryl group having 6 to 20 carbon atoms, Z 11 Each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, or a group which may be replaced by Z 13 Substituted aryl group having 6 to 20 carbon atoms, Z 12 Each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a Z 13 The alkyl group having 1 to 20 carbon atoms may be substituted or may be Z 13 Substituted alkenyl having 2 to 20 carbon atoms, Z 13 represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group or a cyano group. Specific examples of these alkyl groups, alkenyl groups and aryl groups include the same groups as described above.

[0267] Among them, in Z 01 ~Z 09 When present, nitro or an alkyl group having 1 to 5 carbon atoms which may be substituted with a fluorine atom is preferred. 10 A phenyl group which may be substituted with a fluorine atom is preferred.

[0268] Furthermore, the substituent Z in the aromatic ring p When there are a plurality of (p=', 01 to 09), they may be the same as 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 denote the number of fluorine atoms substituted at 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 denote the number of Z 01 to Z 09 substituted at the aromatic ring, a 75 and a 76 denote the number of Z' substituted at the aromatic ring.

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

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

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

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

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

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

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

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

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

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

[0280] In particular, 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 is preferably 0, a 75 and a 76 is 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 perfluorobiphenylene group represented by formula (A02-1-1) if considering use as a charge transport substance.

[0283] [Chemical Formula 29]

[0284]

[0285] (In the formula, a 21 to a 24 and Z 02 have 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-, fluorene-9,9-diyl, -NH- or -NZ 100 -.

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

[0297] L 13 and L 14 each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 20 which can be substituted with Z 130 , an alkenyl group having a carbon number of 2 to 20 which can be substituted with Z 130 , or an aryl group having a carbon number of 6 to 20 which can be substituted with Z 131 , as specific examples of these alkyl group, alkenyl group and aryl group, the same groups as mentioned above can be listed. Among these, as L 13 and L 14 , a hydrogen atom, an alkyl group having a carbon number of 1 to 5, an aryl group having a carbon number of 6 to 10 are preferred, and a hydrogen atom, a methyl group, a phenyl group are more preferred.

[0298] Z 100 represents an alkyl group having a carbon number of 1 to 20 which can be substituted with Z 130 , an alkenyl group having a carbon number of 2 to 20 which can be substituted with Z 130 , or an aryl group having a carbon number of 6 to 20 which can be substituted with Z 131 , a phenyl group which can be substituted with a fluorine atom is preferred.

[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 a carbon number of 1 to 20 which can be substituted with Z 130 , an alkenyl group having a carbon number of 2 to 20 which can be substituted with Z 130 , or an aryl group having a carbon number of 6 to 20 which can be substituted with Z 131 , a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having a carbon number of 1 to 20 which can be substituted with Z 108 , an alkenyl group having a carbon number of 2 to 20 which can be substituted with Z 130substituted C1-20 alkyl, Z 130 substituted C2-20 alkenyl, or Z 131 substituted C6-20 aryl, Z 108 may combine to form a ring, Z 130 each independently represents a fluorine atom, a chlorine atom, a bromine atom, or Z 132 substituted C6-20 aryl, Z 131 each independently represents a fluorine atom, a chlorine atom, a bromine atom, or Z 132 substituted C1-20 alkyl, or Z 132 substituted C2-20 alkenyl, Z 132 represents a fluorine atom, a chlorine atom, or a bromine atom, and as specific examples of these alkyl groups, alkenyl groups, and aryl groups, the same examples as described above can be given. Among these, Z 101 ~Z 107 and Z 109 ~Z 121 is preferably a hydrogen atom. Z 108 is preferably a hydrogen atom or at least one set of Z 108 combined between the different benzene rings at the ortho position of the nitrogen atom. Further, as Z 108 forms a single bond between the different benzene rings, for example, a structure represented by the following formula (B08') can be given.

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

[0301] [Chem. 34]

[0302]

[0303] Ar 1 each independently represents a C6-20 aryl group, and as this aryl group, the same aryl groups as described above can be given. Among these, 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 a C6-20 arylene group. As specific examples of the C6-20 arylene group, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,5-naphthylene, 1,8-naphthylene, 2,6-naphthylene, 2,7-naphthylene, and the like can be given. Among these, Ar 2 is preferably a single bond, a 1,4-phenylene group.

[0305] In particular, Y 211 and Y 212are each independently a monovalent group represented by any one of formulae (B01), (B02), (B04), (B08), and (B18).

[0306] Further, the present application relates to another fluoroaniline derivative represented by the following formula (T2).

[0307] [Chemical Formula 35]

[0308]

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

[0310] [Chemical Formula 36]

[0311]

[0312] wherein 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, 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 to Z 09 substituted on the aromatic ring, b 75 and b 76 represent the number of Z' substituted on the aromatic ring.

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

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

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

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

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

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

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

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

[0321] b 91 is an integer of 1 to 3, b 93 is an integer of 1 to 4, b 92 is an integer of 0 to 2, b 94 is an integer of 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 is preferably an integer of 2 or more.

[0323] Further, b 12 , b 22 , b 24 , b 32 , b 34 , b 42 , b 52 , b 62 , b 72 , b 74 , b 82 , b 84 , b 92 and b 94 is preferably 0, b 75 and b 76 is preferably 0.

[0324] Note that L 01 to L 04 , Z' and Z 01 to Z 09 have the same meanings as described above.

[0325] In particular, if the ease of synthesis, charge transportability, and the like are taken into consideration, X 221 and X 222 are preferably the same monovalent group, more preferably both are monovalent groups represented by formula (C01), and further preferably both are monovalent groups represented by the following formula (C01-1).

[0326] [Chemical Formula 37]

[0327]

[0328] On the other hand, Y 221represents a divalent group represented by any one of formulae (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 carbons, and as specific examples of the arylene group, the same examples as described above can be cited.

[0338] In addition, L 11 ~ L 14 , Z 101 ~ 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 further 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 meanings as described above.

[0343] Further, the fluorine-containing aniline derivative of the present application does not contain a compound represented by the following formulae [1] to

[13] .

[0344] [Chemical Formula 43]

[0345]

[0346] As specific examples of the fluorine-containing aniline derivative of the present application, compounds represented by the following formulae can be cited, but are not limited to these.

[0347] [Chemical Formula 44]

[0348]

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

[0350] [3] Polymer

[0351] The polymer according to the present application contains a repeating unit represented by the following formula (P1-2).

[0352] [Chemical Formula 45]

[0353]

[0354] In the formula (P1-2), X 211 The same groups as exemplified in the above fluorine-containing aniline derivatives can be exemplified, and the preferable range is also the same as above.

[0355] Further, Y 221 The same groups as exemplified in the above fluorine-containing aniline derivatives can be exemplified, and the preferable range is also the same as above.

[0356] The molecular weight of the polymer according to the present application is not particularly limited, and if the electric conductivity and solubility in organic solvents and the like when used as a charge transport substance are taken into consideration, the weight average molecular weight is preferably from 1000 to 100000, more preferably from 2000 to 50000, and further preferably from 5000 to 30000. Note that the weight average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography.

[0357] As specific examples of the polymer according to the present application, the following examples represented by the following formulae can be exemplified, but are not limited thereto.

[0358] [Chemical Formula 46]

[0359]

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

[0361] [4] Method for producing fluorine-containing aniline derivative and polymer

[0362] The fluorine-containing aniline derivative and the polymer according to the present application described above can be synthesized using the above-described method for producing fluorinated aromatic secondary amine according to the present application.

[0363] For example, the fluoroaniline derivative can be obtained by reacting a fluorinated primary aromatic diamine compound represented by the above formula (X2) with 2 equivalents of a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudo-halogenated aromatic hydrocarbon represented by the above formula (Y1), or with 0.5 equivalents of a dichlorinated, dibrominated or diiodinated aromatic hydrocarbon or a di-pseudo-halogenated aromatic hydrocarbon represented by the above formula (Y2) in the presence of a palladium 0-valence complex of dibenzylideneacetone, a ligand represented by the above formula (L) and a base.

[0364] On the other hand, the polymer can be obtained by reacting a fluorinated primary aromatic diamine compound represented by the above formula (X2) with a dichlorinated, dibrominated or diiodinated aromatic hydrocarbon or a di-pseudo-halogenated aromatic hydrocarbon represented by the above formula (Y2) in the presence of a palladium 0-valence 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 transportable substance, charge transportable composition and charge transportable thin film

[0366] The above fluoroaniline derivative and polymer of the present application have excellent transparency due to the fluorine atom in the molecule, and show conductivity in the case of being alone or in combination with a dopant substance, and thus can be preferably used as a charge transportable substance, and a charge transportable composition can be easily prepared by dissolving the fluoroaniline derivative or polymer of the present application in a solvent.

[0367] For example, as the charge transportable composition of the present application, there can be cited a composition comprising a charge transportable substance composed of the above fluoroaniline derivative or polymer and an organic solvent, and a dopant substance can be contained for the purpose of improving the charge transportability of the obtained thin film or the like, according to the use of the thin film.

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

[0369] Specific examples of dopant substances include strong inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid; Lewis acids such as aluminum (III) chloride (AlCl3), titanium (IV) tetrachloride (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), and tris(4-bromophenyl)aluminum hexachloroantimonate (TBPAH); and naphthalene disulfonic acids such as benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, dodecylbenzenesulfonic acid, and 1,5-naphthalene disulfonic acid. Strong organic acids such as trisulfonic acid, naphthalenetrisulfonic acid such as 1,3,6-naphthalenetrisulfonic acid, polystyrenesulfonic acid, 1,4-benzodioxanedisulfonic acid compounds described in International Publication No. 2005 / 000832, naphthalene or anthracenesulfonic acid compounds described in International Publication No. 2006 / 025342, and arylsulfonic acid compounds such as dinonylnaphthalenesulfonic acid compounds described in Japanese Patent Application Laid-Open No. 2005-108828; organic oxidants such as 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and iodine; and inorganic oxidants such as heteropoly acids such as phosphomolybdic acid, phosphotungstic acid, and phosphotungstomolybdic acid described in International Publication No. 2010 / 058777 can be used in combination.

[0370] Among these, arylsulfonic acid compounds are preferred, and arylsulfonic acid compounds represented by formula (H1) or (H2) are preferred. Furthermore, the molecular weight of the arylsulfonic acid compound used as a dopant substance is preferably 3000 or less, more preferably 2500 or less, taking into account solubility in organic solvents.

[0371] [Chemistry 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, and p represents A 1 With A 3 The binding number of A is an integer satisfying 2≤p≤4. 3 is a perfluorobiphenylene group, preferably a perfluorobiphenyl-4,4′-diyl group, and p is 2.

[0376] q represents the same as A 2The number of the combined sulfonic acid groups is an integer satisfying 1 ≤ q ≤ 4, most preferably 2.

[0377] A 4 ~A 8 independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having a carbon number of 1 to 20, a haloalkyl group having a carbon number of 1 to 20, or a haloalkenyl group having a carbon number of 2 to 20, at least three of A 4 ~A 8 are halogen atoms.

[0378] As the haloalkyl group having a carbon number of 1 to 20, there can be mentioned a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 1,1,2,2,3,3,3-heptafluoropropyl group, a 4,4,4-trifluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a 1,1,2,2,3,3,4,4,4-nonafluorobutyl group, and the like.

[0379] As the haloalkenyl group having a carbon number of 2 to 20, there can be mentioned a perfluorovinyl group, a perfluoropropenyl group (perfluoroallyl group), a perfluorobutenyl group, and the like.

[0380] As the halogen atom, there can be mentioned a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, preferably a fluorine atom.

[0381] Further, as examples of the alkyl group having a carbon number of 1 to 20, there can be mentioned the same examples as mentioned above.

[0382] Among these, A 4 ~A 8 is preferably a hydrogen atom, a halogen atom, a cyano group, an alkyl group having a carbon number of 1 to 10, a haloalkyl group having a carbon number of 1 to 10, or a haloalkenyl group having a carbon number of 2 to 10, and at least three of A 4 ~A 8 are fluorine atoms, more preferably a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having a carbon number of 1 to 5, a fluoroalkyl group having a carbon number of 1 to 5, or a fluoroalkenyl group having a carbon number of 2 to 5, and at least three of A 4 ~A 8 are fluorine atoms, further preferably a hydrogen atom, a fluorine atom, a cyano group, a perfluoroalkyl group having a carbon number of 1 to 5, or a perfluoroalkenyl group having a carbon number of 1 to 5, and at least three of A 4 , A 5 , and A 8 are fluorine atoms.

[0383] It should be noted that the perfluoroalkyl group means a group in which all the hydrogen atoms of the alkyl group are replaced with fluorine atoms, and the perfluoroalkenyl group means a group in which all the hydrogen atoms of the alkenyl group are replaced with 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] The following specifically exemplify preferred aryl sulfonic acid compounds, 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 transport substance and the dopant substance, and examples thereof include benzene, toluene, o-xylene, m-xylene, p-xylene, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, cyclohexanol, ethylene glycol, 1,3-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexylene glycol, tetrahydrofurfuryl alcohol, butyl cellosolve, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl carbitol, diacetone alcohol, γ-butyrolactone, ethyl lactate, n-hexyl acetate, and the like. One of these can be used alone, or two or more of them can be used in combination.

[0389] The viscosity of the charge transport composition of the present application 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] The viscosity and the surface tension of the charge transport composition of the present application are adjusted by changing the kind of the organic solvent used, the ratio thereof, the solid content concentration, and the like, in consideration of the coating method to be used, the desired film thickness, and the like.

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

[0392] Note that the solid content of the solid content concentration referred to herein means a component other than the solvent contained in the charge transport composition of the present application.

[0393] The charge transportable composition of the present application can be produced by mixing the charge transportable substance of the present application, an organic solvent, and a dopant substance, if desired. The order of mixing is not particularly limited.

[0394] In producing the composition, the components can be heated as appropriate within a range where the components do not decompose or deteriorate.

[0395] In the present application, in the case of a charge transportable composition, from the viewpoint of obtaining a thin film having higher planarity with good reproducibility, after dissolving the charge transportable substance or the like in an organic solvent, it is preferable to perform filtration using a submicron filter or the like.

[0396] By applying the above-described charge transportable composition on a substrate and baking, a charge transportable thin film of the present application can be formed on the substrate.

[0397] As the method of applying the composition, there are no particular limitations, and examples include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating, an inkjet method, a spray coating method, a slit coating method, and the like, and the viscosity and surface tension of the composition are preferably adjusted according to the method of application.

[0398] In the case of using the charge transportable composition of the present application, the baking atmosphere is also not particularly limited, and a thin film having a uniform film surface and high charge transportability can be obtained not only in an atmospheric atmosphere (under air) but also in a non-reactive gas such as nitrogen, a vacuum, but is typically under air.

[0399] In addition, the baking conditions are also not particularly limited, and, for example, a hot plate is used to heat and bake. Typically, the baking temperature is appropriately determined within a range of 100 to 260°C, and the baking time is appropriately determined within a range of 1 minute to 1 hour, taking into account the desired charge transportability or the like. Furthermore, if desired, multistage baking can be performed at two or more different temperatures.

[0400] The film thickness of the charge transportable thin film is not particularly limited, and in the case of use as a functional layer of an organic EL element, it is preferably 5 to 300 nm. As a method of changing the film thickness, there are methods of changing the solid content concentration in the charge transportable composition, changing the liquid amount at the time of application, and the like.

[0401] The fluorine-containing aniline derivative or the polymer of the present application can be used as an additive added to a charge transportable composition containing another charge transportable substance, because it contains a fluorine atom, and is mainly aimed at improving the coatability, improving the transparency of the obtained film, adjusting the wettability of the film surface, and the like, to adjust the film properties.

[0402] [6] Organic EL Element

[0403] The organic EL element of the present application has a pair of electrodes, between which the charge-transporting film of the present application described above is provided.

[0404] As representative configurations of the organic EL element, the following (a) to (f) can be listed, but are not limited to these. Note that in the following configurations, an electron-blocking layer or the like can be provided as needed 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. In addition, the hole-injecting layer, the hole-transporting layer, or the hole-injecting and transporting layer can have a function as an electron-blocking layer or the like, and the electron-injecting layer, the electron-transporting layer, or the electron-injecting and transporting layer can have a function as a hole (hole) blocking layer or the like.

[0405] (a) anode / hole-injecting layer / hole-transporting layer / light-emitting layer / electron-transporting layer / electron-injecting layer / cathode

[0406] (b) anode / hole-injecting layer / hole-transporting layer / light-emitting layer / electron-injecting and transporting layer / cathode

[0407] (c) anode / hole-injecting and transporting layer / light-emitting layer / electron-transporting layer / electron-injecting layer / cathode

[0408] (d) anode / hole-injecting and transporting layer / light-emitting layer / electron-injecting and transporting layer / cathode

[0409] (e) anode / hole-injecting layer / hole-transporting layer / light-emitting layer / cathode

[0410] (f) anode / hole-injecting and transporting layer / light-emitting layer / cathode

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

[0412] The "electron-injecting layer", "electron-transporting layer", and "electron-injecting and transporting layer" are layers formed between the light-emitting layer and the cathode, and have a function of transporting electrons from the cathode to the light-emitting layer. In the case where only one layer of an electron-transporting material is provided between the light-emitting layer and the cathode, it is an "electron-injecting and transporting layer", and in the case where two or more layers of an electron-transporting material are provided between the light-emitting layer and the cathode, the layer close to the cathode is an "electron-injecting layer", and the other layer is an "electron-transporting layer".

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

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

[0415] As the use material and the production method when an organic EL element is produced using the charge-transporting composition of the present application, the following use material and production method can be exemplified, but are not limited thereto.

[0416] An example of the production method of an OLED element having a hole-injection layer composed of a thin film obtained from the charge-transporting composition of the present application is described below. In the case of an electrode, it is preferable to perform cleaning using alcohol, pure water, or the like in advance within a range not adversely affecting the electrode; and to perform surface treatment using UV ozone treatment, oxygen-plasma treatment, or the like.

[0417] On an anode substrate, a hole-injection layer is formed using the above-described charge-transporting composition by the above-described method. This is introduced into a vacuum evaporation device, and a hole-transporting layer, a light-emitting layer, an electron-transporting layer / hole-blocking layer, an electron-injection layer, and a cathode metal are sequentially evaporated. Alternatively, in this method, instead of forming a hole-transporting layer and a light-emitting layer by evaporation, a hole-transporting layer-forming composition containing a hole-transporting high molecule and a light-emitting layer-forming composition containing a light-emitting high molecule are used, and these layers are formed by a wet method. Further, an electron-blocking layer can be provided between the light-emitting layer and the hole-transporting layer as needed.

[0418] As the anode material, a transparent electrode represented by indium tin oxide (ITO), indium zinc oxide (IZO), a metal anode composed of a metal represented by aluminum, an alloy thereof, or the like, and an anode material subjected to a planarization treatment are exemplified. A polythiophene derivative and a polyaniline derivative having high charge transportability can also be used.

[0419] Further, as other metals constituting the metal anode, gold, silver, copper, indium, an alloy thereof, or the like can be exemplified, but are not limited thereto.

[0420] As a material forming a hole-transporting layer, there can be mentioned (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spirodimers, 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 the like triarylamine-based compounds, 5,5"-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2':5',2"-terthiophene (BMA-3T) and the like oligothiophene-based compounds.

[0421] As a material forming a light-emitting layer, there can be mentioned low-molecular light-emitting materials such as metal complexes such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo[h]quinoline, a bisstyrylbenzene derivative, a bisstyrylarylene derivative, a metal complex of (2-hydroxyphenyl)benzothiazole, a thiophene derivative, and the like; a system in which a light-emitting material and an electron-transporting material are mixed in a high-molecular compound such as poly(p-phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], poly(3-alkylthiophene), polyvinylcarbazole, and the like.

[0422] In addition, in the case where the light-emitting layer is formed by evaporation, a light-emitting dopant can be co-evaporated, and as the light-emitting dopant, there can be mentioned metal complexes such as tris(2-phenylpyridine)iridium(III) (Ir(ppy)3), perylene derivatives such as rubrene, fused polycyclic aromatic rings such as a perylenetetracarboxylic acid derivative, a quinacridone derivative, and a perylenetetracarboxylic acid derivative, and the like.

[0423] As a material forming an electron-transporting layer / hole-blocking layer, there can be mentioned oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, pyrimidine derivatives, and the like.

[0424] As a material forming an electron-injecting layer, there can be mentioned metal oxides such as lithium oxide (Li2O), magnesium oxide (MgO), and aluminum oxide (Al2O3), metal fluorides such as lithium fluoride (LiF) and sodium fluoride (NaF), but not limited to these.

[0425] As a cathode material, there can be mentioned aluminum, a magnesium-silver alloy, an aluminum-lithium alloy, and the like.

[0426] As a material forming an electron-transporting layer / hole-blocking layer, there can be mentioned oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, pyrimidine derivatives, and the like.

[0427] As the hole-transporting polymer, poly[(9,9-dihexylfluorene-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene)], poly[(9,9-dioctylfluorene-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,1'-biphenyl-4,4-diamine)], poly[(9,9-bis{1'-penten-5'-yl}fluorene-2,7-diyl)-co-(N,N'-bis{p-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-(p-butylphenyl))diphenylamine)], and the like can be exemplified.

[0428] As the light-emitting polymer, polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), polyphenylenevinylene derivatives such as poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and the like can be exemplified.

[0429] For the organic EL element of the present application, in order to prevent deterioration of characteristics, sealing can be performed as needed together with a water-trapping agent or the like in accordance with a conventional method.

[0430] Examples

[0431] The following examples and comparative examples are given to more specifically illustrate the present application, but the present application is not limited to the following examples.

[0432] [Apparatus]

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

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

[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] Automatic sampler: SIL-20A

[0441] Column: Poroshell 120 EC-C18 (2.7 μm, 3.0 x 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 (measurement of molecular weight of polymer)

[0446] Apparatus: 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] Automatic sampler: SIL-20A

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

[0454] Column temperature: 40°C

[0455] Solvent: Tetrahydrofuran

[0456] Detector: UV

[0457] (3) Coating of composition: manufactured by Mikasa Corporation, spin coater MS-A100

[0458] (4) Production of element: manufactured by Chugoku Industry Corporation, multi-functional vapor deposition device system C-E2L1G1-N

[0459] (5) Measurement of current density of element: manufactured by Tech World, I-V-L measurement system

[0460] (6) Measurement of glass transition temperature (Tg): manufactured by Perkin Elmer, Diamond DSC

[0461] Measurement conditions: under nitrogen atmosphere

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

[0463] (7) 5% weight reduction temperature (Td5%) measurement

[0464] Apparatus: TG8120 manufactured by Rigaku Corporation

[0465] Measurement conditions: under air atmosphere

[0466] Temperature increase rate: 10°C / minute (40-500°C)

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

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

[0469] Internal standard

[0470] 19 F-NMR chemical shift correction

[0471] Trifluoromethylbenzene = -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 Sunjin Chemical Co., Ltd.]

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

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

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

[0488] Lithium hexamethyldisilylamide (LHMDS) 1 mol / L toluene solution [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 Sunjin Chemical Co., Ltd.]

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

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

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

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

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

[0513] 2-Bronaphthalene [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 Industries, Ltd.]

[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 Industries, Ltd.]

[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] [Chemistry 49]

[0526]

[0527] [Comparative Example 1-1]

[0528] In a 30 mL reaction flask equipped with a reflux condenser, Pd(PPh3)40.05 mmol (57.8 mg), (±)BINAP 0.075 mmol (46.7 mg), cesium carbonate 1.2 mmol (391.0 mg), and pentafluoroaniline 1.2 mmol (219.7 mg) were weighed out, and the system was replaced with nitrogen. To this were added dioxane 4 mL, 4-bromoanisole 1 mmol (187.0 mg), and stirring was performed at room temperature for 5 minutes, and then heating was performed in a 110°C bath for 5 hours (internal temperature 92°C). In liquid chromatography using a small amount of solution taken from the flask, a peak attributable to the starting material could be confirmed, but a peak attributable to the target product could not be confirmed.

[0529] [Comparative Example 1-2]

[0530] In a 30 mL reaction flask equipped with a reflux condenser, Pd(PPh3)40.05 mmol (57.8 mg), (±)BINAP 0.075 mmol (46.7 mg), cesium carbonate 1.2 mmol (391.0 mg), and pentafluoroaniline 1.2 mmol (219.7 mg) were weighed out, and the system was replaced with nitrogen. To this were added dioxane 4 mL, 4-bromoanisole 1 mmol (187.0 mg), and stirring was performed at room temperature for 5 minutes, and then heating was performed in a 110°C bath for 5 hours (internal temperature 92°C). In liquid chromatography using a small amount of solution taken from the flask, a peak attributable to the starting material could be confirmed, but a peak attributable to the target product could not be confirmed.

[0531] [Comparative Example 1-3]

[0532] In a 30 mL reaction flask equipped with a reflux condenser, Pd(PPh3)40.05 mmol (57.8 mg), (±)BINAP 0.075 mmol (46.7 mg), pentafluoroaniline 1.2 mmol (219.7 mg) were weighed out, and the system was replaced with nitrogen. To this were added dioxane 4 mL, 4-bromoanisole 1 mmol (187.0 mg), and further, LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (corresponding to LHMDS 1.2 mmol), and stirring was performed at room temperature for 5 minutes, and then heating was performed in a 110°C bath for 5 hours (internal temperature 92°C). In liquid chromatography using a small amount of solution taken from the flask, a peak attributable to the starting material could be confirmed, but a peak attributable to the target product could not be confirmed.

[0533] [Comparative Example 1-4]

[0534] The same operation as Comparative Example 1-3 was performed except that RuPhos 0.075 mmol (35.0 mg) represented by the following formula (L2) was used instead of (±)BINAP, and in liquid chromatography using a small amount of the solution taken from the flask, a peak attributable to the starting material could be confirmed, but a peak attributable to the target product 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] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.05 mmol (28.8 mg), 4-bromoanisole 1 mmol (187.0 mg), and cesium carbonate 1.2 mmol (391.0 mg) were weighed, and the system was replaced with nitrogen. To this were added dioxane 4 mL, and LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (equivalent to LHMDS 1.2 mmol), and after stirring at room temperature for 5 minutes, heating and stirring were performed in a bath at 110°C for 5 hours (internal temperature 92°C), and in liquid chromatography using a small amount of the solution taken from the flask, a peak attributable to the starting material could be confirmed, but a peak attributable to the target product could not be confirmed.

[0540] [Comparative Example 1-6]

[0541] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.05 mmol (28.8 mg), (±)BINAP 0.075 mmol (46.7 mg), pentafluoroaniline 1.2 mmol (219.7 mg), and cesium carbonate 1.2 mmol (391.0 mg) were weighed, and the system was replaced with nitrogen. To this were added dioxane 4 mL, and 4-bromoanisole 1 mmol (187.0 mg), and after stirring at room temperature for 5 minutes, heating and stirring were performed in a bath at 110°C for 5 hours (internal temperature 92°C), and in liquid chromatography using a small amount of the solution taken from the flask, a peak attributable to the starting material could be confirmed, but a peak attributable to the target product could not be confirmed.

[0542] [Comparative Example 1-7]

[0543] In a 30 mL reaction flask equipped with a reflux condenser, Pd(DBA)2 0.05 mmol (28.8 mg), (±)BINAP 0.075 mmol (46.7 mg), pentafluoroaniline 1.2 mmol (219.7 mg) were weighed, and the system was replaced with nitrogen. To this, dioxane 4 mL, 4-bromoanisole 1 mmol (187.0 mg) were added, and then LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (LHMDS 1.2 mmol) was added. After stirring at room temperature for 5 minutes, stirring was performed with heating in a bath at 110°C for 5 hours (internal temperature 92°C). It should be noted that, in the middle of the reaction, 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 starting material decreased, the area of the peak attributable to the target product increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0544] [Example 1-1]

[0545] In a 30 mL reaction flask equipped with a reflux condenser, Pd(DBA)2 0.05 mmol (28.8 mg), RuPhos 0.075 mmol (35.0 mg), cesium carbonate 1.2 mmol (391.0 mg), pentafluoroaniline 1.2 mmol (219.7 mg) were weighed, and the system was replaced with nitrogen. To this, dioxane 4 mL, 4-bromoanisole 1 mmol (187.0 mg) were added, and then LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (LHMDS 1.2 mmol) was added. After stirring at room temperature for 5 minutes, stirring was performed with heating in a bath at 110°C for 5 hours (internal temperature 92°C). It should be noted that, in the middle of the reaction, 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 starting material decreased, the area of the peak attributable to the target product increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0546] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was put in a separatory funnel together with saturated aqueous ammonium chloride solution 50 mL, ethyl acetate 30 mL, and extraction was performed, and the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was put in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, put in a separatory funnel, and ethyl acetate 20 mL was put therein, and extraction was performed, and the organic layer was recovered, and the recovered entire organic layer was combined, and this was dried with magnesium sulfate.

[0547] 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 toluene 3 mL, and column chromatography was performed using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3), and fractions containing the target product were fractionated.

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

[0549] 1 H NMR (500.13 MHz, CDC13): δ = 3.76 (s, 3H), 5.14 (br s, 1H), 6.72-6.75 (m, 6H), 6.8 (d, J = 9.0 Hz, 2H)

[0550] 13 C NMR (125.77 MHz, CDC13): 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, CDC13): δ = -167.6 (t, J = 21.7 Hz, IF), -164.5 (td, J = 21.7, 5.2 Hz, 2F), -153.3 (br d, 2F); IR (neat)

[0552] v ~ = 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 289.0526, found 290.0589.

[0554] [Example 1-2]

[0555] The reaction and work-up were carried out analogously to Example 1-1, except that t-BuONal.2 mmol (115.3 mg) was used instead of cesium carbonate, to obtain the target 286.1 mg (yield > 99%).

[0556] [Example 1-3]

[0557] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.05 mmol (28.8 mg), RuPhos 0.075 mmol (35.0 mg), pentafluoroaniline 1.2 mmol (219.7 mg) were weighed and the system was replaced with nitrogen. To this, dioxane 4 mL, 4-bromoanisole 1 mmol (187.0 mg) were added and stirred for 5 minutes at room temperature. Next, LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (corresponding to LHMDS 1.2 mmol) was added and stirred for 5 minutes at room temperature. After that, the system was heated in a 110°C bath and stirred for 3 hours (internal temperature 92°C). Note that, in the middle of the reaction, a small amount of the solution in the flask was taken and the reaction was traced by liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target product increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0558] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was put in a separatory funnel together with saturated aqueous ammonium chloride solution 50 mL, ethyl acetate 30 mL, extraction was performed, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was put in the separatory funnel, the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, put in a separatory funnel, ethyl acetate 20 mL was put in the separatory funnel, extraction was performed, and the organic layer was recovered. The recovered entire organic layer was combined, and dried with magnesium sulfate.

[0559] 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 toluene 3 mL, and column chromatography was performed using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3), and fractions containing the target product were collected.

[0560] Finally, the solvent was removed from the fraction collected at 80°C under reduced pressure, and the target product 287.3 mg (yield > 99%) was obtained.

[0561] [Example 1-4]

[0562] The reaction and the post-treatment were performed in the same manner as in Example 1-3 except that RuPhos 0.2 mmol (93.3 mg) was used and the reaction time was 5 hours, and the target product 286.0 mg (yield > 99%) was obtained.

[0563] [Example 1-5]

[0564] Reaction and post-treatment were carried out in the same manner as in Example 1-3 except that t-BuXPhos represented by the following formula (L4) 0.075 mmol (31.8 mg) was used instead of RuPhos and the reaction time was 5 hours, to obtain the target 243.9 mg (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] Reaction and post-treatment were carried out in the same manner as in Example 1-3 except that SPhos represented by the following formula (L1) 0.075 mmol (30.8 mg) was used instead of RuPhos and the reaction time was 5 hours, to obtain the target 246.0 mg (yield 85%).

[0570] [Chemical Formula 52]

[0571]

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

[0573] [Example 1-7]

[0574] Reaction and post-treatment were carried out in the same manner as in Example 1-3 except that t-BuMePhos represented by the following formula (L5) 0.075 mmol (23.4 mg) was used instead of RuPhos and the reaction time was 5 hours, to obtain the target 246.3 mg (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] Reaction and post-treatment were carried out in the same manner as in Example 1-3 except that JhonPhos represented by the following formula (L6) 0.075 mmol (22.4 mg) was used instead of RuPhos and the reaction time was 5 hours, to obtain the target 268.2 mg (yield 95%).

[0580] [Chemical Formula 54]

[0581]

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

[0583] [Examples 1-9]

[0584] The reaction and post-treatment were carried out in the same manner as in Example 1-3, except that CyJhonPhos represented by the following formula (L7) was used instead of RuPhos, 0.075 mmol (26.3 mg), and the reaction time was 5 hours, to obtain the target 208.9 mg (yield 73%).

[0585] [Formula 55]

[0586]

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

[0588] A summary of the above Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-7 is shown in Table 1.

[0589] [Table 1]

[0590]

[0591] (Example 1-4: RuPhos usage amount 0.2 mmol)

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

[0593] [Formula 56]

[0594]

[0595] [Comparative Example 1-8]

[0596] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.05 mmol (28.8 mg), RuPhos 0.075 mmol (35.0 mg), pentafluoroaniline 1.2 mmol (219.7 mg) were weighed, and the system was replaced with nitrogen. To this, dioxane 4 mL, fluorobenzene 1 mmol (96.1 mg) were added, and stirring was carried out at room temperature for 5 minutes, and then LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (corresponding to LHMDS 1.2 mmol) was added, and after stirring at room temperature for 5 minutes, heating and stirring were carried out in a bath at 110°C for 5 hours (internal temperature 92°C). Note that, in the middle, using a small amount of solution taken from the flask, the reaction was traced using liquid chromatography, and in addition to peaks attributable to the starting materials, a large number of clear peaks attributable to the target could be confirmed.

[0597] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was put into a separatory funnel together with saturated ammonium chloride aqueous solution 50 mL, ethyl acetate 30 mL, extraction was performed, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was put into the separatory funnel, the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, put into a separatory funnel, ethyl acetate 20 mL was put into the separatory funnel, extraction was performed, and the organic layer was recovered. The recovered entire organic layer was combined, and dried with 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 toluene 3 mL, and column chromatography was performed using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3), and fractions other than a fraction mainly containing the starting material were collected.

[0599] Finally, the solvent was removed from the fraction collected at 80°C under reduced pressure, and a solid was obtained. However, the obtained solid was not analyzed, and the analysis was performed on the filtrate. 1 In the H-NMR spectrum, a large number of peaks which could not be attributed to the starting material or the target were found. This mixture was a mixture containing a plurality of by-products, and it was judged that it was difficult to isolate the target from this mixture, and no purification other than this was attempted.

[0600] [Example 1-10]

[0601] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.05 mmol (28.8 mg), RuPhos 0.075 mmol (35.0 mg), and pentafluoroaniline 1.2 mmol (219.7 mg) were weighed, and the system was replaced with nitrogen. To this, dioxane 4 mL, chlorobenzene 1 mmol (112.6 mg) were added, and stirring was performed at room temperature for 5 minutes, and then LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (corresponding to LHMDS 1.2 mmol) was added, and after stirring at room temperature for 5 minutes, stirring was performed with heating in a bath at 110°C for 3 hours (internal temperature 92°C). Note that, in the middle of the reaction, 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 starting material decreased, the area of the peak attributable to the target increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0602] After reaction mixture is cooled to room temperature, cooling reaction mixture is put into separating funnel together with saturated aqueous ammonium chloride solution 50mL, ethyl acetate 30mL, extract, make organic layer remain in separating funnel, water layer is reclaimed.Saturated aqueous common salt 50mL is put into separating funnel, remaining organic layer is cleaned, reclaim water layer, organic layer respectively.Then, whole water layers that reclaim are merged, put into separating funnel, put into ethyl acetate 20mL wherein, extract, organic layer is reclaimed, whole organic layers that reclaim are merged, it is dried over mgso.

[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 the obtained solution was subjected to column chromatography (eluting solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3) to collect fractions containing the target product.

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

[0605] [Examples 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 changed to 5 hours, to obtain 256.6 mg of the target product (yield > 99%).

[0607] [Examples 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 a 1 mol / L toluene solution of LHMDS (equivalent to 1.2 mmol of LHMDS) was used instead of a 1.3 mol / L tetrahydrofuran solution of LHMDS, and the reaction time was changed to 5 hours, to obtain 243.5 mg of the target product (yield 94%).

[0609] [Examples 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 product (yield > 99%).

[0611] [Examples 1-14]

[0612] [Chemistry 57]

[0613]

[0614] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.05 mmol (28.8 mg), RuPhos 0.075 mmol (35.0 mg), pentafluoroaniline 1.2 mmol (219.7 mg), 4-fluorobromobenzene 1 mmol (175.0 mg) were weighed, and the system was replaced with nitrogen. To this, dioxane 4 mL was added, and stirred for 5 minutes, and then LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (corresponding to LHMDS 1.2 mmol) was added, and after stirring for 5 minutes at room temperature, it was heated and stirred in a 110°C bath for 5 hours (internal temperature 92°C). Note that in the middle, 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 starting material decreased, the area of the peak attributable to the target increased. At this time, no significant peak corresponding to a byproduct was confirmed.

[0615] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was placed in a separatory funnel together with saturated aqueous ammonium chloride solution 50 mL, ethyl acetate 30 mL, and extraction was performed, and the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, and placed in a separatory funnel, and ethyl acetate 20 mL was placed therein, and extraction was performed, and the organic layer was recovered, and the recovered entire organic layer was combined, and dried with magnesium sulfate.

[0616] 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 toluene 3 mL, and the obtained solution was used for column chromatography (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3), and fractions containing the target were collected.

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

[0618] 1 H NMR (500.13 MHz, CDC13): δ = 5.39 (br s, 1H), 6.84 (m, 2H), 7.00 (br t, 2H)

[0619] 13 C NMR (125.77 MHz, CDC13): δ = 116.0, 116.2, 118.9, 119.0, 138.3, 157.8, 159.7

[0620] 19F NMR (470.53 MHz, CDCI3): δ -165.6 (br t, IF), -164.0 (br dt, F), 151.8 (br d, 2F), 122.6 (br s, IF);

[0621] IR (neat) v = 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 summary of the above Examples 1-10 to 1-14 and Comparative Example 1-8 is shown in Table 2.

[0623] [Table 2]

[0624]

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

[0626] [Chemical Formula 58]

[0627]

[0628] [Example 1-15]

[0629] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.05 mmol (28.8 mg), RuPhos 0.075 mmol (35.0 mg) were weighed and the system was replaced with nitrogen. To this, dioxane 4 mL was added, followed by 2-fluoroaniline 1.2 mmol (133.3 mg), 4-bromoanisole 1 mmol (187.0 mg), and the system was stirred for 5 minutes at room temperature. Next, LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (equivalent to LHMDS 1.2 mmol) was added, and after stirring for 5 minutes at room temperature, the system was heated and stirred for 5 hours in a bath at 110°C (internal temperature 92°C). Note that at the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was tracked using liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0630] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was put into a separatory funnel together with saturated ammonium chloride aqueous solution 50 mL, ethyl acetate 30 mL, extraction was performed, and the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was put into the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, put into a separatory funnel, ethyl acetate 20 mL was put into the separatory funnel, extraction was performed, and the organic layer was recovered. The recovered entire organic layer was combined, and dried with magnesium sulfate.

[0631] 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 toluene 3 mL, and column chromatography was performed using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3), and fractions containing the target product were collected.

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

[0633] 1 H NMR (500.13 MHz, CDCI3): δ = 3.84 (s, 3H), 5.68 (br s, 1H), 6.77-6.79 (m, 1H), 6.93 (d, J = 9.0 Hz, 2H), 7.00 (br t, 1H), 7.07-7.12 (m, 2H); 7.15 (d, J = 9.0 Hz, 2H)

[0634] 13 C NMR (125.77 MHz, CDCI3): 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, CDCI3): δ -136.1 (br s); IR (neat)

[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) + Calcd 217.0903, Found 218.0963.

[0638] [Example 1-16]

[0639] The reaction and work-up were carried out analogously to Example 1-15, except that 3-fluoroaniline 1.2 mmol (133.3 mg) was used instead of 2-fluoroaniline. The target compound was obtained 210.6 mg (yield 97 %).

[0640] 1 H NMR (500.13 MHz, CDC13): δ = 3.79 (s, 3H), 5.57 (br s, 1H), 6.47 (ddd, J = 8.3, 2.3, 0.9 Hz, 1H), 6.56 (dt, J = 11.4, 2.3 Hz, 1H), 6.59 (ddd, J = 8.3, 2.2, 0.9 Hz, 1H), 6.87 (d, J = 8.9, 6.7 Hz, 2H), 7.07 (dd, J = 8.9, 6.7 Hz, 2H), 7.11 (td, J = 8.3, 6.7 Hz, 2H)

[0641] 13 C NMR (125.77 MHz, CDC13): 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, CDC13): δ = -113.7 (ms)

[0643] IR (neat): v ~ = 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) + Calcd 217.0903, Found 218.0969.

[0645] [Example 1-17]

[0646] The reaction and work-up were carried out analogously to Example 1-15, with the exception that 1.2 mmol (133.3 mg) of 4-fluoroaniline was used instead of 2-fluoroaniline. The target compound was obtained in 161.7 mg (yield 74%).

[0647] 1 H NMR (500.13 MHz, CDCI3): δ = 3.79 (s, 3H), 5.36 (br s, 1 H), 6.84-7.25 (m, 8H)

[0648] 13 C NMR (125.77 MHz, CDCI3): 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, CDCI3): δ = -125.6 (s)

[0650] IR (neat): v ~ = 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) + Calcd 217.0903, Found 218.0965.

[0652] [Example 1-18]

[0653] The reaction and work-up were carried out analogously to Example 1-15, except that 2,6-difluoroaniline 1.2 mmol (154.9 mg) was used instead of 2-fluoroaniline. The target compound was obtained in 216.2 mg (yield 92%).

[0654] 1 H NMR (500.13 MHz, CDC13): δ = 3.77 (s, 3H), 5.37 (br s, 1H), 6.81 (br s, 4H), 6.91-6.93 (m, 3H)

[0655] 13 C NMR (125.77 MHz, CDC13): 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, CDC13): δ = -123.4 (m)

[0657] IR (neat): v ~ = 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) + Calcd 235.0809, Found 236.0867.

[0659] [Example 1-19]

[0660] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.05 mmol (28.8 mg), RuPhos 0.075 mmol (35.0 mg), 2,4,6-trifluoroaniline 1.2 mmol (176.5 mg) were weighed and the system was replaced with nitrogen. To this, dioxane 4 mL was added, followed by the addition of 4-bromoanisole 1 mmol (187.0 mg). After stirring for 5 minutes, LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (corresponding to LHMDS 1.2 mmol) was added, and the stirring was performed at 110°C (internal temperature 92°C) for 4 hours. Note that, in the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was tracked by liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target product increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0661] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was placed in a separatory funnel together with saturated aqueous ammonium chloride solution 50 mL and ethyl acetate 30 mL, and extraction was performed. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was placed in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined and placed in a separatory funnel, ethyl acetate 20 mL was placed in the separatory funnel, and extraction was performed. The organic layer was recovered, and the recovered entire organic layer was combined and dried with 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 toluene 3 mL, and column chromatography was performed using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 97 / 3), and fractions containing the target product were collected.

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

[0664] 1 H NMR (500.13 MHz, CDC13): δ = 3.76 (s, 3H), 5.14 (br s, 1H), 6.72-6.75 (m, 3H), 6.80 (d, J = 9.0 Hz, 2H)

[0665] 13 C NMR (125.77 MHz, CDC13): δ = 55.8, 100.9, 114.7, 117.4, 117.9, 137.6, 154.8, 156.7, 157.8

[0666] 19F NMR (470.45 MHz, CDCl3): δ = -119.8 (br s), -116.9 (br s)

[0667] IR (neat): v ~ 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) + Calculated 253.0714, found 254.0772.

[0669] [Example 1-20]

[0670] The reaction and work-up were carried out analogously to Example 1-19, with the exception that 2,3,5,6-tetrafluoroaniline 1.2 mmol (154.9 mg) was used instead of 2,4,6-trifluoroaniline. The target compound 243.9 mg (yield 90%) was obtained.

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

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

[0673] 19F NMR (470.45 MHz, CDC13): δ = -154.00, -154.08 (m, 2F), -141.49, -141.57 (m, 2F); IR (neat): v ~ = 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) + Calcd 271.0620, Found 272.0694.

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

[0676] [Table 3]

[0677]

[0678] [Example 1-21]

[0679] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.2 mmol (115.0 mg), RuPhos 0.3 mmol (140.0 mg), 4,4'-diaminooctafluorobiphenyl 2.5 mmol (656.3 mg) were weighed and the system was replaced with nitrogen. To this, dioxane 8 mL was added, and then bromobenzene 4.8 mmol (753.6 mg) was added, and after stirring for 5 minutes, LHMDS 1.3 mol / L tetrahydrofuran solution 3.7 mL (equivalent to LHMDS 4.8 mmol) was added, and heating and stirring were carried out in a bath at 110°C for 5 hours (internal temperature 92°C). Note that, in the middle, 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 starting material decreased, the area of the peak attributable to the target increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0680] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was put into a separatory funnel together with saturated ammonium chloride aqueous solution 50 mL, ethyl acetate 30 mL, extraction was performed, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was put into the separatory funnel, the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, put into a separatory funnel, ethyl acetate 20 mL was put into the separatory funnel, extraction was performed, and the organic layer was recovered. The recovered entire organic layer was combined, and dried with magnesium sulfate.

[0681] 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 toluene 3 mL, and column chromatography was performed using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 90 / 10), and fractions containing the target product were collected.

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

[0683] 1 H NMR (500.13 MHz, CDC13): δ = 5.45 (br s, 1H), 6.85 (br d, 2H), 7.02 (br t, 1H), 7.30 (br t, 2H)

[0684] 13 C NMR (125.77 MHz, CDC13): δ = 116.7, 122.2, 129.5, 142.3

[0685] 19 F NMR (470.53 MHz, CDC13): δ = -164.9 (br t, IF), -164.1 (dt, J = 22.1, 5.8 Hz, 2F), -150.7 (br d, 2F), IR (neat): v ~ = 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] The reaction and the post-treatment were performed in the same manner as in Example 1-21 except that 1-bromo-4-tert-butylbenzene 4.8 mmol (1023.0 mg) was used instead of bromobenzene, and the target product 1.07 g (yield 91%) was obtained.

[0688] 1H 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 (br s, 2H)

[0689] 13 C 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 F NMR (470.45 MHz, acetone): δ = -152.67 (br d, F), -143.45 - (-143.1) (m, 4F)

[0691] IR (neat): v ~ 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) + Calcd 592.2125, Found 593.2170.

[0693] [Examples 1-23]

[0694] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.2 mmol (115.0 mg), RuPhos 0.3 mmol (140.0 mg), 4,4'-diamino octafluorobiphenyl 2.5 mmol (656.3 mg), 4-bromo-4'-tert-butylbiphenyl 4.8 mmol (1388.2 mg) were weighed and the system was replaced with nitrogen. To this, dioxane 8 mL was added, after stirring for 5 minutes, LHMDS 1.3 mol / L tetrahydrofuran solution 3.7 mL (equivalent to LHMDS 4.8 mmol) was added, and stirring was performed at 110°C for 5 hours (internal temperature 92°C). Note that, in the middle, a small amount of the solution in the flask was taken, and the reaction was tracked using liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0695] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was placed in a separatory funnel together with saturated aqueous ammonium chloride solution 50 mL, ethyl acetate 30 mL, extraction was performed, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was placed in the separatory funnel, the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, placed in a separatory funnel, ethyl acetate 20 mL was placed therein, extraction was performed, and the organic layer was recovered. The recovered entire organic layer was combined, and dried with magnesium sulfate.

[0696] 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 toluene 3 mL, and column chromatography was performed using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 90 / 10), and fractions containing the target were collected.

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

[0698] 1 H NMR (500.13 MHz, THF): δ = 1.38 (s, 18H), 7.09 (br d, 4H), 7.47 (br d, 4H), 7.56 (br t, 8H), 8.07 (br s, 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] 19F NMR (470.45 MHz, THF): δ = -152.14 (br d, F), -143.24, -143.29 (m, 4F)

[0701] IR (neat): v ~ 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) + Calculated 744.2751, found 745.2794.

[0703] [Example 1-24]

[0704] The reaction and work-up were carried out analogously to Example 1-23, except that 1-bromonaphthalene 4.8 mmol (993.9 mg) was used instead of 4-bromo-4'-tert-butylbiphenyl. The target compound was obtained in 617.0 mg (yield 68%).

[0705] 1 H NMR (500.13 MHz, DMF): δ = 7.27 (br d, 2H), 7.51 (t, J = 7.8 Hz, 2H), 7.59-7.64 (m, 4H), 7.74 (br d, 2H), 8.00-8.03 (m, 2H), 8.47-8.50 (m, 2H), 8.82 (br s, 2H)

[0706] 13 C 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] 19F NMR (470.45 MHz, DMF): δ = -153.18 (br d, J = 13.9 Hz, 4F), -143.45 - (-143.35) (m, 4F)

[0708] IR (neat): v ~ 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) + Calculated 580.1186, found 581.1249.

[0710] [Example 1-25]

[0711] The reaction and work-up were carried out analogously to Example 1-23, with the exception that 2-bromonaphthalene 4.8 mmol (993.9 mg) was used instead of 4-bromo-4'-tert-butylbiphenyl. The target compound was obtained in 770.2 mg (yield 53%).

[0712] 1 H NMR (500.13 MHz, DMSO): δ = 7.23 - 7.35 (m, 6H), 7.43 (br t, 2H), 7.77 (br d, 2H), 7.83 (br t, 4H), 9.00 (br s, 2H)

[0713] 13 C NMR (125.77 MHz, DMSO): δ = 98.2, 111.9, 119.9, 124.2, 124.4, 126.9, 127.0, 128.0, 129.0, 129.4, 134.3, 140.3, 140.9, 144.9

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

[0715] IR (neat): v ~ 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) + Calcd 580.1186, Found 581.1249.

[0717] [Example 1-26]

[0718] The reaction and work-up were carried out analogously to Example 1-23, with the exception that 4-bromo-triphenylamine 4.8 mmol (1556.2 mg) was used instead of 4-bromo-4'-tert-butylbiphenyl. This yielded 1417.3 mg of the target product (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 (br s, 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 (br d, J = 13.9 Hz, 4F), -143.27 (m, 4F)

[0722] IR (neat): v ~ = 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) + Calcd 814.2343, Found 814.2312.

[0724] [Example 1-27]

[0725] The reaction and work-up were performed analogously to Example 1-23, except that 4-iodotriphenylamine 4.8 mmol (1781.9 mg) was used instead of 4-bromo-4'-tert-butylbiphenyl, to give the target 1101.3 mg (yield 68 %).

[0726] [Example 1-28]

[0727] The reaction and work-up were performed analogously to Example 1-23, except that 4-bromo-4'-(diphenylamino)biphenyl 4.8 mmol (1921.5 mg) was used instead of 4-bromo-4'-tert-butylbiphenyl, to give the target 1903.1 mg (yield 99 %).

[0728] [Example 1-29]

[0729] The reaction and work-up were performed analogously to Example 24, except that 2-bromo-9,9'-spirobi[9H-fluorene] 4.8 mmol (1897.4 mg) was used instead of 4-bromo-4'-tert-butylbiphenyl, to give the target 1.88 g (yield 98 %).

[0730] 1H NMR (500.13 MHz, Acetone): δ = 6.39 (br s, 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 (br dd, 4H) 7.97 (br d, J = 7.5, 4H)

[0731] 13 C NMR (125.77 MHz, Acetone): δ = 66.9, 99.0, 114.6, 118.0, 120.5, 121.1, 121.5, 124.5, 124.8, 125.1, 127.9, 128.6, 128.88, 136.9, 141.2, 142.7, 142.8, 142.9, 145.8, 149.4, 149.9, 151.0

[0732] 19 F NMR (470.45 MHz, Acetone): δ = -152.3 (br d, 4F), -143.2 (m, 4F)

[0733] IR (neat): v ~ 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 956.2438, found 812.4212.

[0735] [Examples 1-30]

[0736] [Formula 59]

[0737]

[0738] In a 100 mL reaction flask equipped with a reflux column, Pd(dppf)Cl20.45 mmol (367.5 mg), potassium acetate 45 mmol (4416.3 mg), 3-bromo-N-phenylcarbazole 15 mmol (4833.2 mg), bis(pinacolato)diboron 11 mmol (4190.0 mg) were weighed and the system was replaced with nitrogen. To this, N,N-dimethylformamide 150 mL was added and after stirring for 5 minutes, it was heated in a 90°C bath for 3 hours. Further, the reaction was followed by chromatography (TLC) using a small amount of the reaction mixture taken from the system.

[0739] After the reaction mixture was cooled to room temperature, the solvent was removed from the cooled reaction mixture under reduced pressure and concentrated, the concentrate was put in a separatory funnel together with ion exchange water 50 mL, washed, and next chloroform 50 mL was put in and extraction was performed, and the organic layer was recovered from the separatory funnel. Then, the recovered organic layer was dried with magnesium sulfate.

[0740] The 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 fractions containing the target were collected.

[0741] Finally, the solvent was removed from the fraction collected under reduced pressure, and N-phenylcarbazol-3-yl-pinacol borate 4.21 g (yield 76%) was obtained.

[0742] 1 H NMR (500.13 MHz, CDCI3): δ = 1.41 (s, 12H), 7.29 (ddd, J = 7.9, 6.0, 2.0 Hz, 1H), 7.37 (br d, 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] [Compound 60]

[0744]

[0745] In a 50 mL reaction flask equipped with a reflux column, Pd(PPh3)40.09 mmol (104.1 mg), sodium hydroxide 9 mmol (359.9 mg), N-phenylcarbazol-3-yl-boronic acid pinacol ester 3 mmol (1107.8 mg), and 4-bromo-4'-iodobiphenyl 3.3 mmol (1184.7 mg) were weighed out, and the system was replaced with nitrogen. To this was added a mixed solvent of tetrahydrofuran and water (2 / 1 (v / v)) 13.5 mL, and after stirring for 5 minutes, the system was heated and stirred in a 50°C bath for 5 hours. Further, the reaction was followed by a chromatography (TLC) method using a small amount of the reaction mixture taken from the system.

[0746] After the reaction mixture was cooled to room temperature, the solvent was removed from the cooled reaction mixture under reduced pressure, and the concentrate was placed in a separatory funnel together with ion exchange water 50 mL, washed, and then placed in tetrahydrofuran 50 mL and extracted. The organic layer was recovered from the separatory funnel. Then, the recovered organic layer was dried with magnesium sulfate.

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

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

[0749] 1 H NMR (500.13 MHz, CDC13): 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 (br s, 1H)

[0750] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.5 mmol (28.8 mg), RuPhos 0.75 mmol (35.0 mg), 4,4'-diamino-octafluorobiphenyl 0.5 mmol (164.1 mg) were weighed and the system was replaced with nitrogen. To this, dioxane 8 mL was added, and then 4-bromo-4'-(N-phenylcarbazol-3-yl)-biphenyl 1.05 mmol (498.1 mg) was added. After stirring for 5 minutes, LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (1.2 mmol) was added, and the stirring was performed at 110°C for 5 hours (internal temperature 92°C). Note that, in the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was traced by liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target product increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0751] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was put in a separatory funnel together with saturated aqueous ammonium chloride solution 50 mL and ethyl acetate 30 mL, and extraction was performed. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was put in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined and put in a separatory funnel, ethyl acetate 20 mL was put in the separatory funnel, and extraction was performed. The organic layer was recovered, and the recovered entire organic layer was combined and dried with magnesium sulfate.

[0752] 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 toluene 3 mL, and column chromatography was performed using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 90 / 10), and fractions containing the target product were collected.

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

[0754] 1 H NMR (500.13 MHz, CDC13): δ = 5.94 (br s, 2H), 7.11 (br d, 2H), 7.32 (br quin, 1H), 7.43 (br d, 2H), 7.48-7.51 (m, 2H), 7.60-7.66 (m, 6H), 7.70-7.72 (br m, 3H), 7.80-7.82 (m, 3H), 8.21 (br d, 2H), 8.41 (br s, 1H)

[0755] [Example 1-31]

[0756] [Compound 61]

[0757]

[0758] In a 100 mL reaction flask equipped with a reflux column, Pd(dppf)Cl20.45 mmol (367.5 mg), potassium acetate 45 mmol (4416.3 mg), 2-bromo-9,9'- spirobi[9H-fluorene] 15 mmol (5929.5 mg), bis(pinacolato)diboron 16.5 mmol (4190.0 mg) were weighed and the system was replaced with nitrogen. To this, N,N-dimethylformamide 150 mL was added and after stirring for 5 minutes, it was heated in a 90°C bath for 3 hours. Further, the reaction was followed by chromatography (TLC) using a small amount of the reaction mixture taken from the system.

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

[0760] The 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 fractions containing the target were collected.

[0761] Finally, the solvent was removed from the fractions collected under reduced pressure, and 9,9'-spirobi[9H-fluorene]-2-yl-boronic acid pinacol ester 1.85 g (yield 28%) was obtained.

[0762] 1 H NMR (500.13 MHz, CDCI3): δ = 1.25 (s, 12H), 6.68 (br d, J = 7.5 Hz 1H), 6.71 (br d, 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 (br s, 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 column, Pd(PPh3)40.09 mmol (104.1 mg), sodium hydroxide 9 mmol (359.9 mg), 9,9'-spirobi[9H-fluorene]-2-yl-boronic acid pinacol ester 3 mmol (1327.1 mg), 4-bromo-4'-iodobiphenyl 3.3 mmol (1184.7 mg) were weighed, and the system was replaced with nitrogen. To this, a mixed solvent of tetrahydrofuran and water (2 / 1 (v / v)) 13.5 mL was added, and after stirring for 5 minutes, it was heated and stirred in a 50°C bath for 5 hours. Further, the reaction was traced by a chromatography (TLC) method using a small amount of the reaction mixture taken from the system.

[0766] After the reaction mixture was cooled to room temperature, the solvent was removed from the cooled reaction mixture under reduced pressure, and the concentrate was put into a separatory funnel together with ion exchange water 50 mL, washed, and then put into tetrahydrofuran 50 mL, extracted, and the organic layer was recovered from the separatory funnel. Then, the recovered organic layer was dried with magnesium sulfate.

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

[0768] Finally, the solvent was removed from the fraction collected under reduced pressure, and 2-(4'-bromobiphenyl-4-yl)-9,9'-spirobi[9H-fluorene] 836.4 mg (yield 51%) was obtained.

[0769] 1 H NMR (500.13 MHz, CDC13): δ = 6.73 (d, J = 7.6 Hz, 1H), 6.78 (d, J = 7.6 Hz, 2H), 6.97 (s, 1H), 7.12 (br t, 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, Pd(DBA)2 0.5 mmol (28.8 mg), RuPhos 0.75 mmol (35.0 mg), 4,4'-diamino octafluorobiphenyl 0.5 mmol (164.1 mg) were weighed and the system was replaced with nitrogen. To this, dioxane 8 mL was added, and then 2-(4'-bromobiphenyl-4-yl)-9,9'- spirobi[9H-fluorene] 1.05 mmol (574.9 mg) was added. After stirring for 5 minutes, LHMDS 1.3 mol / L tetrahydrofuran solution 0.923 mL (corresponding to LHMDS 1.2 mmol) was added, and the stirring was performed at 110°C for 5 hours (internal temperature 92°C). Note that, in the middle of the reaction, a small amount of the solution in the flask was taken, and the reaction was tracked using liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0771] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was put in a separatory funnel together with saturated aqueous ammonium chloride solution 50 mL, ethyl acetate 30 mL, and extraction was performed. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was put in the separatory funnel, and the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined and put in a separatory funnel, ethyl acetate 20 mL was put in the separatory funnel, and extraction was performed. The organic layer was recovered, and the recovered entire organic layer was combined and dried with magnesium sulfate.

[0772] 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 toluene 3 mL, and column chromatography was performed using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 90 / 10), and fractions containing the target were collected.

[0773] Finally, the solvent was removed from the fraction collected at 80°C under reduced pressure, and the target 532 mg (yield 86%) was obtained.

[0774] 1 H NMR (500.13 MHz, CDC13): δ = 6.78 (br d, 2H), 6.83 (br d, 4H), 7.05 (br m, 6H), 7.15 (br t, 6H), 7.41 (br t, 6H), 7.54 (br m, 12H), 7.70 (br d, 2H), 7.90 (br d, 6H), 7.95 (br d, 2H),

[0775] 13C NMR (125.77 MHz, CDC13): 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 F NMR (470.45 MHz, CDC13): δ = -151.41 (br d, 4F), -140.63 (m, 4F)

[0777] IR (neat): v ~ = 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 summary of the above Examples 1-21 to 1-31 is shown in Table 4.

[0779] [Table 4]

[0780]

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

[0782] [Chemical 63]

[0783]

[0784] [Example 1-32]

[0785] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.1 mmol (57.5 mg), RuPhos 0.15 mmol (69.8 mg), and 4,4'-dibromobiphenyl 1 mmol (312.7 mg) were weighed out, and the system was replaced with nitrogen. To this, dioxane 8 mL and pentafluoroaniline 2.4 mmol (439.3 mg) were added, and after stirring for 5 minutes, LHMDS 1.3 mol / L tetrahydrofuran solution 1.84 mL (equivalent to LHMDS 2.4 mmol) was added, and stirring was performed at 110°C in a bath (internal temperature 92°C) for 5 hours. Note that, at the middle of the reaction, a small amount of the solution in the flask was taken out, and the reaction was tracked using liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0786] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was placed in a separatory funnel together with saturated aqueous ammonium chloride solution 50 mL and ethyl acetate 30 mL, extraction was performed, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was placed in the separatory funnel, the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, placed in a separatory funnel, ethyl acetate 20 mL was placed therein, extraction was performed, and the organic layer was recovered. The recovered entire organic layer was combined, and dried with magnesium sulfate.

[0787] 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 toluene 3 mL, and column chromatography was performed using the obtained solution (elution solvent: hexane / ethyl acetate = 100 / 0 → 90 / 10), and fractions containing the target were collected.

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

[0789] 1 H NMR (500.13 MHz, DMSO): δ = 6.86 (br d, J = 8.1 Hz, 4H), 7.45 (br d, J = 8.1 Hz, 4H), 8.32 (br s, 2H)

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

[0791] 19F NMR (470.45 MHz, DMSO): δ = -165.04 (br t, 2F), -163.81 (br t, 4F), -148.47 (br d, 4H)

[0792] IR (neat): v ~ 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: effect of base

[0794] [Formula 64]

[0795]

[0796] [Examples 1-33]

[0797] The reaction and work-up were carried out in the same way as in Example 1-11 except that pentafluoroaniline (1 mmol), bromobenzene (2.4 mmol), LHMDS 1.3 mol / L in tetrahydrofuran 1.85 mL (corresponding to LHMDS 2.4 mmol) were used, and the target product was obtained as 179.8 mg (yield 69%).

[0798] [Example 1-34]

[0799] The reaction and work-up were carried out in the same way as in Example 1-11 except that pentafluoroaniline (2.4 mmol), bromobenzene (1 mmol), LHMDS 1.3 mol / L in tetrahydrofuran 1.85 mL (corresponding to LHMDS 2.4 mmol) were used, and the target product was obtained as 193.6 mg (yield 75%).

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

[0801] [Table 5]

[0802]

[0803] (6) Synthesis of polymers

[0804] [Formula 65]

[0805]

[0806] [Example 2-1]

[0807] In a 30 mL reaction flask equipped with a reflux tower, 20.08 mmol (46.0 mg) of Pd(DBA), 0.12 mmol (56.0 mg) of RuPhos, and 4.2 mmol (1378.3 mg) of 4,4'-diaminooctafluorobiphenyl were weighed and the system was purged with nitrogen. 8 mL of dioxane and 10 mmol (943.6 mg) of 1,4-dibromobenzene were added, and after stirring for 5 minutes, 7.1 mL of a 1.3 mol / L tetrahydrofuran solution of LHMDS (equivalent to 9.2 mmol of LHMDS) was added, and the mixture was heated and stirred in a 110°C bath for 5 hours (internal temperature 92°C). It should be noted that a small amount of the solution in the flask was collected during the reaction and the reaction was monitored 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 clear peak corresponding to the by-product was confirmed.

[0808] After reaction mixture is cooled to room temperature, cooling reaction mixture is put into separating funnel together with saturated aqueous ammonium chloride solution 100mL, ethyl acetate 50mL, extract, make organic layer remain in separating funnel, water layer is reclaimed.Saturated aqueous common salt 50mL is put into separating funnel, remaining organic layer is cleaned, reclaim water layer, organic layer respectively.Then, whole water layers that reclaim are merged, put into separating funnel, put into ethyl acetate 30mL wherein, extract, organic layer is reclaimed, whole organic layers that reclaim are merged, it is dried over mgso.

[0809] 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 added dropwise to 500 mL of a mixed solvent of hexane and toluene (2 / 1 (v / v)). The generated solid was recovered by filtration, and the filtrate was dried at 80° C. under reduced pressure to obtain 0.47 g of the target product.

[0810] 1 H NMR (500.13MHz, DMSO): δ = 7.08 (brd, J = 7.7Hz, 4H), 7.56 (brd, J = 7.7Hz, 4H), 8.68 (brs, 2H)

[0811] 13 C NMR (125.77MHz, DMSO): δ=97.2,117.6,123.9,126.1,127.8,128.5,132.9,140.0,140.7,144.2

[0812] 19F NMR (470.45 MHz, DMSO): δ = -148.76 (d, J = 17.3 Hz, 4F), -140.67 (s, 4F)

[0813] IR (neat): v ~ 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] The reaction and the post-treatment were carried out in the same manner as in Example 2-1 except that Pd(DBA)2 0.4 mmol (230.0 mg), RuPhos 0.6 mmol (280.0 mg) were used, to obtain the target 1.60 g.

[0816] The summary of Example 2-1 and Example 2-2 is shown in Table 6. As shown in Table 6, it was found that the molecular weight of the obtained polymer could be controlled by changing the amount of catalyst.

[0817] [Table 6]

[0818]

[0819] [Chem. 66]

[0820]

[0821] [Example 2-3]

[0822] [Chem. 67]

[0823]

[0824] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.5 mmol (287.5 mg), 0.75 mmol (350.0 mg), 4,4'-diamino octafluorobiphenyl 2.5 mmol (820.4 mg), 4,4'-dibromo biphenyl 2.38 mmol (742.9 mg) were weighed and the system was replaced with nitrogen. To this, dioxane 8 mL was added and after stirring for 5 minutes, LHMDS 1.3 mol / L tetrahydrofuran solution 7.1 mL (equivalent to LHMDS 9.2 mmol) was added and the stirring was carried out at 110°C for 5 hours (internal temperature 92°C). It should be noted that at the middle of the reaction, a small amount of the solution in the flask was taken and the reaction was traced by liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target increased. At this time, no significant 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 saturated aqueous ammonium chloride solution 100 mL, ethyl acetate 50 mL, extraction was carried out, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was placed in the separatory funnel, the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, placed in a separatory funnel, ethyl acetate 30 mL was placed therein, extraction was carried out, and the organic layer was recovered. The recovered entire organic layer was combined, and dried with magnesium sulfate.

[0826] 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 tetrahydrofuran 10 mL, the obtained solution was dropped into a mixed solvent of hexane and toluene (2 / 1 (v / v)) 500 mL, the generated solid was recovered by filtration, and the obtained filtrate was dried at 80°C under reduced pressure, to obtain the target 1.01 g. The obtained polymer had Mw = 32000, Mn = 15000, Mw / Mn = 2.13, and ΔT5 was 321.6°C, and no Tg was observed.

[0827] [Example 2-4]

[0828] [Formula 68]

[0829]

[0830] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.3 mmol (172.5 mg), RuPhos 0.45 mmol (210.0 mg), 4,4'-diamino octafluorobiphenyl 1.5 mmol (492.3 mg), and 3,6-dibromo-9-phenylcarbazole 1.43 mmol (572.3 mg) were weighed out, and the system was replaced with nitrogen. To this was added dioxane 8 mL, and after stirring for 5 minutes, LHMDS 1.3 mol / L tetrahydrofuran solution 2.54 mL (corresponding to LHMDS 3.3 mmol) was added, and the stirring was performed at 110°C for 5 hours (internal temperature 92°C). Note that, in the middle of the reaction, a small amount of the solution in the flask was taken out, and the reaction was traced by liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0831] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was put in a separatory funnel together with saturated ammonium chloride aqueous solution 100 mL and ethyl acetate 50 mL, extraction was performed, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was put in the separatory funnel, the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, put in a separatory funnel, ethyl acetate 30 mL was put in the separatory funnel, extraction was performed, and the organic layer was recovered. The recovered entire organic layer was combined, and dried with magnesium sulfate.

[0832] 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 tetrahydrofuran 10 mL, the obtained solution was dropped into a mixed solvent of hexane and toluene (2 / 1 (v / v)) 500 mL, the generated solid was recovered by filtration, and the obtained filtrate was dried at 80°C under reduced pressure, to obtain the target 928 mg. The obtained polymer had Mw = 12000, Mn = 7000, Mw / Mn = 1.71, and 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 (br s, H), 5.80 (br s, 4H), 6.07 (d, 2H), 7.62 (br d, J = 8.0 Hz, 2H), 8.06 (br s, 2H)

[0834] 13C 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 F NMR (470.45 MHz, THF): δ = -151.34 (br d, 4F), -145.89 (br d, 4F)

[0836] IR (neat): v ~ 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] [Formula 69]

[0839]

[0840] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.4 mmol (230.0 mg), RuPhos 0.6 mmol (280.0 mg), 4,4'-diaminooctafluorobiphenyl 2 mmol (656.3 mg), 2,7-dibromo-9,9-dimethylfluorene 1.90 mmol (670.6 mg) were weighed and the system was replaced with nitrogen. To this, dioxane 8 mL was added and after stirring for 5 minutes, LHMDS 1.3 mol / L tetrahydrofuran solution 3.2 mL (equivalent to LHMDS 4.2 mmol) was added, and stirring was performed for 5 hours at 110°C (internal temperature 92°C) in a bath. Note that, in the middle, 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 starting material decreased, the area of the peak attributable to the target increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0841] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was put into a separatory funnel together with saturated aqueous ammonium chloride solution 100 mL, ethyl acetate 50 mL, extraction was performed, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was put into the separatory funnel, the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, put into a separatory funnel, ethyl acetate 30 mL was put into the separatory funnel, extraction was performed, and the organic layer was recovered. The recovered entire organic layer was combined, and dried with 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 tetrahydrofuran 10 mL, the obtained solution was dropped into a mixed solvent of hexane and toluene (2 / 1 (v / v)) 500 mL, the generated solid was recovered by filtration, and dried at 80°C under reduced pressure to obtain the target 926 mg. The obtained polymer was 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 (br d, J = 8.0 Hz, 2H), 7.18 (s, 2H), 7.62 (br d, J = 8.0 Hz, 2H), 8.06 (br s, 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 (br d, 4F), -142.20 (br d, 4F)

[0846] IR (neat): v ~ = 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] [Formula 70]

[0849]

[0850] In a 30 mL reaction flask equipped with a reflux column, Pd(DBA)2 0.3 mmol (172.5 mg), RuPhos 0.45 mmol (210.0 mg), 4,4'-diamino octafluorobiphenyl 1.5 mmol (492.3 mg), 9,10-dibromoanthracene 1.43 mmol (480 mg) were weighed and the system was replaced with nitrogen. To this, dioxane 8 mL was added, after stirring for 5 minutes, LHMDS 1.3 mol / L tetrahydrofuran solution 2.54 mL (corresponding to LHMDS 3.3 mmol) was added, and stirring was performed at 110°C for 5 hours (internal temperature 92°C). Note that, in the middle, a small amount of the solution in the flask was taken, and the reaction was tracked using liquid chromatography. As the area of the peak attributable to the starting material decreased, the area of the peak attributable to the target increased. At this time, no significant peak corresponding to a by-product was confirmed.

[0851] After the reaction mixture was cooled to room temperature, the cooled reaction mixture was placed in a separatory funnel together with saturated aqueous ammonium chloride solution 100 mL, ethyl acetate 50 mL, extraction was performed, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. Saturated brine 50 mL was placed in the separatory funnel, the remaining organic layer was washed, and the aqueous layer and the organic layer were recovered, respectively. Then, the recovered entire aqueous layer was combined, placed in a separatory funnel, ethyl acetate 30 mL was placed therein, extraction was performed, and the organic layer was recovered. The recovered entire organic layer was combined, and dried with magnesium sulfate.

[0852] 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 tetrahydrofuran 10 mL, the obtained solution was dropped into a mixed solvent of hexane and toluene (2 / 1 (v / v)) 500 mL, the generated solid was recovered by filtration, and the filtrate was dried at 80°C under reduced pressure, to obtain the target 928 mg. The obtained polymer had Mw = 18000, Mn = 8100, 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] 13C NMR (125.77 MHz, CDCI3): δ = 123.9, 126.4, 128.7, 129.3, 131.3, 135.8, 137.7, 143.5, 145.5

[0855] 19 F NMR (470.53 MHz, CDCI3): δ = -160.0 (br s, 4F), -143.2 (br s, 4F)

[0856] IR (neat): v ~ = 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] Charge transportable composition and production of charge transportable film

[0858] [Example 3-1]

[0859] In a sample bottle (10 mL), 35.9 mg of the fluorinated aryl amine compound having a naphthyl group represented by the following formula (H1) and 56.2 mg of the aryl sulfonic acid compound represented by the following formula (D2) synthesized in Example 1-24 were weighed, 3 g of tetrahydrofurfuryl alcohol was added, and stirred at room temperature until it became uniform, to obtain a solution of 3 mass% of solid content. After the solution was coated on an ITO substrate using a spin coater, it was dried under the atmosphere at 80°C for 1 minute, and then, baked at 230°C for 15 minutes, to produce a thin film of 50 nm in thickness. As the ITO substrate, a glass substrate on the surface of which indium tin oxide (ITO) was formed in a film thickness of 50 nm was used. On the thin film, an aluminum thin film was formed using an evaporation device (vacuum degree 4.0 x 10 -5 Pa) to obtain a single layer element. The evaporation was performed under the condition of an evaporation rate of 0.2 nm / sec. The film thickness of the aluminum thin film was set to 80 nm. Note that the aryl sulfonic acid compound represented by the following formula (D2) was synthesized according to the method described in International Publication No. 2006 / 025342.

[0860] [Formula 71]

[0861]

[0862] [Example 3-2]

[0863] In a sample bottle (10 mL), 44 mg of the fluorinated aryl amine compound having a triphenyl amine group represented by the following formula (H2) synthesized in Example 1-26 and 49 mg of the aryl sulfonic acid compound represented by the above formula (D2) were weighed, 3 g of tetrahydrofurfuryl alcohol was added, and stirred at room temperature until it became uniform, to obtain a 3 mass% solution of solid content. 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 aryl amine copolymer having a biphenyl skeleton represented by the following formula (H3) synthesized in Example 2-3 and 40 mg of the aryl sulfonic acid compound represented by the above formula (D2) were weighed, 3 g of tetrahydrofurfuryl alcohol was added, and stirred at room temperature until it became uniform, to obtain a 2 mass% solution of solid content. 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 aryl amine copolymer having a phenylcarbazole group represented by the following formula (H4) synthesized in Example 2-4 and 57 mg of the aryl sulfonic acid compound represented by the above formula (D2) were weighed, 3 g of tetrahydrofurfuryl alcohol was added, and stirred at room temperature until it became uniform, to obtain a 3 mass% solution of solid content. 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 aryl amine copolymer having a 9,9-dimethylfluorene group represented by the following formula (H5) synthesized in Example 2-5 and 59 mg of the aryl sulfonic acid compound represented by the above formula (D2) were weighed, 3 g of tetrahydrofurfuryl alcohol was added, and stirred at room temperature until it became uniform, to obtain a 3 mass% solution of solid content. Except for using this solution, a single layer element was produced in the same manner as in Example 3-1.

[0876] [Para 75]

[0877]

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

[0879] [Table 7]

[0880]

[0881] As shown in Table 7, it was found that the thin film containing the fluorinated arylamine compound or the polymer of the present application as the charge transport substance showed good electric conductivity.

Claims

1. A polymer comprising a repeating unit represented by the following formula (P1-2): Where, X 211 is a divalent group represented by the following formula (A02-1-1), Y 221 represents a divalent group represented by any one of the following formulae (D05), (D17), and (D19), Where, L 12 Represents hydrogen atoms, which can be Z 130 Alkyl groups with 1 to 20 carbon atoms, which may be substituted by Z 130 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 131 a substituted aryl group having 6 to 20 carbon atoms, L 13 and L 14 Each independently represents a hydrogen atom, which may be replaced by Z 130 Alkyl groups with 1 to 20 carbon atoms, which may be substituted by Z 130 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 131 a substituted aryl group having 6 to 20 carbon atoms, Z 105 , Z 117 and Z 121 Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a Z 130 Alkyl groups with 1 to 20 carbon atoms, which may be substituted by Z 130 The substituted alkenyl group having 2 to 20 carbon atoms may be Z 131 a substituted aryl group having 6 to 20 carbon atoms, Z 130 Each independently represents a fluorine atom, a chlorine atom, a bromine atom or Z 132 a substituted aryl group having 6 to 20 carbon atoms, Z 131 Each independently represents a fluorine atom, a chlorine atom, a bromine atom, which may be Z 132 The alkyl group having 1 to 20 carbon atoms may be substituted or may be Z 132 a substituted alkenyl group having 2 to 20 carbon atoms, Z 132 represents a fluorine atom, a chlorine atom, or a bromine atom. 2 . The polymer according to claim 1 , which is composed only of the repeating unit represented by the formula (P1-2).

3. The polymer according to claim 1 or 2, wherein The Y 221 It is a divalent group represented by any one of the formulae (D17) and (D19).

4. The polymer according to claim 1 or 2, wherein The Z 105 , Z 117 and Z 121 A hydrogen atom, an alkyl group with 1 to 20 carbon atoms, which may be Z 130 a substituted alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

5. The polymer according to claim 1 or 2, wherein The Z 105 , Z 117 and Z 121 A hydrogen atom.

6. The polymer according to claim 2, which is represented by any one of the following formulas, , In the formula, m each independently represents an integer of 2 or greater.

7. A charge transporting substance composed of the polymer according to any one of claims 1 to 6. 8 . A charge-transporting composition comprising the charge-transporting substance according to claim 7 and an organic solvent. 9 . The charge-transporting composition according to claim 8 , comprising a dopant substance. 10 . A charge-transporting thin film obtained from the charge-transporting composition according to claim 8 .

11. An electronic component comprising the charge transport thin film according to claim 10. 12 . An organic electroluminescent element comprising the charge transport thin film according to claim 11 .

13. The organic electroluminescent element according to claim 12, wherein The charge transport thin film is a hole injection layer or a hole transport layer.

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