JPWO2020027258A1 - Method for producing fluorinated aromatic secondary amine compound - Google Patents

Abstract

A catalyst containing a fluorinated aromatic primary amine compound and a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon, and a palladium zero-valent complex of dibenzylideneacetone, the following formula (L ) A fluorinated aromatic amine compound can be chlorinated or brominated without using a special catalyst by a method for producing a fluorinated aromatic secondary amine compound which is reacted in the presence of a ligand and a base. Alternatively, a secondary amine compound having a fluoroaryl moiety in the molecule can be simply and efficiently produced by a coupling reaction with an iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon. (R1 independently represents an alkyl group having 1 to 20 carbon atoms, R2 to R5 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbons, and R6 to R8 are , Each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

Description

The present invention relates to a method for producing a fluorinated aromatic secondary amine compound.

Cross-coupling of an amine with a halide or pseudohalide using a palladium catalyst to form a C—N bond is useful for synthesizing an aromatic amine or forming a heterocycle. This cross-coupling has become an important technology in many fields such as the medical field and the material field (Non-Patent Document 1), and research on the catalyst used in this reaction and the reaction process has been widely conducted. ..

On the other hand, since fluorine has the highest electronegativity of all elements, not only the feature that it can change the electronic state of the whole molecule by introducing it into the molecule, but its atomic radius is Since they are about the same, even if a fluorine atom is introduced into the molecule instead of a hydrogen atom, it has a feature that the change in molecular size can be suppressed as compared with the case where another atom or a substituent is introduced. ..
Therefore, studies on fluorides have been actively conducted, and many reports on fluorides for medicines and electronic materials have been made. For example, in the field of electronic materials, it has been reported that an amine compound having a fluorine atom in the molecule is suitable as a charge transporting substance (Patent Document 1).

Under these circumstances, as a method for synthesizing a fluoroaryl compound having an amino group, a reaction between an aromatic amine and perfluoroarylboronic acid catalyzed by copper acetate (Non-Patent Document 2), in the presence of lithium hydroxide Of formanilide with perfluorobenzene (Non-Patent Document 3), reaction of aniline with perfluorobenzene in the presence of t-BuONa (Non-Patent Document 4), etc. have been reported. In each of the two raw materials used for the coupling reaction, the amino group, which is the reaction site, is present on the aromatic compound side having no fluorine atom.

There are few reports on the coupling reaction of a fluoroarylamine compound having a fluorine atom and an amino group with a haloaryl compound. For example, in Non-Patent Document 5, a special palladium carbene complex is used as a catalyst to give a fluoroarylamine compound. Although a method of coupling with a haloaryl compound has been reported, there are problems that the catalyst is expensive and the yield of the target product is low.

International Publication No. 2008/032617

Chem. Rev. 2016, 116, 12564-12649 Angew. Chem. Int. Ed. 2014, 53, 3223 Journal of Fluorine Chemistry, 74(2), 177-9; 1995 RSC Advances, 5(10), 7035-7048; 2015 Angew. Chem. Int. Ed. 2014, 53, 3223

The present invention has been made in view of the above circumstances, and a fluorinated aromatic amine compound, a chlorinated, brominated or iodinated aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon without using a special catalyst. An object of the present invention is to provide a method for easily and efficiently producing a secondary amine compound having a fluoroaryl moiety in the molecule by coupling with and.

The present inventor has conducted extensive studies to achieve the above object, and in the presence of a predetermined palladium catalyst, a predetermined ligand and a base, an amino group of a fluorinated aromatic amine compound and chlorination, Coupling reaction of brominated or iodinated aromatic hydrocarbons or pseudohalogenated aromatic hydrocarbons with chlorine atom, bromine atom, iodine atom or pseudohalogen group proceeds efficiently and has a fluoroaryl moiety in the molecule The present invention has been completed by finding that a secondary amine compound can be selectively obtained in high yield.

（式中、Ｒ¹は、それぞれ独立して、炭素数１〜２０のアルキル基または炭素数６〜２０のアリール基を表し、Ｒ²〜Ｒ⁵は、それぞれ独立して、水素原子、炭素数１〜２０のアルキル基または炭素数１〜２０のアルコキシ基を表し、Ｒ⁶〜Ｒ⁸は、それぞれ独立して、水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、またはＮＲ⁹ ₂基を表し、Ｒ⁹は、それぞれ独立して、炭素数１〜２０のアルキル基を表す。）
２． 前記触媒が、ジベンジリデンアセトンのパラジウム０価錯体であり、前記配位子が、前記式（Ｌ）で表されるビフェニルホスフィン化合物である１のフッ化芳香族第二級アミン化合物の製造方法、
３． 前記Ｒ¹が、それぞれ独立して、リン原子と結合する炭素原子が第２級または第３級炭素原子である炭素数３〜２０の分岐鎖状アルキル基または環状アルキル基である１または２のフッ化芳香族第二級アミンの製造方法、
４． 前記Ｒ¹が、ともにシクロヘキシル基またはｔ−ブチル基である３のフッ化芳香族第二級アミンの製造方法、
５． 前記Ｒ²およびＲ⁵が、それぞれ独立して、水素原子または炭素数１〜５のアルコキシ基を表し、前記Ｒ³およびＲ⁴が、ともに水素原子であり、前記Ｒ⁶〜Ｒ⁸が、それぞれ独立して、水素原子、炭素数１〜５のアルキル基、または炭素数１〜５のアルコキシ基を表す１〜４のいずれかのフッ化芳香族第二級アミンの製造方法、
６． 前記式（Ｌ）で表されるビフェニルホスフィン化合物が、下記式（Ｌ１）〜（Ｌ４）のいずれかで表されるビフェニルホスフィン化合物である１〜５のいずれかのフッ化芳香族第二級アミンの製造方法、

（式中、Ｍｅはメチル基を、ｉ−Ｐｒはイソプロピル基を、Ｃｙはシクロヘキシル基を、ｔ−Ｂｕはｔ−ブチル基を意味する。）
７． 前記ジベンジリデンアセトンのパラジウム０価錯体が、ビス（ジベンジリデンアセトン）パラジウム（０）である１〜６のいずれかのフッ化芳香族第二級アミンの製造方法、
８． 前記フッ化芳香族第一級アミン化合物が、分子内にフッ素原子を２個以上有するフッ化芳香族第一級モノアミン化合物またはジアミン化合物である１〜７のいずれかのフッ化芳香族第二級アミンの製造方法、
９． 前記塩素化、臭素化もしくはヨウ素化芳香族炭化水素が、モノもしくはジクロロ芳香族炭化水素、モノもしくはジブロモ芳香族炭化水素、またはモノもしくはジヨード芳香族炭化水素である１〜８のいずれかのフッ化芳香族第二級アミンの製造方法、
１０． 式（Ｔ１）または（Ｔ２）で表される含フッ素アニリン誘導体（但し、下記式［１］〜［１３］で表される化合物を除く。）、

〔式中、Ｘ²¹¹は、式（Ａ０１−１）〜（Ａ０９）のいずれかで表される２価の基を表し、

（式中、Ｌ⁰¹は、−Ｓ−、−Ｏ−、−ＣＯ−、−ＣＨ₂−、−（ＣＨ₂）₂−、−Ｃ（ＣＨ₃）₂−、−ＣＦ₂−、−（ＣＦ₂）₂−、−Ｃ（ＣＦ₃）₂−、フルオレン−９，９−ジイル基、−ＮＨ−または−ＮＺ¹⁰−を表し、
Ｌ⁰²およびＬ⁰³は、それぞれ独立して、水素原子、Ｚ¹¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹¹で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｌ⁰⁴は、水素原子、Ｚ¹¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹¹で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ′は、芳香環の置換基を表し、それぞれ独立して、Ｚ¹¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹¹で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ⁰¹〜Ｚ⁰⁹は、芳香環の置換基を表し、それぞれ独立して、塩素原子、臭素原子、ニトロ基、シアノ基、Ｚ¹¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹¹で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹⁰は、Ｚ¹¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹¹で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹¹は、それぞれ独立して、フッ素原子、塩素原子、臭素原子、ニトロ基、シアノ基またはＺ¹³で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹²は、それぞれ独立して、フッ素原子、塩素原子、臭素原子、ニトロ基、シアノ基、Ｚ¹³で置換されていてもよい炭素数１〜２０のアルキル基またはＺ¹³で置換されていてもよい炭素数２〜２０のアルケニル基を表し、
Ｚ¹³は、フッ素原子、塩素原子、臭素原子、ニトロ基またはシアノ基を表し、
a¹¹、a¹³、a²¹、a²³、a³¹、a³³、a⁴¹、a⁵¹、a⁶¹、a⁷¹、a⁷³、a⁸¹、a⁸³、a⁹¹およびa⁹³は、芳香環に置換するフッ素原子の数を表し、
a¹²、a¹⁴、a²²、a²⁴、a³²、a³⁴、a⁴²、a⁵²、a⁶²、a⁷²、a⁷⁴、a⁸²、a⁸⁴、a⁹²およびa⁹⁴は、芳香環に置換するＺ⁰¹〜Ｚ⁰⁹の数を表し、
a⁷⁵およびa⁷⁶は、芳香環に置換するＺ′の数を表し、
a¹¹は、２〜４の整数であり、a¹²は、０〜２の整数であり、かつ、a¹¹＋a¹²≦４を満たし、
a¹³は、２〜４の整数であり、a¹⁴は、０〜２の整数であり、かつ、a¹³＋a¹⁴≦４を満たし、
a²¹およびa²³は、それぞれ独立して１〜４の整数であり、a²²およびa²⁴は、それぞれ独立して０〜３の整数であり、かつ、a²¹＋a²²≦４およびa²³＋a²⁴≦４を満たし、
a³¹およびa³³は、それぞれ独立して１〜４の整数であり、a³²およびa³⁴は、それぞれ独立して０〜３の整数であり、かつ、a³¹＋a³²≦４およびa³³＋a³⁴≦４を満たし、
a⁴¹は、１〜６の整数であり、a⁴²は、０〜５の整数であり、かつ、a⁴¹＋a⁴²≦６を満たし、
a⁵¹は、１〜８の整数であり、a⁵²は、０〜７の整数であり、かつ、a⁵¹＋a⁵²≦８を満たし、
a⁶¹は、１〜８の整数であり、a⁶²は、０〜７の整数であり、かつ、a⁶¹＋a⁶²≦８を満たし、
a⁷¹およびa⁷³は、それぞれ独立して１〜３の整数であり、a⁷²およびa⁷⁴は、それぞれ独立して０〜２の整数であり、かつ、a⁷¹＋a⁷²≦３およびa⁷³＋a⁷⁴≦３を満たし、a⁷⁵およびa⁷⁶は、それぞれ独立して０〜４の整数であり、
a⁸¹およびa⁸³は、それぞれ独立して１〜３の整数であり、a⁸²およびa⁸⁴は、それぞれ独立して０〜２の整数であり、かつ、a⁸¹＋a⁸²≦３およびa⁸³＋a⁸⁴≦３を満たし、
a⁹¹およびa⁹³は、それぞれ独立して１〜３の整数であり、a⁹²およびa⁹⁴は、それぞれ独立して０〜２の整数であり、かつ、a⁹¹＋a⁹²≦３およびa⁹³＋a⁹⁴≦３を満たす。）
Ｙ²¹¹およびＹ²¹²は、それぞれ独立して、式（Ｂ０１）〜（Ｂ２１）のいずれかで表される１価の基を表し、

（式中、Ｌ¹¹は、−Ｓ−、−Ｏ−、−ＣＯ−、−ＣＨ₂−、−（ＣＨ₂）₂−、−Ｃ（ＣＨ₃）₂−、−ＣＦ₂−、−（ＣＦ₂）₂−、−Ｃ（ＣＦ₃）₂−、フルオレン−９，９−ジイル基、−ＮＨ−または−ＮＺ¹⁰⁰−を表し、
Ｌ¹²は、水素原子、Ｚ¹³⁰で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹³⁰で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹³¹で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｌ¹³およびＬ¹⁴は、それぞれ独立して、水素原子、Ｚ¹³⁰で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹³⁰で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹³¹で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹⁰⁰は、Ｚ¹³⁰で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹³⁰で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹³¹で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹⁰¹〜Ｚ¹⁰⁷およびＺ¹⁰⁹〜Ｚ¹²¹は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ニトロ基、シアノ基、Ｚ¹³⁰で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹³⁰で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹³¹で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹⁰⁸は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ニトロ基、シアノ基、Ｚ¹³⁰で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹³⁰で置換されていてもよい炭素数２〜２０のアルケニル基もしくはＺ¹³¹で置換されていてもよい炭素数６〜２０のアリール基を表すが、異なるベンゼン環上に存在するＺ¹⁰⁸同士が結合して環を形成していてもよく、
Ｚ¹³⁰は、それぞれ独立して、フッ素原子、塩素原子、臭素原子またはＺ¹³²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹³¹は、それぞれ独立して、フッ素原子、塩素原子、臭素原子、Ｚ¹³²で置換されていてもよい炭素数１〜２０のアルキル基またはＺ¹³²で置換されていてもよい炭素数２〜２０のアルケニル基を表し、
Ｚ¹³²は、フッ素原子、塩素原子または臭素原子を表し、
Ａｒ¹は、それぞれ独立して、炭素数６〜２０のアリール基を表し、
Ａｒ²は、単結合または炭素数６〜２０のアリーレン基を表す。）
Ｘ²²¹およびＸ²²²は、それぞれ独立して、式（Ｃ０１）〜（Ｃ０９）のいずれかで表される１価の基を表し、

（式中、b¹¹、b²¹、b²³、b³¹、b³³、b⁴¹、b⁵¹、b⁶¹、b⁷¹、b⁷³、b⁸¹、b⁸³、b⁹¹およびb⁹³は、芳香環に置換するフッ素原子の数を表し、
b¹²、b²²、b²⁴、b³²、b³⁴、b⁴²、b⁵²、b⁶²、b⁷²、b⁷⁴、b⁸²、b⁸⁴、b⁹²およびb⁹⁴は、芳香環に置換するＺ⁰¹〜Ｚ⁰⁹の数を表し、
b⁷⁵およびb⁷⁶は、芳香環に置換するＺ′の数を表し、
b¹¹は、２〜５の整数であり、b¹²は、０〜３の整数であり、かつ、b¹¹＋b¹²≦５を満たし、
b²¹は、１〜４の整数であり、b²³は、１〜５の整数であり、b²²は、０〜３の整数であり、b²⁴は、０〜４の整数であり、かつ、b²¹＋b²²≦４およびb²³＋b²⁴≦５を満たし、
b³¹は、１〜４の整数であり、b³³は、１〜５の整数であり、ｂ³²は、０〜３の整数であり、ｂ³⁴は、０〜４の整数であり、かつ、ｂ³¹＋ｂ³²≦４およびｂ³³＋ｂ³⁴≦５を満たし、
b⁴¹は、１〜７の整数であり、b⁴²は、０〜６の整数であり、かつ、b⁴¹＋b⁴²≦７を満たし、
b⁵¹は、１〜９の整数であり、b⁵²は、０〜８の整数であり、かつ、b⁵¹＋b⁵²≦９を満たし、
b⁶¹は、１〜９の整数であり、b⁶²は、０〜８の整数であり、かつ、b⁶¹＋b⁶²≦９を満たし、
b⁷¹は、１〜３の整数であり、b⁷³は、１〜４の整数であり、b⁷²は、０〜２の整数であり、b⁷⁴は、０〜３の整数であり、かつ、b⁷¹＋b⁷²≦３およびb⁷³＋b⁷⁴≦４を満たし、b⁷⁵およびb⁷⁶は、それぞれ独立して、０〜４の整数であり、
b⁸¹は、１〜３の整数であり、b⁸³は、１〜４の整数であり、b⁸²は、０〜２の整数であり、b⁸⁴は、０〜３の整数であり、かつ、b⁸¹＋b⁸²≦３およびb⁸³＋b⁸⁴≦４を満たし、
b⁹¹は、１〜３の整数であり、b⁹³は、１〜４の整数であり、b⁹²は、０〜２の整数であり、b⁹⁴は、０〜３の整数であり、かつ、b⁹¹＋b⁹²≦３およびb⁹³＋b⁹⁴≦４を満たし、
Ｌ⁰¹〜Ｌ⁰⁴、Ｚ′およびＺ⁰¹〜Ｚ⁰⁷は、前記と同じ意味を表す。）
Ｙ²²¹は、式（Ｄ０１−１）〜（Ｄ２１）のいずれかで表される２価の基を表す。

（式中、Ａｒ³は、それぞれ独立して、炭素数６〜２０のアリーレン基を表し、Ｌ¹¹〜Ｌ¹⁴、Ｚ¹⁰¹〜Ｚ¹²¹、およびＡｒ¹は、前記と同じ意味を表す。）〕

１１． 前記Ｘ²¹¹が、前記式（Ａ０２）で表される２価の基である１０の含フッ素アニリン誘導体、
１２． 前記Ｘ²¹¹が、下記式（Ａ０２−１）で表される２価の基である１１の含フッ素アニリン誘導体、

（式中、a²¹〜a²⁴およびＺ⁰²は前記と同じ意味を表す。）
１３． 前記Ｙ²¹¹およびＹ²¹²が、同一の１価の基である１０〜１２のいずれかの含フッ素アニリン誘導体、
１４． 前記Ｙ²¹¹およびＹ²¹²が、ともに前記式（Ｂ０１）、（Ｂ０２）、（Ｂ０４）、（Ｂ０８）および（Ｂ１８）のいずれかで表される１価の基である１３の含フッ素アニリン誘導体、
１５． 前記Ｙ²²¹が、前記式（Ｄ０２）で表される２価の基である１０の含フッ素アニリン誘導体、
１６． 前記Ｙ²²¹が、下記式（Ｄ０２−１）で表される２価の基である１５の含フッ素アニリン誘導体、

１７． Ｘ²²¹およびＸ²²²が、同一の１価の基である１０、１５または１６の含フッ素アニリン誘導体、
１８． Ｘ²²¹およびＸ²²²が、ともに前記式（Ｃ０１）で表される１価の基である１７の含フッ素アニリン誘導体、
１９． 下記式（Ｐ１−２）で表される繰り返し単位を含む重合体、

〔式中、Ｘ²¹¹は、式（Ａ０１−１）〜（Ａ０９）のいずれかで表される２価の基を表し、

（式中、Ｌ⁰¹は、−Ｓ−、−Ｏ−、−ＣＯ−、−ＣＨ₂−、−（ＣＨ₂）₂−、−Ｃ（ＣＨ₃）₂−、−ＣＦ₂−、−（ＣＦ₂）₂−、−Ｃ（ＣＦ₃）₂−、フルオレン−９，９−ジイル基、−ＮＨ−または−ＮＺ¹⁰−を表し、
Ｌ⁰²およびＬ⁰³は、それぞれ独立して、水素原子、Ｚ¹¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹¹で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｌ⁰⁴は、水素原子、Ｚ¹¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹¹で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ′は、芳香環の置換基を表し、それぞれ独立して、Ｚ¹¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹¹で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ⁰¹〜Ｚ⁰⁹は、芳香環の置換基を表し、それぞれ独立して、塩素原子、臭素原子、ニトロ基、シアノ基、Ｚ¹¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹¹で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹⁰は、Ｚ¹¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹¹で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹¹は、それぞれ独立して、フッ素原子、塩素原子、臭素原子、ニトロ基、シアノ基またはＺ¹³で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹²は、それぞれ独立して、フッ素原子、塩素原子、臭素原子、ニトロ基、シアノ基、Ｚ¹³で置換されていてもよい炭素数１〜２０のアルキル基またはＺ¹³で置換されていてもよい炭素数２〜２０のアルケニル基を表し、
Ｚ¹³は、フッ素原子、塩素原子、臭素原子、ニトロ基またはシアノ基を表し、
a¹¹、a¹³、a²¹、a²³、a³¹、a³³、a⁴¹、a⁵¹、a⁶¹、a⁷¹、a⁷³、a⁸¹、a⁸³、a⁹¹およびa⁹³は、芳香環に置換するフッ素原子の数を表し、
a¹²、a¹⁴、a²²、a²⁴、a³²、a³⁴、a⁴²、a⁵²、a⁶²、a⁷²、a⁷⁴、a⁸²、a⁸⁴、a⁹²およびa⁹⁴は、芳香環に置換するＺ⁰¹〜Ｚ⁰⁹の数を表し、
a⁷⁵およびa⁷⁶は、芳香環に置換するＺ′の数を表し、
a¹¹は、２〜４の整数であり、a¹²は、０〜２の整数であり、かつ、a¹¹＋a¹²≦４を満たし、
a¹³は、２〜４の整数であり、a¹⁴は、０〜２の整数であり、かつ、a¹³＋a¹⁴≦４を満たし、
a²¹およびa²³は、それぞれ独立して１〜４の整数であり、a²²およびa²⁴は、それぞれ独立して０〜３の整数であり、かつ、a²¹＋a²²≦４およびa²³＋a²⁴≦４を満たし、
a³¹およびa³³は、それぞれ独立して１〜４の整数であり、a³²およびa³⁴は、それぞれ独立して０〜３の整数であり、かつ、a³¹＋a³²≦４およびa³³＋a³⁴≦４を満たし、
a⁴¹は、１〜６の整数であり、a⁴²は、０〜５の整数であり、かつ、a⁴¹＋a⁴²≦６を満たし、
a⁵¹は、１〜８の整数であり、a⁵²は、０〜７の整数であり、かつ、a⁵¹＋a⁵²≦８を満たし、
a⁶¹は、１〜８の整数であり、a⁶²は、０〜７の整数であり、かつ、a⁶¹＋a⁶²≦８を満たし、
a⁷¹およびa⁷³は、それぞれ独立して１〜３の整数であり、a⁷²およびa⁷⁴は、それぞれ独立して０〜２の整数であり、かつ、a⁷¹＋a⁷²≦３およびa⁷³＋a⁷⁴≦３を満たし、a⁷⁵およびa⁷⁶は、それぞれ独立して０〜４の整数であり、
a⁸¹およびa⁸³は、それぞれ独立して１〜３の整数であり、a⁸²およびa⁸⁴は、それぞれ独立して０〜２の整数であり、かつ、a⁸¹＋a⁸²≦３およびa⁸³＋a⁸⁴≦３を満たし、
a⁹¹およびa⁹³は、それぞれ独立して１〜３の整数であり、a⁹²およびa⁹⁴は、それぞれ独立して０〜２の整数であり、かつ、a⁹¹＋a⁹²≦３およびa⁹³＋a⁹⁴≦３を満たす。）
Ｙ²²¹は、式（Ｄ０１−１）〜（Ｄ２１）のいずれかで表される２価の基を表す。

（式中、Ｌ¹¹は、−Ｓ−、−Ｏ−、−ＣＯ−、−ＣＨ₂−、−（ＣＨ₂）₂−、−Ｃ（ＣＨ₃）₂−、−ＣＦ₂−、−（ＣＦ₂）₂−、−Ｃ（ＣＦ₃）₂−、フルオレン−９，９−ジイル基、−ＮＨ―または−ＮＺ⁰²−を表し、
Ｌ¹²は、水素原子、Ｚ¹³⁰で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹³⁰で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹³¹で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｌ¹³およびＬ¹⁴は、それぞれ独立して、水素原子、Ｚ¹³⁰で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹³⁰で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹³¹で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹⁰¹〜Ｚ¹⁰⁷およびＺ¹⁰⁹〜Ｚ¹²¹は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ニトロ基、シアノ基、Ｚ¹³⁰で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹³⁰で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ¹³¹で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹⁰⁸は、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ニトロ基、シアノ基、Ｚ¹³⁰で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹³⁰で置換されていてもよい炭素数２〜２０のアルケニル基もしくはＺ¹³¹で置換されていてもよい炭素数６〜２０のアリール基を表すが、異なるベンゼン環上に存在するＺ¹⁰⁸同士が結合して環を形成していてもよく、
Ｚ¹³⁰は、それぞれ独立して、フッ素原子、塩素原子、臭素原子またはＺ¹³²で置換されていてもよい炭素数６〜２０のアリール基を表し、
Ｚ¹³¹は、それぞれ独立して、フッ素原子、塩素原子、臭素原子、Ｚ¹³²で置換されていてもよい炭素数１〜２０のアルキル基またはＺ¹³²で置換されていてもよい炭素数２〜２０のアルケニル基を表し、
Ｚ¹³²は、フッ素原子、塩素原子または臭素原子を表し、
Ａｒ¹は、それぞれ独立して、炭素数６〜２０のアリール基を表し、
Ａｒ³は、それぞれ独立して、炭素数６〜２０のアリーレン基を表す。）〕
２０． 前記Ｘ²¹¹が、前記式（Ａ０２）で表される２価の基である１９の重合体、
２１． 前記Ｘ²¹¹が、下記式（Ａ０２−１）で表される２価の基である２０の重合体、

（式中、a²¹〜a²⁴およびＺ⁰²は前記と同じ意味を表す。）
２２． 前記Ｙ²²¹が、前記式（Ｄ０２）、（Ｄ１７）および（Ｄ１９）のいずれかで表される２価の基である１９〜２１のいずれかの重合体、
２３． １０〜１８のいずれかのアニリン誘導体からなる電荷輸送性物質、
２４． １９〜２２のいずれかの重合体からなる電荷輸送性物質、
２５． ２３または２４の電荷輸送性物質と、有機溶媒とを含む電荷輸送性組成物、
２６． ドーパント物質を含む２５の電荷輸送性組成物、
２７． ２５または２６の電荷輸送性組成物から得られる電荷輸送性薄膜、
２８． ２７の電荷輸送性薄膜を備える電子素子、
２９． ２７の電荷輸送性薄膜を備える有機エレクトロルミネッセンス素子、
３０． 前記電荷輸送性薄膜が、正孔注入層または正孔輸送層である２９の有機エレクトロルミネッセンス素子
を提供する。That is, the present invention is
1. 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. A method for producing a fluorinated aromatic secondary amine compound, wherein the catalyst comprises a palladium zero-valent complex of dibenzylideneacetone, and the ligand is a biphenylphosphine compound represented by the following formula (L). A method for producing a fluorinated aromatic secondary amine compound, which comprises:

(In the formula, each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ^{2 to} R ⁵ each independently represent a hydrogen atom or a carbon number. Represents an alkyl group having 1 to 20 or an alkoxy group having 1 to 20 carbon atoms, and R ^{6 to} R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. , or an NR ⁹ ₂ group, R ⁹ each independently represent an alkyl group having 1 to 20 carbon atoms.)
2. The catalyst is a palladium zero-valent complex of dibenzylideneacetone, and the ligand is a biphenylphosphine compound represented by the formula (L).
3. ¹ or 2 wherein each R ¹ is independently a branched chain alkyl group having 3 to 20 carbon atoms or a cyclic alkyl group in which the carbon atom bonded to the phosphorus atom is a secondary or tertiary carbon atom; A method for producing a fluorinated aromatic secondary amine,
4. The method for producing a fluorinated aromatic secondary amine of 3, wherein R ¹ is both a cyclohexyl group or a t-butyl group,
5. R ² and R ⁵ each independently represent a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, R ³ and R ⁴ are both hydrogen atoms, and R ^{6 to} R ⁸ are respectively Independently, a method for producing a fluorinated aromatic secondary amine of any one of 1 to 4, which represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms,
6. The biphenylphosphine compound represented by the formula (L) is a biphenylphosphine compound represented by any of the following formulas (L1) to (L4), and the fluorinated aromatic secondary amine according to any one of 1 to 5 Manufacturing method of

(In the formula, Me means a methyl group, i-Pr means an isopropyl group, Cy means a cyclohexyl group, and t-Bu means a t-butyl group.)
7. The method for producing a fluorinated aromatic secondary amine according to any one of 1 to 6, wherein the palladium zero-valent complex of dibenzylideneacetone is bis(dibenzylideneacetone)palladium(0),
8. The fluorinated aromatic primary amine compound is a fluorinated aromatic primary monoamine compound having two or more fluorine atoms in the molecule or a diamine compound, and the fluorinated aromatic secondary amine according to any one of 1 to 7 above. A method for producing an amine,
9. Fluorination of any one of 1 to 8 wherein the chlorinated, brominated or iodinated aromatic hydrocarbon is a mono or dichloro aromatic hydrocarbon, a mono or dibromo aromatic hydrocarbon, or a mono or diiodo aromatic hydrocarbon. A method for producing an aromatic secondary amine,
10. A fluorine-containing aniline derivative represented by the formula (T1) or (T2) (however, the compounds represented by the following formulas [1] to [13] are excluded):

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

(In the formula, L ⁰¹ is —S—, —O—, —CO—, —CH ₂ —, —(CH ₂ ) ₂ —, —C(CH ₃ ) ₂ —, —CF ₂ —, —(CF _{2) 2 -, - C (} CF 3) 2 -, 9,9-diyl group, -NH- or -NZ ¹⁰ - represents,
L ⁰² and L ⁰³ are each independently hydrogen atom, Z ¹¹ alkyl group carbon atoms which may be have 1 to 20 substituents, alkenyl group optionally having 2 to 20 carbon atoms optionally substituted by Z ¹¹ Or represents an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² .
L ⁰⁴ represents a hydrogen atom, optionally substituted alkenyl group or Z ¹² alkyl group, optionally 2 to 20 carbon atoms optionally substituted by Z ¹¹ of carbon atoms which may be have 1-20 substituted with Z ¹¹ Represents an aryl group having 6 to 20 carbon atoms,
Z 'represents a substituent of the aromatic ring, each independently, an alkyl group having carbon atoms which may be have 1-20 replaced by Z ^11, Z ¹¹ which may be 2-20 carbons substituted with Represents an alkenyl group or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² .
Z ^{01 to} Z ⁰⁹ represent a substituent of an aromatic ring, and each independently represent a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹¹ , Represents an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z ¹¹ or an aryl group having 6 to 20 carbon atoms which may be substituted by Z ¹² .
Z ¹⁰ represents an alkyl group having carbon atoms which may be have 1-20 replaced by Z ^11, which may be substituted with alkenyl or Z ¹² good 2 to 20 carbon atoms optionally substituted by Z ¹¹ carbon Represents an aryl group of the number 6 to 20,
Z ^11's each independently represent a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³ .
Z ¹² are each independently a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, optionally substituted with an alkyl group or Z ¹³ of carbon atoms which may be have 1-20 substituted with Z ¹³ Represents a good alkenyl group 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,
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 are substituted with an aromatic ring. Represents the number of fluorine atoms
a ¹² , a ¹⁴ , a ²² , a ²⁴ , a ³² , a ³⁴ , a ⁴² , a ⁵² , a ⁶² , a ⁷² , a ⁷⁴ , a ⁸² , a ⁸⁴ , a ⁹² and a ⁹⁴ are substituted with an aromatic ring. Represents the number of Z ^{01 to} Z ⁰⁹
a ⁷⁵ and a ⁷⁶ represent the number of Z′ substituting the aromatic ring,
a ¹¹ is an integer of 2 to 4, a ¹² is an integer of 0 to 2 and satisfies a ¹¹ +a ¹² ≦4,
a ¹³ is an integer of 2 to 4, a ¹⁴ is an integer of 0 to 2 and satisfies a ¹³ +a ¹⁴ ≦4,
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 Satisfies ²⁴ ≤ 4,
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. Satisfies ³⁴ ≤ 4,
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,
a ⁵¹ is an integer of 1 to 8, a ⁵² is an integer of 0 to 7 and a ⁵¹ +a ⁵² ≦8 is satisfied,
a ⁶¹ is an integer of 1 to 8, a ⁶² is an integer of 0 to 7 and a ⁶¹ +a ⁶² ≦8 is satisfied,
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 a ⁷¹ +a ⁷² ≦3 and a ⁷³ +a ⁷⁴ ≦3 is satisfied, and a ⁷⁵ and a ⁷⁶ are each independently an integer of 0 to 4,
a ⁸¹ and a ⁸³ are each independently an integer of 1 to 3, a ⁸² and a ⁸⁴ are each independently an integer of 0 to 2, and a ⁸¹ +a ⁸² ≦3 and a ⁸³ +a ^{Satisfying 84} ≦3,
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 a ⁹¹ +a ⁹² ≦3 and a ⁹³ +a ⁹⁴ ≦3 is satisfied. )
Y ²¹¹ and Y ²¹² each independently represent a monovalent group represented by any of formulas (B01) to (B21),

(In the formula, L ¹¹ is —S—, —O—, —CO—, —CH ₂ —, —(CH ₂ ) ₂ —, —C(CH ₃ ) ₂ —, —CF ₂ —, —(CF _{2) 2 -, - C (} CF 3) 2 -, 9,9-diyl group, -NH- or -NZ ¹⁰⁰ - represents,
L ¹² represents a hydrogen atom, optionally substituted alkenyl group or Z ¹³¹ of is an alkyl group having 1 to 20 carbon atoms also be good 2-20 carbon atoms substituted with Z ¹³⁰ substituted with Z ¹³⁰ Represents an aryl group having 6 to 20 carbon atoms,
L ¹³ and L ¹⁴ are each independently a hydrogen atom, Z ¹³⁰ with an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ¹³⁰ Or represents an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³¹ ,
Z ¹⁰⁰ represents an alkyl group with carbon atoms which may have 1 to 20 substituted by Z ^130, which may be substituted with alkenyl or Z ¹³¹ good 2 to 20 carbon atoms optionally substituted by Z ¹³⁰ carbon Represents an aryl group of the number 6 to 20,
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, or a C 1-20 optionally substituted with Z ^130. Represents an alkyl group having 2 to 20 carbon atoms, which may be substituted with Z ¹³⁰ , or an aryl group having 6 to 20 carbon atoms, which may be substituted with Z ¹³¹ .
Z ¹⁰⁸ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having carbon atoms which may be have 1-20 substituted with Z ^130, is substituted with Z ¹³⁰ Represents an alkenyl group having 2 to 20 carbon atoms which may be present or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³¹ , and Z ¹⁰⁸ existing on different benzene rings are bonded to each other to form a ring. May be formed,
Z ^{130 s} each independently represent a fluorine atom, a chlorine atom, a bromine atom or an aryl group having 6 to 20 carbon atoms, which may be substituted with Z ¹³² .
Z ¹³¹ are each independently a fluorine atom, a chlorine atom, a bromine atom, an alkyl group or Z ¹³² carbon atoms which may be have 2-20 substituted with 1 to 20 carbon atoms which may be substituted with Z ¹³² Represents an alkenyl group of
Z ¹³² represents a fluorine atom, a chlorine atom or a bromine atom,
Ar ^1's each independently represent an aryl group having 6 to 20 carbon atoms,
Ar ² represents a single bond or an arylene group having 6 to 20 carbon atoms. )
X ²²¹ and X ²²² each independently represent a monovalent group represented by any of formulas (C01) to (C09),

(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 are aromatic rings. Represents the number of fluorine atoms to be substituted,
b ¹² , b ²² , b ²⁴ , b ³² , b ³⁴ , b ⁴² , b ⁵² , b ⁶² , b ⁷² , b ⁷⁴ , b ⁸² , b ⁸⁴ , b ⁹² and b ⁹⁴ are substituted with an aromatic ring Z ⁰¹ ~ Represents the number of Z ⁰⁹ ,
b ⁷⁵ and b ⁷⁶ represent the number of Z′ substituting the aromatic ring,
b ¹¹ is an integer of 2 to 5, b ¹² is an integer of 0 to 3 and satisfies b ¹¹ +b ¹² ≦5,
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 satisfying b ²¹ +b ²² ≦4 and b ²³ +b ²⁴ ≦5,
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 are satisfied,
b ⁴¹ is an integer of 1 to 7, b ⁴² is an integer of 0 to 6, and b ⁴¹ +b ⁴² ≦7 is satisfied,
b ⁵¹ is an integer of 1 to 9, b ⁵² is an integer of 0 to 8 and satisfies b ⁵¹ +b ⁵² ≦9,
b ⁶¹ is an integer of 1 to 9, b ⁶² is an integer of 0 to 8 and satisfies b ⁶¹ +b ⁶² ≦9,
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 are satisfied, and b ⁷⁵ and b ⁷⁶ are each independently an integer of 0 to 4,
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,
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 b ⁹¹ +b ⁹² ≤3 and b ⁹³ +b ⁹⁴ ≤4 are satisfied,
L ^{01 to} L ⁰⁴ , Z′ and Z ^{01 to} Z ⁰⁷ have the same meanings as described above. )
Y ²²¹ represents a divalent group represented by any of formulas (D01-1) to (D21).

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

11. Wherein X ²¹¹ is a fluorine-containing aniline derivative of 10, which is a divalent group represented by the formula (A02),
12. Wherein X ²¹¹ is a fluorine-containing aniline derivative of 11, which is a divalent group represented by the following formula (A02-1),

(In the formula, a ^{21 to} a ²⁴ and Z ⁰² have the same meanings as described above.)
13. Y ²¹¹ and Y ²¹² are fluorine-containing aniline derivatives according to any one of 10 to 12 in which the same monovalent groups are present.
14. 13. The fluorine-containing aniline derivative of 13, wherein Y ²¹¹ and Y ²¹² are each a monovalent group represented by any of the formulas (B01), (B02), (B04), (B08) and (B18),
15. The Y ²²¹ is a fluorine-containing aniline derivative of 10, which is a divalent group represented by the formula (D02),
16. Y ²²¹ is a divalent group represented by the following formula (D02-1), a fluorine-containing aniline derivative of 15;

17. X ²²¹ and X ²²² are 10, 15 or 16 fluorine-containing aniline derivatives, wherein X ²²¹ and X ²²² are the same monovalent group,
18. X ²²¹ and X ²²² are 17 fluorinated aniline derivatives, each of which is a monovalent group represented by the above formula (C01);
19. A polymer containing a repeating unit represented by the following formula (P1-2),

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

(In the formula, L ⁰¹ is —S—, —O—, —CO—, —CH ₂ —, —(CH ₂ ) ₂ —, —C(CH ₃ ) ₂ —, —CF ₂ —, —(CF _{2) 2 -, - C (} CF 3) 2 -, 9,9-diyl group, -NH- or -NZ ¹⁰ - represents,
L ⁰² and L ⁰³ are each independently hydrogen atom, Z ¹¹ alkyl group carbon atoms which may be have 1 to 20 substituents, alkenyl group optionally having 2 to 20 carbon atoms optionally substituted by Z ¹¹ Or represents an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² .
L ⁰⁴ represents a hydrogen atom, optionally substituted alkenyl group or Z ¹² alkyl group, optionally 2 to 20 carbon atoms optionally substituted by Z ¹¹ of carbon atoms which may be have 1-20 substituted with Z ¹¹ Represents an aryl group having 6 to 20 carbon atoms,
Z 'represents a substituent of the aromatic ring, each independently, an alkyl group having carbon atoms which may be have 1-20 replaced by Z ^11, Z ¹¹ which may be 2-20 carbons substituted with Represents an alkenyl group or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² .
Z ^{01 to} Z ⁰⁹ represent a substituent of an aromatic ring, and each independently represent a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹¹ , Represents an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z ¹¹ or an aryl group having 6 to 20 carbon atoms which may be substituted by Z ¹² .
Z ¹⁰ represents an alkyl group having carbon atoms which may be have 1-20 replaced by Z ^11, which may be substituted with alkenyl or Z ¹² good 2 to 20 carbon atoms optionally substituted by Z ¹¹ carbon Represents an aryl group of the number 6 to 20,
Z ^11's each independently represent a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³ .
Z ¹² are each independently a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, optionally substituted with an alkyl group or Z ¹³ of carbon atoms which may be have 1-20 substituted with Z ¹³ Represents a good alkenyl group 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,
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 are substituted with an aromatic ring. Represents the number of fluorine atoms
a ¹² , a ¹⁴ , a ²² , a ²⁴ , a ³² , a ³⁴ , a ⁴² , a ⁵² , a ⁶² , a ⁷² , a ⁷⁴ , a ⁸² , a ⁸⁴ , a ⁹² and a ⁹⁴ are substituted with an aromatic ring. Represents the number of Z ^{01 to} Z ⁰⁹
a ⁷⁵ and a ⁷⁶ represent the number of Z′ substituting the aromatic ring,
a ¹¹ is an integer of 2 to 4, a ¹² is an integer of 0 to 2 and satisfies a ¹¹ +a ¹² ≦4,
a ¹³ is an integer of 2 to 4, a ¹⁴ is an integer of 0 to 2 and satisfies a ¹³ +a ¹⁴ ≦4,
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 Satisfies ²⁴ ≤ 4,
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. Satisfies ³⁴ ≤ 4,
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,
a ⁵¹ is an integer of 1 to 8, a ⁵² is an integer of 0 to 7 and a ⁵¹ +a ⁵² ≦8 is satisfied,
a ⁶¹ is an integer of 1 to 8, a ⁶² is an integer of 0 to 7 and a ⁶¹ +a ⁶² ≦8 is satisfied,
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 a ⁷¹ +a ⁷² ≦3 and a ⁷³ +a ⁷⁴ ≦3 is satisfied, and a ⁷⁵ and a ⁷⁶ are each independently an integer of 0 to 4,
a ⁸¹ and a ⁸³ are each independently an integer of 1 to 3, a ⁸² and a ⁸⁴ are each independently an integer of 0 to 2, and a ⁸¹ +a ⁸² ≦3 and a ⁸³ +a ^{Satisfying 84} ≦3,
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 a ⁹¹ +a ⁹² ≦3 and a ⁹³ +a ⁹⁴ ≦3 is satisfied. )
Y ²²¹ represents a divalent group represented by any of formulas (D01-1) to (D21).

(In the formula, L ¹¹ is —S—, —O—, —CO—, —CH ₂ —, —(CH ₂ ) ₂ —, —C(CH ₃ ) ₂ —, —CF ₂ —, —(CF _{2) 2 -, - C (} CF 3) 2 -, 9,9-diyl group, -NH- or -NZ ⁰² - represents,
L ¹² represents a hydrogen atom, optionally substituted alkenyl group or Z ¹³¹ of is an alkyl group having 1 to 20 carbon atoms also be good 2-20 carbon atoms substituted with Z ¹³⁰ substituted with Z ¹³⁰ Represents an aryl group having 6 to 20 carbon atoms,
L ¹³ and L ¹⁴ are each independently a hydrogen atom, Z ¹³⁰ with an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ¹³⁰ Or represents an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³¹ ,
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, or a C 1-20 optionally substituted with Z ^130. Represents an alkyl group having 2 to 20 carbon atoms, which may be substituted with Z ¹³⁰ , or an aryl group having 6 to 20 carbon atoms, which may be substituted with Z ¹³¹ .
Z ¹⁰⁸ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having carbon atoms which may be have 1-20 substituted with Z ^130, is substituted with Z ¹³⁰ Represents an alkenyl group having 2 to 20 carbon atoms which may be present or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³¹ , and Z ¹⁰⁸ existing on different benzene rings are bonded to each other to form a ring. May be formed,
Z ^{130 s} each independently represent a fluorine atom, a chlorine atom, a bromine atom or an aryl group having 6 to 20 carbon atoms, which may be substituted with Z ¹³² .
Z ¹³¹ are each independently a fluorine atom, a chlorine atom, a bromine atom, an alkyl group or Z ¹³² carbon atoms which may be have 2-20 substituted with 1 to 20 carbon atoms which may be substituted with Z ¹³² Represents an alkenyl group of
Z ¹³² represents a fluorine atom, a chlorine atom or a bromine atom,
Ar ^1's each independently represent an aryl group having 6 to 20 carbon atoms,
Ar ^3's each independently represent an arylene group having 6 to 20 carbon atoms. )]
20. The polymer of 19 wherein X ²¹¹ is a divalent group represented by the formula (A02),
21. A polymer of 20, wherein X ²¹¹ is a divalent group represented by the following formula (A02-1),

(In the formula, a ^{21 to} a ²⁴ and Z ⁰² have the same meanings as described above.)
22. The polymer according to any one of 19 to 21, wherein Y ²²¹ is a divalent group represented by any of the formulas (D02), (D17) and (D19),
23. A charge-transporting substance consisting of the aniline derivative of any of 10 to 18,
24. A charge-transporting substance made of the polymer of any one of 19 to 22,
25. A charge-transporting composition containing 23 or 24 charge-transporting substances and an organic solvent,
26. 25 charge transporting compositions comprising a dopant material,
27. A charge transporting thin film obtained from the charge transporting composition of 25 or 26,
28. An electronic device comprising 27 charge transporting thin films,
29. 27. An organic electroluminescent device comprising 27 charge transporting thin films,
30. 29. The organic electroluminescent device according to 29, wherein the charge transporting thin film is a hole injecting layer or a hole transporting layer.

According to the method for producing a fluorinated aromatic secondary amine compound of the present invention, a fluorinated aromatic amine compound is chlorinated, brominated or iodinated using a commercially available palladium catalyst and a ligand having a biphenyl skeleton. A secondary amine compound (fluorine-containing aniline derivative) having a fluoroaryl moiety in the molecule can be efficiently and inexpensively produced from an aromatic hydrocarbon or a pseudohalogenated aromatic hydrocarbon at low cost. it can.
Further, in this reaction, the polymerization reaction proceeds by using a bifunctional compound for each of the fluorinated aromatic amine compound and the chlorinated, brominated or iodinated aromatic hydrocarbon or the pseudohalogenated aromatic hydrocarbon, A polymer such as an oligoaniline derivative or a polyaniline derivative having a fluoroaryl moiety in the molecule can be efficiently produced.
The fluorine-containing aniline derivative obtained by the production method of the present invention, the fluorine-containing amine compound such as a polymer is excellent in transparency because it has a fluorine atom in the molecule, and also exhibits charge transportability. It can be suitably used as a material for forming a charge-transporting thin film for an electronic element such as an organic EL element, alone or in combination with another charge-transporting material or a dopant substance.

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

(1) Catalyst The catalyst used in the present invention contains a palladium zero-valent complex of dibenzylideneacetone.
Specific examples of the palladium zero-valent complex of dibenzylideneacetone include bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), tris(dibenzylideneacetone)(chloroform)dipalladium(0). ) And the like, and of these, bis(dibenzylideneacetone)palladium(0) is preferable.
The amount of the palladium zero-valent complex of dibenzylideneacetone used is not particularly limited as long as the desired coupling reaction proceeds, but the amount of palladium is based on 1 mol of NH at the amine moiety of the fluorinated aromatic primary amine compound. The metal is preferably 0.0001 to 0.2 mol, more preferably 0.005 to 0.15 mol, even more preferably 0.01 to 0.12 mol, and further preferably 0.02 to 0.1 mol.

Further, in the present invention, other metal catalysts may be used together with the palladium zero-valent complex of dibenzylideneacetone within a range that does not impair the effects of the present invention.
Examples of other metal catalysts include copper catalysts such as copper chloride, copper bromide, and copper iodide; Pd(PPh ₃ ) ₄ (tetrakis(triphenylphosphine)palladium), Pd(PPh ₃ ) ₂ Cl ₂ (bis (triphenylphosphine) dichloropalladium), Pd (P-t- Bu 3) 2 ( bis (tri (t-butylphosphine)) palladium), and the like palladium catalysts such as Pd (OAc) ₂ (palladium acetate) ..
When these other metal catalysts are used, the amount thereof is not generally specified, but it is usually less than 100 mol% based on the palladium zero-valent complex of dibenzylideneacetone.

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

In formula (L), R ^1's each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ^{2 to} R ⁵ are each independently a hydrogen atom, Represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and R ^{6 to} R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. an alkoxy group, or NR ⁹ ₂ group,, R ⁹ each independently represent an alkyl group having 1 to 20 carbon atoms.

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

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

Among these, R ¹ is preferably a relatively bulky group independently from the viewpoint of obtaining the target product with good reproducibility, and the carbon atom having a bond is a secondary carbon atom or a tertiary carbon atom. A branched chain alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms are preferable, and the carbon number is more preferable from the viewpoint of solubility and stability in a solvent. A branched alkyl group having 3 to 5 and a cyclic alkyl group having 5 to 7 carbon atoms are more preferable, and a t-butyl group and a cyclohexyl group are even more preferable.
In addition, it is preferable that two R ¹ are the same from the viewpoint of easiness of synthesis.

Further, from the viewpoint of stability of the compound and obtaining the target product with good reproducibility, R ^{2 to} R ⁵ are each independently preferably a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, and R ² and R ⁵ Are each independently a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, R ³ and R ⁴ are more preferably a combination of hydrogen atoms, and R ^{2 to} R ⁵ are all more preferably hydrogen atoms.

Further, from the viewpoint of stability of the compound and obtaining the target compound with good reproducibility, R ^{6 to} R ⁸ are each a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, or a carbon atom having a bond. A branched chain alkyl group having 3 to 20 carbon atoms, which is a primary carbon atom or a secondary carbon atom, and an alkoxy group having 1 to 20 carbon atoms are preferable. Further, from the viewpoint of solubility and stability in a solvent, a hydrogen atom or a carbon atom. A straight chain alkyl group having 1 to 5 carbon atoms, a branched chain alkyl group having 3 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms are more preferable, and a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, A methoxy group and an isopropoxy group are even more preferable.

Particularly, as R ⁶ and R ⁸ , a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms is preferable, and a hydrogen atom, a methyl group, an isopropyl group, a methoxy group or an isopropoxy group is preferable. More preferable.
R ⁷ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an isopropyl group.

Examples of the ligand preferably used in the present invention include those represented by the following formulas (L1) to (L7), but the ligands are not limited thereto.

（式中、Ｍｅはメチル基を、ｉ−Ｐｒはイソプロピル基を、ｔ−Ｂｕはｔ−ブチル基を、Ｃｙはシクロヘキシル基を意味する。）

(In the formula, Me means a methyl group, i-Pr means an isopropyl group, t-Bu means a t-butyl group, and Cy means a cyclohexyl group.)

The ligand represented by the above formula (L) is available as a commercial product, and is commercially available, for example, as a Buchwald ligand or the like from Aldrich, JohnPhos, CyjohnPhos, DavePhos, XPhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, tBuDavePhos, PhDavePhos, 2'-Dicyclohexylphosphino-2,4,6-trimethoxybiphenyl, BrettPhos, tBuBrettPhos, AdBrettPhos, Me ₃ (OMe)tBuXPhos, (2-Biphenyl)phine-manemanada Etc.
The ligand represented by the above formula (L) can also be synthesized by a known method.

The amount of the ligand represented by the formula (L) used is preferably 1 to 2 equivalents with respect to the catalyst used. Particularly, when the amount is less than 1 equivalent, palladium black may occur.

In the present invention, other ligands may be used together with the ligand represented by the formula (L) as long as the effects of the present invention are not impaired.
Specific examples of other coordination positions include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine, di-t-butyl. (Phenyl)phosphine, di-t-butyl(4-dimethylaminophenyl)phosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenyl) Examples include tertiary phosphines such as phosphino)butane and 1,1′-bis(diphenylphosphino)ferrocene, and tertiary phosphites such as trimethylphosphite, triethylphosphite, and triphenylphosphite.
When other ligands are used, their use amount cannot be unconditionally specified, but it is usually less than 100 mol% with respect to the ligand represented by the formula (L).

(3) Fluorinated aromatic primary amine compound Since the production method of the present invention is characterized by the above-mentioned catalyst and ligand, a fluorinated aromatic primary amine that is a raw material to be subjected to the coupling reaction. There is no particular limitation on the compound.
The fluorinated aromatic primary amine compound may be a monoamine compound or a diamine compound, and examples thereof include those represented by the following formulas (X1) and (X2).

（式中、Ａｒ^F1は、フッ化アリール基を表し、Ａｒ^F2は、フッ化アリーレン基を表す。）

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

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

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group; 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2 -Fused ring aromatics such as phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl, 5-naphthacenyl, 2-chrysenyl, 1-pyrenyl, 2-pyrenyl, pentacenyl, benzopyrenyl, triphenylenyl groups A group derived by removing one hydrogen atom on the aromatic ring of a group hydrocarbon compound; biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, paraterphenyl-4-yl, metaterphenyl -4-yl, orthoterphenyl-4-yl, 1,1'-binaphthyl-2-yl, 2,2'-binaphthyl-1-yl group and the like, the hydrogen atom on the aromatic ring of the ring-linked hydrocarbon compound is Examples include groups that are derived by removing one.
The arylene group is preferably an arylene group having 6 to 20 carbon atoms, and specific examples thereof include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene group; 1,5-naphthalenediyl, 1, 8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6 -Anthracene diyl, 1,7-anthracene diyl, 1,8-anthracene diyl, 2,3-anthracene diyl, 2,6-anthracene diyl, 2,7-anthracene diyl, 2,9-anthracene diyl, 2,10- A group derived by removing two hydrogen atoms on the aromatic ring of a condensed ring aromatic hydrocarbon compound such as anthracenediyl or 9,10-anthracenediyl group; biphenyl-4,4′-diyl group, paraterphenyl- Examples thereof include groups derived by removing two hydrogen atoms on the aromatic ring of a ring-linked hydrocarbon compound such as a 4,4″-diyl group group.

(4) Chlorinated, brominated or iodinated aromatic hydrocarbons or pseudohalogenated aromatic hydrocarbons As chlorinated, brominated or iodinated aromatic hydrocarbons or pseudohalogenated aromatic hydrocarbons, monochloro, monobromo or Even compounds having one reactive site which reacts with the amino group of a fluorinated aromatic primary amine, such as monoiodo or mono-pseudohalogen compounds, such as dichloro, dibromo or diiodo or dipseudohalogen compounds, It may be a compound having two or more reaction sites that react with an amino group of a fluorinated aromatic primary amine, and examples thereof include those represented by the following formulas (Y1) and (Y2).

（式中、Ａｒ⁴は、アリール基を表し、Ａｒ⁵は、アリーレン基を表し、Ｘは、それぞれ独立して、塩素原子、臭素原子、ヨウ素原子または擬ハロゲン基を表す。）

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

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

In particular, the chlorinated, brominated or iodinated aromatic hydrocarbons or pseudohalogenated aromatic hydrocarbons used in the present invention are mono or dichloro aromatic hydrocarbons, mono or dibromo aromatic hydrocarbons, or mono or diiodo aromatics. Hydrocarbons are preferred, with mono or dibromo aromatic hydrocarbons, or mono or diiodo aromatic hydrocarbons being more preferred.

(5) Base The base is not particularly limited, and examples thereof include lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium and t. -Alkali metal simple substance such as potassium butoxy, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, alkali metal hydride, alkali metal hydroxide, alkoxy alkali metal, alkali metal carbonate, carbonic acid Alkali hydrogen metal; alkaline earth metal carbonate such as calcium carbonate; n-butyllithium, s-butyllithium, t-butyllithium, lithium diisopropylamide (LDA), lithium 2,2,6,6-tetramethylpiperidine (LiTMP) ), organic lithium such as lithium hexamethyldisilazane (LHMDS); amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, pyridine, etc., but secondary amines such as LDA, LiTMP, LHMDS are lithio. A modified lithium amide reagent or an alkoxyalkali metal such as t-butoxylithium is suitable.

(6) Coupling Reaction In the production method of the present invention, the charging ratio of the fluorinated aromatic primary amine compound to the chlorinated, brominated or iodinated aromatic hydrocarbon or the pseudohalogenated aromatic hydrocarbon is A reaction site of about 1.0 to 1.2 mol which is chlorine, bromine or iodine of an aromatic hydrocarbon or pseudohalogen is suitable for 1 mol of NH ₂ group of a fluorinated aromatic primary amine compound.
For example, in the reaction between the formula (X1) and the formula (Y1) in terms of the amount of substance (mol), about (Y1)1 to 1.2 is preferable with respect to (X1)1. In the reaction with (Y2), (Y1) is preferably about 0.5 to 0.6 with respect to (X1)1, and in the reaction between formula (X2) and formula (Y1), (X2)1. To (Y1) 2 to 2.4 are suitable, and in the reaction of the formulas (X2) and (Y2), (Y2) 1 to 1.2 are suitable for (X2) 1. is there.

The coupling reaction of the present invention is carried out in a solvent when all the raw material compounds are solid or from the viewpoint of efficiently obtaining the desired fluorinated aromatic secondary amine compound.
When a solvent is used, its type is not particularly limited as long as it does not adversely affect the reaction. Specific examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic Group 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.), urea (N,N-dimethylimidazolidinone, tetramethylurea, etc.), sulfoxides (dimethyl sulfoxide, sulfolane, etc.), nitrites (acetonitrile, propionitrile, butyronitrile, etc.), etc., and these solvents are used alone. They may be used, or two or more kinds may be mixed and used.
In particular, in the present invention, it is preferable to use ethers as the solvent, and it is more preferable to use dioxane.

The lower limit of the reaction temperature cannot be unconditionally specified because it depends on the reactivity of the reaction substrate and the like, but if it is 45° C. or higher, the coupling reaction normally proceeds well. In particular, in consideration of further improving the reactivity, the reaction temperature is preferably 60° C. or higher, more preferably 75° C. or higher, even more preferably 90° C. or higher, and it is particularly preferable to carry out the reaction under heating reflux of the solvent. It is suitable. On the other hand, the upper limit of the reaction temperature cannot be unconditionally specified because it depends on the boiling point of the solvent used, but it is usually about 200° C. or lower.
After completion of the reaction, post-treatment is carried out by a conventional method to obtain the desired fluorinated aromatic secondary amine compound.

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

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

Here, L ⁰¹ is, -S -, - O -, - CO -, - CH 2 -, - (CH 2) 2 -, - C (CH 3) 2 -, - CF 2 -, - (CF 2 _{) 2 -, - C (CF} 3) 2 -, 9,9-diyl group, -NH- or -NZ ¹⁰ - represents a.
L ⁰² and L ⁰³ are each independently hydrogen atom, Z ¹¹ alkyl group carbon atoms which may be have 1 to 20 substituents, alkenyl group optionally having 2 to 20 carbon atoms optionally substituted by Z ¹¹ Or, it represents an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² , and a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an aryl group having 6 to 20 carbon atoms are preferable, and both are a hydrogen atom and methyl. A group and a phenyl group are more preferable.
Specific examples of the alkyl group and aryl group include the same ones as described above.
Specific examples of the alkenyl group having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, n- Examples thereof include a 1-eicosenyl group.

L ⁰⁴ represents a hydrogen atom, optionally substituted alkenyl group or Z ¹² alkyl group, optionally 2 to 20 carbon atoms optionally substituted by Z ¹¹ of carbon atoms which may be have 1-20 substituted with Z ¹¹ And the aryl group having 6 to 20 carbon atoms is preferable, and specific examples of these alkyl group, alkenyl group and aryl group include the same ones as described above. Among these, L ⁰⁴ is preferably a hydrogen atom or a phenyl group.
Z 'represents a substituent of the aromatic ring, each independently, an alkyl group having carbon atoms which may be have 1-20 replaced by Z ^11, Z ¹¹ which may be 2-20 carbons substituted with The alkenyl group or the aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² is represented, and specific examples of these alkyl group, alkenyl group and aryl group include the same ones as described above.

Z ^{01 to} Z ⁰⁹ represent a substituent of an aromatic ring, each independently a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹¹ , Represents an alkenyl group having 2 to 20 carbon atoms which may be substituted with Z ¹¹ or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² , wherein Z ¹⁰ may be substituted with Z ^11. an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or Z ¹² in the 6 to 20 carbon atoms which may be substituted aryl group which may C2-20 optionally substituted by Z ^11, Z ¹¹ Each independently represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³ , and Z ¹² is each independently , a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, alkenyl group or Z ¹³ good 2-20 carbon atoms which may be substituted with the carbon atoms which may be have 1-20 substituted with Z ¹³ Represents a group, Z ¹³ represents a fluorine atom, a chlorine atom, a bromine atom, a nitro group or a cyano group, and specific examples of these alkyl group, alkenyl group and aryl group include the same ones as described above.
Among them, when Z ^{01 to} Z ⁰⁹ are present, a nitro group and an alkyl group having 1 to 5 carbon atoms which may be substituted with a fluorine atom are preferable. Further, Z ¹⁰ is preferably a phenyl group which may be substituted with a fluorine atom.
When there are a plurality of aromatic ring substituents Z ^p (p=′, 01 to 09), they may be the same or different.

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 are substituted with an aromatic ring. Represents the number of fluorine atoms, a ¹² , a ¹⁴ , a ²² , a ²⁴ , a ³² , a ³⁴ , a ⁴² , a ⁵² , a ⁶² , a ⁷² , a ⁷⁴ , a ⁸² , a ⁸⁴ , a ⁹² and a ⁹⁴ represents the number of Z ^{01 to} Z ⁰⁹ substituted on the aromatic ring, and a ⁷⁵ and a ⁷⁶ represent the number of Z′ substituted on the aromatic ring.
a ¹¹ is an integer of 2 to 4, a ¹² is an integer of 0 to 2 and satisfies a ¹¹ +a ¹² ≦4.
a ¹³ is an integer of 2 to 4, a ¹⁴ is an integer of 0 to 2 and satisfies a ¹³ +a ¹⁴ ≦4.
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 is satisfied.
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 is satisfied.
a ⁴¹ is an integer of 1 to 6, a ⁴² is an integer of 0 to 5 and satisfies a ⁴¹ +a ⁴² ≦6.
a ⁵¹ is an integer of 1 to 8, a ⁵² is an integer of 0 to 7, and a ⁵¹ +a ⁵² ≦8 is satisfied.
a ⁶¹ is an integer of 1 to 8, a ⁶² is an integer of 0 to 7, and a ⁶¹ +a ⁶² ≦8 is satisfied.
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 a ⁷¹ +a ⁷² ≦3 and a ⁷³ +a ⁷⁴ ≦3 is satisfied, and a ⁷⁵ and a ⁷⁶ are each independently an integer of 0 to 4.
a ⁸¹ and a ⁸³ are each independently an integer of 1 to 3, a ⁸² and a ⁸⁴ are each independently an integer of 0 to 2, and a ⁸¹ +a ⁸² ≦3 and a ⁸³ +a ^It satisfies ⁸⁴ ≦3.
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 a ⁹¹ +a ⁹² ≦3 and a ⁹³ +a ⁹⁴ ≦3 is satisfied.
Particularly, a ⁴¹ , a ⁵¹ , and a ⁶¹ are preferably integers of 2 or more.
Also, a ¹² , a ¹⁴ , a ²² , a ²⁴ , a ³² , a ³⁴ , a ⁴² , a ⁵² , a ⁶² , a ⁷² , a ⁷⁴ , a ⁸² , a ⁸⁴ , a ⁹² and a ⁹⁴ are 0. Preferably, a ⁷⁵ and a ⁷⁶ are 0.

Among these, X ²¹¹ is preferably a divalent group represented by the formula (A02), more preferably a divalent group represented by the following formula (A02-1), and used as a charge transporting substance. Considering this, the perfluorobiphenylene group represented by the formula (A02-1-1) is even more preferable.

（式中、a²¹〜a²⁴およびＺ⁰²は、上記と同じ意味を表す。）

(In the formula, a ^{21 to} a ²⁴ and Z ⁰² have the same meanings as described above.)

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

Here, L ¹¹ is, -S -, - O -, - CO -, - CH 2 -, - (CH 2) 2 -, - C (CH 3) 2 -, - CF 2 -, - (CF 2 _{) 2 -, - C (CF} 3) 2 -, 9,9-diyl group, -NH- or -NZ ¹⁰⁰ - represents a.
L ¹² represents a hydrogen atom, optionally substituted alkenyl group or Z ¹³¹ of is an alkyl group having 1 to 20 carbon atoms also be good 2-20 carbon atoms substituted with Z ¹³⁰ substituted with Z ¹³⁰ The same as the above is mentioned as a specific example of the alkyl group, the alkenyl group and the aryl group. Among these, L ¹² is preferably a hydrogen atom or a phenyl group.
L ¹³ and L ¹⁴ are each independently a hydrogen atom, Z ¹³⁰ with an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ¹³⁰ Or, it represents an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³¹ , and specific examples of these alkyl group, alkenyl group and aryl group include the same ones as described above. Among these, as L ¹³ and L ¹⁴ , a hydrogen atom, an alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 10 carbon atoms are preferable, and a hydrogen atom, a methyl group and a phenyl group are more preferable.

Z ¹⁰⁰ represents an alkyl group with carbon atoms which may have 1 to 20 substituted by Z ^130, which may be substituted with alkenyl or Z ¹³¹ good 2 to 20 carbon atoms optionally substituted by Z ¹³⁰ carbon It represents an aryl group of the formulas 6 to 20, but a phenyl group which may be substituted with a fluorine atom is preferable.
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, or a C 1-20 optionally substituted with Z ^130. Represents an alkyl group, a C 2-20 alkenyl group which may be substituted with Z ¹³⁰ , or a C 6-20 aryl group which may be substituted with Z ¹³¹ , and Z ¹⁰⁸ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, Z ¹³⁰ with an optionally substituted alkyl group having a carbon number of 1 to 20, Z ¹³⁰ is optionally carbon atoms, which may 2 substituted with 20 represents an alkenyl group having 20 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³¹ , and Z ¹⁰⁸ existing on different benzene rings may be bonded to each other to form a ring. ¹³⁰ each independently represents a fluorine atom, a chlorine atom, a bromine atom or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³² , and Z ¹³¹ each independently represents a fluorine atom or a chlorine atom. atom, a bromine atom, an alkenyl group of an alkyl group or Z ¹³² good 2 to 20 carbon atoms optionally substituted with a carbon atoms which may be have 1-20 substituted with Z ^132, Z ¹³² is a fluorine atom, It represents a chlorine atom or a bromine atom, and specific examples of these alkyl group, alkenyl group and aryl group include the same ones as described above. Of these, Z ^{101 to} Z ¹⁰⁷ and Z ^{109 to} Z ¹²¹ are preferably hydrogen atoms. Z ¹⁰⁸ is preferably a hydrogen atom or a single bond in which at least one set of Z ¹⁰⁸ existing at the ortho positions of nitrogen atoms on different benzene rings are bonded. The formula (B08) in which Z ^{108 s} form a single bond includes, for example, one represented by the following formula (B08′).
Z ^q (q=101 to 121) may be the same or different.

Ar ^1's each independently represent an aryl group having 6 to 20 carbon atoms, and examples of the aryl group include the same ones as described above. Among them, Ar ¹ is preferably a phenyl group, a 1-naphthyl group or a 2-naphthyl group, more preferably a phenyl group.
Ar ² represents a single bond or an arylene group having 6 to 20 carbon atoms. Specific examples of the arylene group having 6 to 20 carbon atoms include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6- Examples thereof include naphthalenediyl and 2,7-naphthalenediyl groups. Above all, Ar ² is preferably a single bond or a 1,4-phenylene group.

Particularly, in consideration of easiness of synthesis and the like, Y ²¹¹ and Y ²¹² are preferably the same monovalent group, and both are represented by formulas (B01), (B02), (B04), (B08) and (B18). More preferably, it is a monovalent group represented by any of the above.

Further, another one of the fluorine-containing aniline derivatives according to the present invention is represented by the following formula (T2).

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

Here, 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 are substituted with aromatic rings. Represents the number of fluorine atoms, b ¹² , b ²² , b ²⁴ , b ³² , b ³⁴ , b ⁴² , b ⁵² , b ⁶² , b ⁷² , b ⁷⁴ , b ⁸² , b ⁸⁴ , b ⁹² and b ⁹⁴ are , And the number of Z ^{01 to} Z ⁰⁹ substituted on the aromatic ring, and b ⁷⁵ and b ⁷⁶ represent the number of Z′ substituted on the aromatic ring.
b ¹¹ is an integer of 2 to 5, b ¹² is an integer of 0 to 3 and satisfies b ¹¹ +b ¹² ≦5.
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 are satisfied.
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 are satisfied.
b ⁴¹ is an integer of 1 to 7, b ⁴² is an integer of 0 to 6 and satisfies b ⁴¹ +b ⁴² ≦7.
b ⁵¹ is an integer of 1 to 9, b ⁵² is an integer of 0 to 8 and satisfies b ⁵¹ +b ⁵² ≦9.
b ⁶¹ is an integer of 1 to 9, b ⁶² is an integer of 0 to 8 and satisfies b ⁶¹ +b ⁶² ≦9.
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 are satisfied, and b ⁷⁵ and b ⁷⁶ are each independently an integer of 0 to 4.
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 b ⁸¹ +b ⁸² ≦3 and b ⁸³ +b ⁸⁴ ≦4 are satisfied.
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 b ⁹¹ +b ⁹² ≤3 and b ⁹³ +b ⁹⁴ ≤4 are satisfied.
In particular, b ⁴¹ , b ⁵¹ and b ⁶¹ are preferably integers of 2 or more.
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 are preferably 0, and b ⁷⁵ And b ⁷⁶ is preferably 0.
L ^{01 to} L ⁰⁴ , Z′ and Z ^{01 to} Z ⁰⁹ have the same meanings as described above.

In particular, in consideration of easiness of synthesis, charge transportability, etc., X ²²¹ and X ²²² are preferably the same monovalent group, more preferably both monovalent groups represented by the formula (C01). The monovalent group represented by the formula (C01-1) is even more preferable.

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

In the formula, Ar ^3's each independently represent an arylene group having 6 to 20 carbon atoms, and specific examples of the arylene group include the same ones as described above.
L ^{11 to} L ¹⁴ , Z ^{101 to} Z ¹²¹ , and Ar ¹ have the same meanings as described above.

Among these, Y ²²¹ is preferably a divalent group represented by the formula (D02), more preferably a divalent group represented by the following formula (D02-1), and a divalent group represented by the following formula (D02-1-1). The biphenylene group represented by the formula (4) is even more preferable.

（式中、Ｚ¹⁰²は、上記と同じ意味を表す。）

(In the formula, Z ¹⁰² has the same meaning as above.)

The fluorine-containing aniline derivative of the present invention does not include compounds represented by the following formulas [1] to [13].

Specific examples of the fluorinated aniline derivative of the present invention include those represented by the following formulas, but the invention is not limited thereto.

（式中、ｔ−Ｂｕは、ｔ−ブチル基を表す。）

(In the formula, t-Bu represents a t-butyl group.)

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

In formula (P1-2), examples of X ²¹¹ include the same groups as those exemplified for the above-mentioned fluorine-containing aniline derivative, and the preferable range thereof is also the same as above.
Examples of Y ²²¹ include the same groups as those exemplified for the above-mentioned fluorine-containing aniline derivative, but among them, a divalent group represented by any one of formulas (D02), (D17) and (D19) is preferable. preferable.

The molecular weight of the polymer of the present invention is not particularly limited, but in consideration of conductivity and solubility in an organic solvent when used as a charge transporting substance, a weight average molecular weight of 1000 to 100000 is preferable, and a weight average molecular weight of 2000 to 50,000 is more preferable, and 5000 to 30,000 is even more preferable. The weight average molecular weight is a polystyrene conversion value by gel permeation chromatography.

Specific examples of the polymer of the present invention include those represented by the following formulas, but the present invention is not limited thereto.

（式中、ｍは、それぞれ独立して、２以上の整数を表す。）

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

[4] Method for Producing Fluorine-Containing Aniline Derivative and Polymer The fluorine-containing aniline derivative and polymer of the present invention described above are synthesized by using the above-described method for producing a fluorinated aromatic secondary amine of the present invention. be able to.
For example, the fluorinated aniline derivative is a fluorinated aromatic first group represented by the above formula (X2) in the presence of a palladium zero-valent complex of dibenzylideneacetone, a ligand represented by the above formula (L) and a base. By reacting a secondary diamine with 2 equivalents of a chlorinated, brominated or iodinated aromatic hydrocarbon or pseudohalogenated aromatic hydrocarbon represented by the above formula (Y1), or in the above formula (X1) Fluorinated aromatic primary amine represented and 0.5 equivalent of dichlorinated, dibrominated or diiodinated aromatic hydrocarbon represented by the above formula (Y2) or dipseudohalogenated aromatic hydrocarbon It can be obtained by reacting with hydrogen.
On the other hand, the polymer is a fluorinated aromatic primary diamine represented by the above formula (X2) in the presence of a palladium zero-valent complex of dibenzylideneacetone, the ligand represented by the above formula (L) and a base. It can be obtained by reacting a compound with a dichlorinated, dibrominated or diiodinated aromatic hydrocarbon or dipseudohalogenated aromatic hydrocarbon represented by the above formula (Y2). In the synthesis of the polymer, the molecular weight is increased by increasing the amount of the catalyst. Therefore, the molecular weight of the obtained polymer can be adjusted by adjusting the amount of the catalyst.

[5] Charge-transporting substance, charge-transporting composition and charge-transporting thin film The above-mentioned fluorine-containing aniline derivative and polymer of the present invention have excellent transparency because they have a fluorine atom in the molecule, and they are used alone. Alternatively, since it exhibits conductivity when combined with a dopant substance, it can be suitably used as a charge-transporting substance. By dissolving the fluorine-containing aniline derivative or polymer of the present invention in a solvent, the charge-transporting property can be easily obtained. The composition can be prepared.
For example, examples of the charge transporting composition of the present invention include those containing a charge transporting substance composed of the above-mentioned fluorine-containing aniline derivative or polymer, and an organic solvent. A dopant substance may be included for the purpose of improving the charge transport ability.
The dopant substance is not particularly limited as long as it is soluble in at least one solvent used in the composition.

Specific examples of the dopant substance include strong inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid and phosphoric acid; aluminum chloride (III) (AlCl ₃ ), titanium tetrachloride (IV) (TiCl ₄ ), boron tribromide (BBr _{3 ).} ), boron trifluoride ether complex (BF ₃ ·OEt ₂ ), iron chloride (III) (FeCl ₃ ), copper (II) chloride (CuCl ₂ ), antimony pentachloride (V) (SbCl ₅ ), pentafluoride Lewis acids such as arsenic (V) (AsF ₅ ), phosphorus pentafluoride (PF ₅ ), tris(4-bromophenyl)aluminum hexachloroantimonate (TBPAH); benzenesulfonic acid, tosylic acid, camphorsulfonic acid, hydroxybenzene Naphthalene disulfonic acid such as sulfonic acid, 5-sulfosalicylic acid, dodecylbenzene sulfonic acid, 1,5-naphthalene disulfonic acid, naphthalene such as 1,3,5-naphthalene trisulfonic acid, 1,3,6-naphthalene trisulfonic acid Trisulfonic acid, polystyrene sulfonic acid, 1,4-benzodioxane disulfonic acid compound described in WO 2005/000832, naphthalene or anthracene sulfonic acid compound described in WO 2006/025342, Organic strong acids such as aryl sulfonic acid compounds such as dinonylnaphthalene sulfonic acid compounds described in JP 2005-108828 A; 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro. Organic oxidizers such as -5,6-dicyano-1,4-benzoquinone (DDQ) and iodine, heteropoly compounds such as phosphomolybdic acid, phosphotungstic acid and phosphotungstomolybdic acid described in WO 2010/058777. Inorganic oxidizing agents such as acids may be used, and these may be used in combination.

Among these, the aryl sulfonic acid compound is preferable, and the aryl sulfonic acid compound represented by the formula (H1) or (H2) is preferable. The molecular weight of the aryl sulfonic acid compound used as the dopant substance is preferably 3000 or less, more preferably 2500 or less in consideration of the solubility in an organic solvent.

A ¹ represents O or S, and O is preferable.
A ² represents a naphthalene ring or an anthracene ring, but a naphthalene ring is preferable.
A ³ represents a divalent to tetravalent perfluorobiphenyl group, p represents the number of bonds between A ¹ and A ^3, and is an integer satisfying 2≦p≦4, but A ³ is perfluorobiphenyldiyl It is preferably a group, preferably a perfluorobiphenyl-4,4′-diyl group, and p is 2.
q represents the number of sulfonic acid groups bonded to A ² , and is an integer satisfying 1≦q≦4, and 2 is optimal.

A ^{4 to} A ⁸ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated group having 2 to 20 carbon atoms. It represents an alkenyl group, but at least three of A ^{4 to} A ⁸ are halogen atoms.

Examples of the halogenated alkyl group having 1 to 20 carbon atoms include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl and 3,3,3-trifluoropropyl. , 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4 , 4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group and the like. To be

Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include perfluorovinyl, perfluoropropenyl (perfluoroallyl), and perfluorobutenyl groups.
Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom, and a fluorine atom is preferable.
In addition, examples of the alkyl group having 1 to 20 carbon atoms include the same ones as described above.

Among these, A ^{4 to} A ⁸ are hydrogen atom, halogen atom, cyano group, alkyl group having 1 to 10 carbon atoms, halogenated alkyl group having 1 to 10 carbon atoms, or alkenyl halide having 2 to 10 carbon atoms. It is a group, and at least three of A ^{4 to} A ⁸ are preferably fluorine atoms, and a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, or a carbon atom having 1 to 5 carbon atoms A fluorinated alkyl group or a fluorinated alkenyl group having 2 to 5 carbon atoms, and at least three of A ^{4 to} A ⁸ are more preferably fluorine atoms, and a hydrogen atom, a fluorine atom, a cyano group, It is even more preferable that it is a perfluoroalkyl group having 1 to 5 carbon atoms or a perfluoroalkenyl group having 1 to 5 carbon atoms, and A ⁴ , A ⁵ and A ⁸ are fluorine atoms.
The perfluoroalkyl group is a group in which all the hydrogen atoms of the alkyl group are replaced with fluorine atoms, and the perfluoroalkenyl group is the group in which all the hydrogen atoms of the alkenyl group are replaced with fluorine atoms.

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.

Specific examples of suitable aryl sulfonic acid compounds are shown below, but the invention is not limited thereto.

The organic solvent is not particularly limited as long as it can dissolve or disperse the charge transporting substance and the dopant substance, and for example, benzene, toluene, o-xylene, m-xylene, p-xylene, N-. Methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, cyclohexanol, ethylene Glycol, 1,3-octylene glycol, 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 Examples thereof include alcohol, γ-butyrolactone, ethyl lactate, and n-hexyl acetate, and these may be used alone or in combination of two or more.

The viscosity of the charge transporting composition of the present invention is usually 1 to 50 mPa·s at 25° C., and the surface tension is usually 20 to 50 mN/m at 25° C.
The viscosity and surface tension of the charge-transporting composition of the present invention should be changed in consideration of various factors such as the coating method used and the desired film thickness, the type of organic solvent used, their ratio, and the solid content concentration. It can be adjusted with.

The solid content concentration of the charge transporting composition of the present invention is appropriately set in consideration of the viscosity and surface tension of the composition, the thickness of the thin film to be produced, etc. It is about 15.0% by mass, and preferably from 10.0% by mass or less, more preferably 8.0% by mass or less, and even more preferably from the viewpoint of suppressing aggregation of the charge transporting substance in the composition. It is 5 mass% or less.
In addition, the solid content of the solid content concentration as used herein means a component other than the solvent contained in the charge transporting composition of the present invention.

The charge-transporting composition of the present invention can be produced by mixing the charge-transporting substance of the present invention, an organic solvent, and a dopant substance used as necessary. The mixing order is not particularly limited.
When the composition is prepared, heating may be appropriately performed within a range in which the components are not decomposed or deteriorated.
In the present invention, the charge-transporting composition is a sub-micrometer order filter or the like after dissolving the charge-transporting substance or the like in an organic solvent, from the viewpoint of obtaining a highly flat thin film with good reproducibility. It is desirable to filter.

The charge-transporting thin film of the present invention can be formed on the substrate by applying the above-described charge-transporting composition onto the substrate and baking the composition.
The method for applying the composition is not particularly limited, and examples thereof include a dip method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an inkjet method, a spray method, and a slit coating method. The viscosity and surface tension of the composition are preferably adjusted accordingly.

When the charge transporting composition of the present invention is used, the firing atmosphere is not particularly limited, and a uniform film formation surface and a high charge can be obtained not only in the air atmosphere (under air) but also in an inert gas such as nitrogen or vacuum. A thin film having transportability can be obtained, but usually under air.
The firing conditions are also not particularly limited, but heating and firing are performed using a hot plate, for example. Usually, in consideration of desired charge transportability and the like, the firing temperature is appropriately determined within the range of 100 to 260° C., and the firing time is appropriately determined within the range of 1 minute to 1 hour. Furthermore, if necessary, multi-step firing may be performed at two or more different temperatures.

The thickness of the charge transporting thin film is not particularly limited, but when used as a functional layer of an organic EL element, it is preferably 5 to 300 nm. As a method for changing the film thickness, there are methods such as changing the solid content concentration in the charge transporting composition and changing the liquid amount at the time of coating.

Since the fluorine-containing aniline derivative or polymer of the present invention contains a fluorine atom, its main purpose is to improve the coating properties, improve the transparency of the obtained film, and adjust the film physical properties such as adjusting the wettability of the film surface. It can also be used as an additive added to a charge transporting composition containing other charge transporting substance.

[6] Organic EL Element The organic EL element of the present invention has a pair of electrodes and the above-described charge transporting thin film of the present invention between the electrodes.
Typical configurations of the organic EL element include the following (a) to (f), but are not limited to these. In the following structure, if necessary, an electron block layer or the like may be provided between the light emitting layer and the anode, and a hole (hole) block layer or the like may be provided between the light emitting layer and the cathode. Further, the hole injecting layer, the hole transporting layer or the hole injecting and transporting layer may also have a function as an electron blocking layer, and the electron injecting layer, the electron transporting layer or the electron injecting and transporting layer may be holes (holes). You may also have the function as a block layer etc.
(A) Anode/hole injecting layer/hole transporting layer/light emitting layer/electron transporting layer/electron injecting layer/cathode (b) anode/hole injecting layer/hole transporting layer/light emitting layer/electron injecting/transporting layer/ Cathode (c) Anode/hole injecting/transporting layer/light emitting layer/electron transporting layer/electron injecting layer/cathode (d) anode/hole injecting/transporting layer/light emitting layer/electron injecting/transporting layer/cathode (e) anode/positive Hole injection layer/hole transport layer/light emitting layer/cathode (f) Anode/hole injection transport layer/light emitting layer/cathode

The "hole injection layer", "hole transport layer" and "hole injection transport layer" are layers formed between a light emitting layer and an anode, and transport holes from the anode to the light emitting layer. In the case where only one layer of the hole-transporting material is provided between the light-emitting layer and the anode, which has a function, it is a "hole injecting and transporting layer", and between the light-emitting layer and the anode, When two or more layers of the hole transporting material are provided, the layer close to the anode is the “hole injection layer” and the other layers are the “hole transporting layers”. In particular, as the hole injecting (transporting) layer, a thin film having excellent hole injecting property to the hole transporting (light emitting) layer as well as the hole accepting property from the anode is used.
"Electron injection layer", "electron transport layer" and "electron injection transport layer" are layers formed between a light emitting layer and a cathode and having a function of transporting electrons from the cathode to the light emitting layer. When only one layer of the electron transporting material is provided between the light emitting layer and the cathode, it is an “electron injecting and transporting layer”, and a layer of the electron transporting material is provided between the light emitting layer and the cathode. When two or more layers are provided, the layer close to the cathode is the “electron injection layer” and the other layers are the “electron transport layer”.
The “light emitting layer” is an organic layer having a light emitting function and includes a host material and a dopant material when a doping system is adopted. At this time, the host material mainly has a function of promoting recombination of electrons and holes and confining excitons in the light-emitting layer, and the dopant material efficiently emits excitons obtained by the recombination. Have a function. In the case of a phosphorescent device, the host material has a function of mainly confining excitons generated by the dopant in the light emitting layer.

The charge-transporting thin film of the present invention can be preferably used as an organic functional film provided between an anode and a light-emitting layer in an organic EL device, and is a hole injection layer, a hole transport layer, a hole injection transport layer. As the hole injecting layer.
Examples of materials used and methods for producing an organic EL device using the charge-transporting composition of the present invention include, but are not limited to, the following.

An example of a method for producing an OLED device having a hole injection layer composed of a thin film obtained from the charge transporting composition of the present invention is as follows. It is preferable that the electrode is previously subjected to cleaning with alcohol, pure water, or the like, or surface treatment such as UV ozone treatment or oxygen-plasma treatment, to the extent that the electrode is not adversely affected.
A hole injection layer is formed on the anode substrate by the above method using the above charge transporting composition. This is introduced into a vacuum vapor deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer/hole block layer, an electron injection layer, and a cathode metal are sequentially deposited. Alternatively, instead of forming the hole transport layer and the light emitting layer by vapor deposition in the method, a hole transport layer forming composition containing the hole transporting polymer and a light emitting layer forming composition containing the light emitting polymer are provided. Are used to form these layers by a wet process. If necessary, an electron blocking layer may be provided between the light emitting layer and the hole transport layer.

Examples of the anode material include a transparent electrode typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and a metal anode composed of a metal typified by aluminum or an alloy thereof. Those subjected to a chemical treatment are preferable. A polythiophene derivative or a polyaniline derivative having a high charge transporting property can also be used.
Other metals that compose the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.

As the material for forming the hole transport layer, (triphenylamine) dimer derivative, [(triphenylamine) dimer] spiro dimer, N,N'-bis(naphthalen-1-yl)-N,N'-bis (Phenyl)-benzidine (α-NPD), 4,4′,4″-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4′,4″-Tris[1 -Triarylamines such as naphthyl(phenyl)amino]triphenylamine (1-TNATA), 5,5"-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2': Examples thereof include oligothiophenes such as 5′,2″-terthiophene (BMA-3T).

As a material for forming the light emitting layer, a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo[h]quinoline, a bisstyrylbenzene derivative, a bisstyrylarylene derivative, (2-hydroxyphenyl)benzo. Low molecular weight light emitting materials such as metal complexes of thiazole and silole derivatives; poly(p-phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly(3-alkyl) Examples thereof include a system in which a light emitting material and an electron transfer material are mixed with a polymer compound such as thiophene) and polyvinylcarbazole.
When the light emitting layer is formed by vapor deposition, it may be co-deposited with a light emitting dopant, and the light emitting dopant may be a metal complex such as tris(2-phenylpyridine)iridium(III)(Ir(ppy) ₃ ). And naphthacene derivatives such as rubrene, quinacridone derivatives, condensed polycyclic aromatic rings such as perylene, and the like.

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

Materials for forming the electron injection layer include metal oxides such as lithium oxide (Li ₂ O), magnesium oxide (MgO), and alumina (Al ₂ O ₃ ), lithium fluoride (LiF), sodium fluoride (NaF). But not limited to.
Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy and the like.
Examples of the material forming the electron block layer include tris(phenylpyrazole)iridium.

Examples of the hole transporting polymer include poly[(9,9-dihexylfluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene. )], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(N,N′-bis{p-butylphenyl}-1,1′-biphenylene-4,4-diamine). )], poly[(9,9-bis{1′-penten-5′-yl}fluorenyl-2,7-diyl)-co-(N,N′-bis{p-butylphenyl}-1,4 -Diaminophenylene)], poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine]-endcapped with polysilcisquinoxane, poly[(9,9- Didioctylfluorenyl-2,7-diyl)-co-(4,4′-(N-(p-butylphenyl))diphenylamine)] and the like.

Examples of the light-emitting polymer include poly(9,9-dialkylfluorene) (PDAF) and other polyfluorene derivatives, poly(2-methoxy-5-(2′-ethylhexoxy)-1,4-phenylenevinylene) (MEH- Examples thereof include polyphenylene vinylene derivatives such as PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

The organic EL device of the present invention may be sealed with a water catching agent or the like according to a conventional method in order to prevent deterioration of characteristics.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

〔apparatus〕
The physical properties of the sample were measured using the following apparatus under the following conditions.
(1) Liquid chromatography (tracing reaction)
Equipment: Shimadzu Corporation
UV-VIS detector: SPD-20A
Column oven: CTO-20A
Degassing unit: DGU-20A
Liquid transfer unit: LC-20AB
Autosampler: SIL-20A
Column: Poroshell 120 EC-C18 (2.7 μm, 3.0×50 mm, Agilent)
Column temperature: 40°C
Solvent: acetonitrile/water Acetonitrile concentration: 40% (0-0.01 min)→40%-100% (0.01-5 min)→100% (5-15 min) (volume ratio)
Detector: UV
(2) Gel permeation chromatography (molecular weight measurement of polymer)
Equipment: Shimadzu Corporation
UV-VIS detector: SPD-20A
Differential refractometer detector: RID-20A
Column oven: CTO-20A
Degassing unit: DGU-20A
Liquid transfer unit: LC-20AD
Autosampler: SIL-20A
Column: Shodex KF-G+KF-804L
Column temperature: 40°C
Solvent: Tetrahydrofuran Detector: UV
(3) Application of composition: Spin coater MS-A100 manufactured by Mikasa Co., Ltd.
(4) Fabrication of device: Choshu Sangyo Co., Ltd. Multifunctional evaporation system C-E2L1G1-N
(5) Measurement of current density of device: (Present) Tech World IVL measuring system (6) Glass transition temperature (Tg) measuring apparatus: Perkin elmer Diamond DSC
Measurement conditions: Temperature rising rate under nitrogen atmosphere: 5°C/min (40 to 300°C)
(7) 5% weight loss temperature (Td5%) measuring device: TG8120 manufactured by Rigaku Corporation
Measurement conditions: Temperature rising rate in air atmosphere: 10°C/min (40 to 500°C)
(8) Automatic column chromatography device (preparation of the target substance): 2CH parallel purification device Purif-espoir2 manufactured by Shoko Scientific Co., Ltd.
(9) NMR: Bruker Avance III 500 MHz
Internal standard
¹⁹ F-NMR chemical shift correction
Trifluoro toluene=-64ppm
¹³ C-NMR chemical shift correction
Acetone-d6=206.68ppm
Chloroform-d1=77.23ppm
N,N-Dimethylformamide-d7=163.15ppm
Tetrahydrofuran-d8=67.57ppm

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

[1] Synthesis of Fluorinated Aromatic Secondary Amine Compound (1) Reaction of Pentafluoroaniline with 4-Bromoanisole

[Comparative Example 1-1]
A 30 mL reaction flask equipped with a reflux tower was weighed with 0.05 mmol (57.8 mg) of Pd(PPh ₃ ) ₄ , 1.2 mmol (115.3 mg) of t-BuONa, and 1.2 mmol (219.7 mg) of pentafluoroaniline. Then, the system was replaced with nitrogen. Dioxane 4 mL and 4-bromoanisole 1 mmol (187.0 mg) were added thereto, and the mixture was stirred at room temperature for 5 minutes and then heated and stirred in a 110°C bath for 5 hours (internal temperature 92°C), but collected from the flask. In liquid chromatography using a small amount of solution, peaks that could be assigned to the raw materials could be confirmed, but peaks that could be attributed to the target substance could not be confirmed.

[Comparative Example 1-2]
In a 30 mL reaction flask equipped with a reflux tower, Pd(PPh ₃ ) ₄ 0.05 mmol (57.8 mg), (±) BINAP 0.075 mmol (46.7 mg), cesium carbonate 1.2 mmol (391.0 mg), penta 1.2 mmol (219.7 mg) of fluoroaniline was weighed in, and the system was replaced with nitrogen. Dioxane 4 mL and 4-bromoanisole 1 mmol (187.0 mg) were added thereto, and the mixture was stirred at room temperature for 5 minutes and then heated and stirred in a 110°C bath for 5 hours (internal temperature 92°C), but collected from the flask. In liquid chromatography using a small amount of solution, peaks that could be assigned to the raw materials could be confirmed, but peaks that could be attributed to the target substance could not be confirmed.

[Comparative Example 1-3]
A 30 mL reaction flask equipped with a reflux tower was charged with 0.05 mmol (57.8 mg) of Pd(PPh ₃ ) ₄ , 0.075 mmol (46.7 mg) of (±) BINAP, and 1.2 mmol (219.7 mg) of pentafluoroaniline. It was weighed in and the system was replaced with nitrogen. Dioxane 4mL, 4-bromoanisole 1mmol (187.0mg) were added there, LHMDS 1.3mol/L tetrahydrofuran solution 0.923mL (LHMDS 1.2mmol equivalent) was added, and after stirring at room temperature for 5 minutes, 110 degreeC bath. The mixture was heated and stirred in the flask for 5 hours (internal temperature: 92° C.), but in the liquid chromatography using a small amount of the solution collected from the flask, a peak attributable to the raw material was confirmed, but a peak attributable to the target substance was confirmed. could not.

[Comparative Example 1-4]
The work was performed in the same manner as in Comparative Example 1-3, except that RuPhos 0.075 mmol (35.0 mg) represented by the following formula (L2) was used instead of (±) BINAP, but the sample was collected from the flask. In liquid chromatography using the trace amount of the solution, a peak attributable to the raw material could be confirmed, but a peak attributable to the target product could not be confirmed.

（式中、ｉ−Ｐｒはイソプロピル基を、Ｃｙはシクロヘキシル基を表す。）

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

[Comparative Example 1-5]
In a 30 mL reaction flask equipped with a reflux tower, 0.05 mmol (28.8 mg) of Pd(DBA) _{2 and} 1.2 mmol (219.7 mg) of pentafluoroaniline were weighed and the system was replaced with nitrogen. Dioxane 4mL, 4-bromoanisole 1mmol (187.0mg) were added there, LHMDS 1.3mol/L tetrahydrofuran solution 0.923mL (LHMDS 1.2mmol equivalent) was added, and after stirring at room temperature for 5 minutes, 110 degreeC bath. The mixture was heated and stirred in the flask for 5 hours (internal temperature: 92° C.), but in the liquid chromatography using a small amount of the solution collected from the flask, a peak attributable to the raw material was confirmed, but a peak attributable to the target substance was confirmed. could not.

[Comparative Example 1-6]
In a 30 mL reaction flask equipped with a reflux tower, Pd(DBA) ₂ 0.05 mmol (28.8 mg), (±) BINAP 0.075 mmol (46.7 mg), pentafluoroaniline 1.2 mmol (219.7 mg), carbonic acid. 1.2 mmol (391.0 mg) of cesium was weighed in, and the system was replaced with nitrogen. Dioxane 4 mL and 4-bromoanisole 1 mmol (187.0 mg) were added thereto, and the mixture was stirred at room temperature for 5 minutes and then heated and stirred in a 110°C bath for 5 hours (internal temperature 92°C), but collected from the flask. In liquid chromatography using a small amount of solution, peaks that could be assigned to the raw materials could be confirmed, but peaks that could be attributed to the target substance could not be confirmed.

[Comparative Example 1-7]
In a 30 mL reaction flask equipped with a reflux tower, Pd(DBA) ₂ 0.05 mmol (28.8 mg), (±) BINAP 0.075 mmol (46.7 mg), and pentafluoroaniline 1.2 mmol (219.7 mg) were weighed. Then, the system was replaced with nitrogen. Dioxane 4mL, 4-bromoanisole 1mmol (187.0mg) were added there, LHMDS 1.3mol/L tetrahydrofuran solution 0.923mL (LHMDS 1.2mmol equivalent) was added, and after stirring at room temperature for 5 minutes, 110 degreeC bath. The mixture was heated and stirred in the flask for 5 hours (internal temperature: 92° C.), but in the liquid chromatography using a small amount of the solution collected from the flask, a peak attributable to the raw material was confirmed, but a peak attributable to the target substance was confirmed. could not.

[Example 1-1]
In a 30 mL reaction flask equipped with a reflux tower, 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) was weighed in and the system was replaced with nitrogen. Dioxane 4mL, 4-bromoanisole 1mmol (187.0mg) were added there, and it stirred at room temperature for 5 minutes, and then LHMDS 1.3mol/L tetrahydrofuran solution 0.923mL (LHMDS1.2mmol) was added, and stirred at room temperature for 5 minutes. Then, the mixture was heated and stirred in a bath at 110°C for 5 hours (internal temperature 92°C). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→97/3) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the target substance was collected. ..
Finally, the solvent was removed from the fractions collected under reduced pressure at 80°C to obtain 67.2 mg of the desired product (yield 26%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 3.76 (s, 3H), 5.14 (brs, 1H), 6.72-6.75 (m, 6H), 6.8 (d, J = 9.0 Hz, 2 H)
¹³ C NMR (125.77 MHz, CDCl ₃ ): δ = 55.8, 114.7, 119.5, 120.1, 135.4, 136.3, 138.5, 140.6, 155.9
¹⁹ F NMR (470.53 MHz, CDCl ₃ ): δ = -167.6 (t, J = 21.7 Hz, 1F), -164.5 (td, J = 21.7, 5.2 Hz, 2F), -153.3 (brd, 2F); IR (neat)
ν~ = 3314 (w), 3063 (w), 2968 (w), 1694 (s), 1670 (m), 1653 (m), 1609 (m), 1590 (m), 1503 (s), 1460 ( m), 1440 (s), 1414 (m), 1295 (m), 1196 (m), 1176 (m), 1138 (w), 1119 (m), 1106 (m), 1073 (w), 1022 ( m), 1008 (m), 982 (s), 905 (m), 845 (m), 765 (s), 753 (m), 735 (m), 697 (m)
HRMS (ESI): Calcd for C ₁₃ H ₈ F ₅ NO (M+H) ⁺ 289.0526, found 290.0589.

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

[Example 1-3]
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 into a 30 mL reaction flask equipped with a reflux tower, and the system was added. The inside was replaced with nitrogen. Dioxane 4mL, 4-bromoanisole 1mmol (187.0mg) were added there, and it stirred at room temperature for 5 minutes, then LHMDS 1.3mol/L tetrahydrofuran solution 0.923mL (equivalent to LHMDS 1.2mmol), and stirred at room temperature for 5 minutes. After that, the mixture was heated and stirred in a bath at 110°C for 3 hours (internal temperature 92°C). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→97/3) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the target substance was collected. ..
Finally, the solvent was removed from the fractions collected under reduced pressure at 80° C. to obtain 287.3 mg of the desired product (yield>99%).

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

[Example 1-5]
Instead of RuPhos, t-BuXPhos 0.075 mmol (31.8 mg) represented by the following formula (L4) was used, and the reaction and post-treatment were carried out in the same manner as in Example 1-3 except that the reaction time was 5 hours. The desired product (243.9 mg) was obtained (yield 84%).

（式中、ｉ−Ｐｒはイソプロピル基を、ｔ−Ｂｕはｔ−ブチル基を表す。）

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

[Example 1-6]
Instead of RuPhos, SPhos 0.075 mmol (30.8 mg) represented by the following formula (L1) was used, and the reaction and post-treatment were performed in the same manner as in Example 1-3 except that the reaction time was 5 hours. 246.0 mg of the target product was obtained (yield 85%).

（式中、Ｍｅはメチル基を、Ｃｙはシクロヘキシル基を表す。）

(In the formula, Me represents a methyl group and Cy represents a cyclohexyl group.)

[Example 1-7]
Instead of RuPhos, t-BuMePhos 0.075 mmol (23.4 mg) represented by the following formula (L5) was used, and the reaction and post-treatment were carried out in the same manner as in Example 1-3 except that the reaction time was 5 hours. Then, 246.3 mg of the desired product was obtained (yield 85%).

（式中、Ｍｅはメチル基を、ｔ−Ｂｕはｔ−ブチル基を表す。）

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

[Example 1-8]
Instead of RuPhos, JhonPhos 0.075 mmol (22.4 mg) represented by the following formula (L6) was used, and the reaction and post-treatment were performed in the same manner as in Example 1-3 except that the reaction time was 5 hours. 268.2 mg of the target product was obtained (yield 95%).

（式中、ｔ−Ｂｕはｔ−ブチル基を表す。）

(In the formula, t-Bu represents a t-butyl group.)

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

（式中、Ｃｙはシクロヘキシル基を表す。）

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

Table 1 shows a summary of Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-7.

（実施例１−４：ＲｕＰｈｏｓ使用量０．２ｍｍｏｌ）

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

(2) Reaction of pentafluoroaniline with aryl halide

[Comparative Example 1-8]
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 into a 30 mL reaction flask equipped with a reflux tower, and the system was added. The inside was replaced with nitrogen. 4 mL of dioxane and 1 mmol (96.1 mg) of fluorobenzene were added thereto and stirred at room temperature for 5 minutes, then 0.923 mL of LHMDS 1.3 mol/L tetrahydrofuran solution (corresponding to LHMDS 1.2 mmol) was added and stirred at room temperature for 5 minutes. The mixture was heated and stirred in a 110°C bath for 5 hours (internal temperature 92°C). Incidentally, the reaction was traced by liquid chromatography using a small amount of the solution collected from the inside of the flask, and a large number of prominent peaks that could not be attributed to the target substance were confirmed in addition to the peaks that could be attributed to the raw material.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→97/3) was carried out using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and fractions other than the fraction mainly containing the raw materials were used. Was collected.
Finally, the solvent was removed from the fractions collected under reduced pressure at 80°C to obtain a solid. However, in the ¹ H-NMR spectrum of the obtained solid, a large number of peaks that could not be assigned to any of the raw material and the target substance were observed. This mixture was a mixture containing a plurality of by-products, and it was judged that isolation of the desired product from this was difficult, and no further purification was attempted.

[Example 1-10]
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 into a 30 mL reaction flask equipped with a reflux tower, and the system was added. The inside was replaced with nitrogen. Dioxane 4mL, chlorobenzene 1mmol (112.6mg) was added thereto, and the mixture was stirred at room temperature for 5 minutes, then LHMDS 1.3mol/L tetrahydrofuran solution 0.923mL (LHMDS 1.2mmol equivalent) was added, and the mixture was stirred at room temperature for 5 minutes, The mixture was heated and stirred in a 110°C bath for 3 hours (internal temperature 92°C). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→97/3) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the target substance was collected. ..
Finally, the solvent was removed from the fractions collected under reduced pressure at 80°C to obtain 195.7 mg of the desired product (yield 81%).

[Example 1-11]
In place of chlorobenzene, 1 mmol (157.0 mg) of bromobenzene was used, and the reaction and post-treatment were carried out in the same manner as in Example 1-10 except that the reaction time was 5 hours, to obtain 256.6 mg of the desired product ( Yield >99%).

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

[Example 1-13]
The reaction and post-treatment were performed 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%).

[Example 1-14]

In a 30 mL reaction flask equipped with a reflux tower, Pd(DBA) ₂ 0.05 mmol (28.8 mg), RuPhos 0.075 mmol (35.0 mg), pentafluoroaniline 1.2 mmol (219.7 mg), 4-fluorobromo. 1 mmol (175.0 mg) of benzene was weighed in and the system was replaced with nitrogen. Dioxane (4 mL) was added thereto, and the mixture was stirred for 5 minutes, then LHMDS 1.3 mol/L tetrahydrofuran solution 0.923 mL (LHMDS 1.2 mmol equivalent) was added, and the mixture was stirred at room temperature for 5 minutes, and then heated and stirred in a bath at 110°C for 5 hours. (Internal temperature 92° C.). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→97/3) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the target substance was collected. ..
Finally, the solvent was removed from the fractions collected under reduced pressure at 50°C to obtain 242.9 mg of the desired product (yield 88%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 5.39 (brs, 1H), 6.84 (m, 2h), 7.00 (brt, 2H)
¹³ C NMR (125.77 MHz, CDCl ₃ ): δ = 116.0, 116.2, 118.9, 119.0,138.3, 157.8, 159.7
¹⁹ F NMR (470.53 MHz, CDCl ₃ ): δ -165.6 (brt, 1F), -164.0 (brdt, F), 151.8 (brd, 2F), 122.6 (brs, 1 F);
IR (neat)ν~ = 3425.6 (m), 1656.9 (w), 1504.5 (s), 1205.5 (s), 1153.4 (m), 1101.4 (m), 1008.8 (s), 997.9 (s), 827.5 (s ), 748.4 (m), 717.5 (m), 702.1 (m), 669.3 (m), 636.5 (m)

Table 2 shows a summary of Examples 1-10 to 1-14 and Comparative Example 1-8.

(3) Reaction of mono-tetrafluoroaniline with 4-bromoanisole

[Example 1-15]
Pd(DBA) ₂ 0.05 mmol (28.8 mg) and RuPhos 0.075 mmol (35.0 mg) were weighed into a 30 mL reaction flask equipped with a reflux tower, and the system was replaced with nitrogen. 4 mL of dioxane was added thereto, 1.2 mmol (133.3 mg) of 2-fluoroaniline and 1 mmol (187.0 mg) of 4-bromoanisole were added, and the mixture was stirred at room temperature for 5 minutes, and then LHMDS 1.3 mol/L tetrahydrofuran solution 0 After adding 923 mL (corresponding to LHMDS 1.2 mmol) and stirring at room temperature for 5 minutes, the mixture was heated and stirred in a bath at 110° C. for 5 hours (internal temperature 92° C.). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→97/3) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the target substance was collected. ..
Finally, the solvent was removed from the fractions collected under reduced pressure at 80°C to obtain 217.6 mg of the desired product (yield 98%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 3.84 (s, 3H), 5.68 (brs, 1H), 6.77-6.79 (m, 1H), 6.93 (d, J = 9.0 Hz, 2H), 7.00 ( brt, 1H), 7.07-7.12 (m, 2H); 7.15 (d, J = 9.0 Hz, 2H)
¹³ C NMR (125.77 MHz, CDCl ₃ ): δ = 55.7, 114.9, 115.2, 115.3, 119.1, 123.3, 124.5, 134.1, 134.7, 152.4, 156.1
¹⁹ F NMR (470.53 MHz, CDCl ₃ ): δ -136.1 (brs); IR (neat)
ν~ = 3382 (m), 3010 (w), 2938 (w), 2906 (w), 2838 (w), 1617 (m), 1585 (w), 1504 (s), 1477 (m), 1464 ( m), 1455 (m), 1442 (m), 1332 (m), 1296 (m), 1288 (m), 1255 (m), 1233 (s), 1222 (s), 1180 (s), 1171 ( m), 1109 (m), 1095 (s), 1029 (s), 1008 (m), 925 (w), 917 (w), 886 (w), 838 (m), 821 (s), 757 ( m), 742 (s), 707 (m), 696 (w)
HRMS (ESI): Calcd for C ₁₃ H ₁₂ FNO (M+H) ⁺ 217.0903, found 218.0963.

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

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

[Example 1-18]
The reaction and post-treatment were carried out in the same manner as in Example 1-15 except that 1.2 mmol (154.9 mg) of 2,6-difluoroaniline was used instead of 2-fluoroaniline, to obtain 216.2 mg of the desired product. (Yield 92%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 3.77 (s, 3H), 5.37 (brs, 1H), 6.81 (brs, 4H), 6.91-6.93 (m, 3H)
¹³ C NMR (125.77 MHz, CDCl ₃ ): δ = 55.8, 112.0, 114.6, 118.8, 121.0, 121.9, 137.1, 154.9, 156.1
¹⁹ F NMR (470.45 MHz, CDCl ₃ ): δ = -123.4 (m)
IR (neat): ν~ = 3411 (w), 2935 (w), 2835 (w), 1623 (w), 1598 (w), 1504 (s), 1456 (m), 1406 (w), 1294 ( m), 1233 (s), 1179 (m), 1111 (w), 1060 (w), 1033 (m), 999 (s), 818 (m), 778 (w), 758 (m), 728 ( w), 707 (w), 695 (w)
HRMS (ESI): Calcd for C ₁₃ H ₁₁ F ₂ NO (M+H) ⁺ 235.0809, found 236.0867.

[Example 1-19]
In a 30 mL reaction flask equipped with a reflux tower, 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). ) Was weighed in and the system was replaced with nitrogen. Dioxane 4mL was added there, 4-bromoanisole 1mmol (187.0 mg) was further added, and after stirring for 5 minutes, LHMDS 1.3mol/L tetrahydrofuran solution 0.923mL (LHMDS 1.2mmol equivalent) was added, and a bath at 110°C. The mixture was heated with stirring for 4 hours (internal temperature: 92° C.). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→97/3) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the target substance was collected. ..
Finally, the solvent was removed from the fractions collected under reduced pressure at 80°C to obtain 237.4 mg of the desired product (yield 91%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 3.76 (s, 3H), 5.14 (brs, 1H), 6.72-6.75 (m, 3H), 6.80 (d, J = 9.0 Hz, 2H)
¹³ C NMR (125.77 MHz, CDCl ₃ ): δ = 55.8, 100.9, 114.7, 117.4, 117.9, 137.6, 154.8, 156.7, 157.8
¹⁹ F NMR (470.45 MHz, CDCl ₃ ): δ = -119.8 (brs), -116.9 (brs)
IR (neat): ν~ = 3396 (w), 3083 (w), 2913 (w), 2837 (w), 1636 (w), 1608 (w), 1504 (s), 1442 (m), 1288 ( w), 1235 (s), 1173 (m), 1116 (s), 1030 (s), 996 (s), 837 (s), 817 (s)
HRMS (ESI): Calcd for C ₁₃ H ₁₀ F ₃ NO (M+H) ⁺ 253.0714, found 254.0772.

[Example 1-20]
Reaction and post-treatment were conducted in the same manner as in Example 1-19, except that 2,3,5,6-tetrafluoroaniline (1.2 mmol, 154.9 mg) was used instead of 2,4,6-trifluoroaniline. The desired product (243.9 mg) was obtained (yield 90%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 3.79 (s, 3H), 5.56 (brs, 1H), 6.63 (tt, J = 10.0, 7.1Hz, 1H), 6.84 (d, J = 8.9 Hz, 2H), 6.92 (brd, J = 8.9 Hz, 2H)
¹³ C NMR (125.77 MHz, CDCl ₃ ): δ = 55.8, 96.8, 114.6, 121.1, 124.6, 134.9, 139.4, 146.8, 156.2
¹⁹ F NMR (470.45 MHz, CDCl ₃ ): δ = -154.00, -154.08 (m, 2F), -141.49, -141.57 (m, 2F); IR (neat): ν~ = 3398 (m), 3083 ( w), 2927 (w), 2845 (w), 1646 (m), 1613 (w), 1526 (s), 1507 (s), 1497 (s), 1456 (s), 1409 (m), 1294 ( m), 1261 (m), 1241 (s), 1172 (s), 1120 (m), 1112 (m), 1077 (m), 1031 (m), 949 (s), 820 (s), 804 ( m), 769 (m), 726 (m), 709 (m), 691 (m)
HRMS (ESI): Calcd for C ₁₃ H ₉ F ₄ NO (M+H) ⁺ 271.0620, found 272.0694.

Table 3 shows a summary of the above Examples 1-15 to 1-20. The results of Examples 1-3 are also shown.

[Example 1-21]
In a 30 mL reaction flask equipped with a reflux tower, 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). ) Was weighed in and the system was replaced with nitrogen. 8 mL of dioxane was added thereto, 4.8 mmol (753.6 mg) of bromobenzene was further added, and the mixture was stirred for 5 minutes, then 3.7 mL of LHMDS 1.3 mol/L tetrahydrofuran solution (equivalent to LHMDS 4.8 mmol) was added, and a bath at 110° C. The mixture was heated and stirred for 5 hours (internal temperature: 92°C). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→90/10) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the target substance was fractionated. ..
Finally, the solvent was removed from the fractions collected under reduced pressure at 80°C to obtain 0.88 g of the desired product (yield 92%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 5.45 (brs, 1H), 6.85 (brd, 2H), 7.02 (brt, 1H), 7.30 (brt, 2H)
¹³ C NMR (125.77 MHz, CDCl ₃ ): δ = 116.7, 122.2, 129.5, 142.3
¹⁹ F NMR (470.53 MHz, CDCl ₃ ): δ = -164.9 (brt, 1F), -164.1 (dt, J = 22.1, 5.8 Hz, 2F), -150.7 (brd, 2F), IR (neat): ν ~ = 3408.2 (m), 1602.9 (m), 1521.8 (s), 1500.6 (s), 1483.3 (s), 1462.0 (S), 1421.54 (S), 1315.5 (m), 1292.31 (m)

[Example 1-22]
1.07 g of the desired product was obtained by the same reaction and post-treatment as in Example 1-21 except that 4.8 mmol (1023.0 mg) of 1-bromo-4-t-butylbenzene was used instead of bromobenzene. Was obtained (yield 91%).
¹ H NMR (500.13 MHz, Acetone): δ = 1.31 (s, 18H), 7.03 (d, J = 8.7 Hz, 4H), 7.36 (d, J = 8.7 Hz, 4H), 7.78 (brs, 2H)
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
¹⁹ F NMR (470.45 MHz, Acetone): δ = -152.67 (brd, F), -143.45-(-143.1) (m, 4F)
IR (neat): ν~ = 3406 (w), 3394 (w), 2966 (w), 2909 (w), 2869 (w), 1651 (m), 1610 (m), 1487 (s), 1449 ( m), 1403 (w), 1394 (w), 1364 (w), 1291 (w), 1263 (m), 1243 (m), 1191 (w), 1125 (w), 1115 (w), 1082 ( m), 996 (m), 976 (s), 829 (m), 821 (s), 728 (m), 723 (s)
HRMS (ESI): Calcd for C ₃₂ H ₂₈ F ₈ N ₂ (M+H) ⁺ 592.2125, found 593.2170.

[Example 1-23]
In a 30 mL reaction flask equipped with a reflux tower, 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). ) And 4-bromo-4′-t-butylbiphenyl (4.8 mmol, 1388.2 mg) were weighed in and the system was replaced with nitrogen. After 8 mL of dioxane was added thereto and stirred for 5 minutes, 3.7 mL of LHMDS 1.3 mol/L tetrahydrofuran solution (equivalent to LHMDS 4.8 mmol) was added, and the mixture was heated with stirring in a 110° C. bath for 5 hours (internal temperature 92° C.). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→90/10) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the target substance was fractionated. ..
Finally, the solvent was removed from the fractions collected under reduced pressure at 80°C to obtain 892.6 mg of the desired product (yield 60%).
¹ H NMR (500.13 MHz, THF): δ = 1.38 (s, 18H), 7.09 (brd, 4H), 7.47 (brd, 4H), 7.56 (brt, 8H), 8.07 (brs, 2H)
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
¹⁹ F NMR (470.45 MHz, THF): δ = -152.14 (brd, F), -143.24, -143.29 (m, 4F)
IR (neat): ν~ = 3421 (w), 3030 (w), 2960 (w), 2902 (w), 2866 (w), 1651 (m), 1608 (m), 1510 (s), 1484 ( s), 1457 (s), 1452 (s), 1394 (w), 1366 (w), 1359 (w), 1314 (w), 1293 (w), 1262 (m), 1238 (w), 1198 ( w), 1184 (w), 1121 (w), 1114 (w), 1085 (m), 997 (m), 972 (m), 816 (s), 778(w), 746 (w), 739 ( w), 721 (s), 667 (w)
HRMS (ESI): Calcd for C ₄₄ H ₃₆ F ₈ N ₂ (M+H) ⁺ 744.2751, found 745.2794.

[Example 1-24]
The reaction and post-treatment were performed in the same manner as in Example 1-23 except that 4.8 mmol (993.9 mg) of 1-bromonaphthalene was used instead of 4-bromo-4′-t-butylbiphenyl to obtain the desired product. 617.0 mg was obtained (yield 68%).
¹ H NMR (500.13 MHz, DMF): δ = 7.27 (brd, 2H), 7.51 (t, J = 7.8 Hz, 2H), 7.59-7.64 (m, 4H), 7.74 (brd, 2H), 8.00-8.03 (m, 2H), 8.47-8.50 (m, 2H), 8.82 (brs, 2H)
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, 129126.9, 127.4, 127.7, 128.6, 129, 135.6, 141.4, 146.1
¹⁹ F NMR (470.45 MHz, DMF): δ =-153.18 (brd, J = 13.9 Hz, 4F), -143.45-(-143.35) (m, 4F)
IR (neat): ν~ = 3396 (w), 3373 (w), 3063 (w), 1653 (m), 1595 (m), 1577 (w), 1522 (m), 1496 (s), 1489 ( s), 1466 (s), 1430 (m), 1401 (m), 1391 (m), 1274 (m), 1267 (m), 1251 (w), 1241 (w), 1168 (w), 1154 ( w), 1131 (w), 1106 (m), 1088 (w), 1075 (w), 1040 (w), 1017 (w), 986 (s), 955 (s), 794 (s), 772 ( s), 727 (s)
HRMS (ESI): Calcd for C ₃₂ H ₁₆ F ₈ N ₂ (M+H) ⁺ 580.1186, found 581.1249.

[Example 1-25]
The reaction and post-treatment were carried out in the same manner as in Example 1-23, except that 4.8 mmol (993.9 mg) of 2-bromonaphthalene was used instead of 4-bromo-4′-t-butylbiphenyl to obtain the desired product. 770.2 mg was obtained (yield 53%).
¹ H NMR (500.13 MHz, DMSO): δ = 7.23-7.35 (m, 6H), 7.43 (brt, 2H), 7.77 (brd, 2H), 7.83 (brt, 4H), 9.00 (brs, 2H)
¹³ C NMR (125.77 MHz, DMSO): δ = 98.2, 111.9, 119.9, 124.2, 124.4, 126.9, 127.0, 128.0, 129.0, 129.4, 134.3, 140.3, 140.9, 144.9.
¹⁹ F NMR (470.45 MHz, DMSO): δ = -148.08 (brd, 4F), -140.33 (brd, 4F)
IR (neat): ν~ = 3412 (m), 3054 (w), 1651 (m), 1627 (s), 1602 (m), 1591 (w), 1506 (s), 1484 (s), 1456 ( s), 1425 (m), 1290, 1276, 1264, 1225 (s), 1183 (m), 1132 (m), 1091 (s), 999 (s), 967 (s), 846 (s), 823 (s), 746 (s), 732 (s), 708 (m), 641 (m)
HRMS (ESI): Calcd for C ₃₂ H ₁₆ F ₈ N ₂ (M+H) ⁺ 580.1186, found 581.1249.

[Example 1-26]
Reaction and post-treatment were carried out in the same manner as in Example 1-23, except that 4.8 mmol (1556.2 mg) of 4-bromotriphenylamine was used instead of 4-bromo-4′-t-butylbiphenyl. 1417.3 mg of the target product was obtained (yield 87%).
¹ H NMR (500.13 MHz, Acetone): δ = 6.98 (t, J = 7.3, 4H), 7.05 (m, 16H), 7.26 (dd, J = 8.6, 7.3 Hz, 8H), 8.86 (brs, 2H)
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.
¹⁹ F NMR (470.45 MHz, Acetone): δ = -152.72 (brd, J = 13.9 Hz, 4F), -143.27 (m, 4F)
IR (neat): ν~ = 3394 (w), 3023 (w), 1649 (m), 1586 (m), 1485 (s), 1410 (m), 1333 (w), 1319 (w), 1293 ( w), 1273 (m), 1260 (m), 1235 (m), 1175 (w), 1156 (w), 1152 (w), 1132 (w), 1118 (w), 1112 (w), 1085 ( m), 995 (m), 974 (m), 968 (m), 899 (w), 891 (w), 826 (m), 817 (m), 749 (s), 739 (m), 722 ( m), 714 (m), 693 (s)
HRMS (ESI): Calcd for C ₄₈ H ₃₀ F ₈ N ₄ (M+H) ⁺ 814.2343, found 814.2312.

[Example 1-27]
The reaction and the post-treatment were performed in the same manner as in Example 1-23, except that 4.8 mmol (1781.9 mg) of 4-iodotriphenylamine was used instead of 4-bromo-4′-t-butylbiphenyl. 1101.3 mg of the target product was obtained (yield 68%).

[Example 1-28]
Instead of 4-bromo-4′-t-butylbiphenyl, 4-bromo-4′-(diphenylamino)biphenyl (4.8 mmol, 1921.5 mg) was used, and the same reaction and reaction as in Example 1-23. Post-treatment was performed to obtain 1903.1 mg of the desired product (yield 99%).

[Example 1-29]
In the same manner as in Example 24 except that 4.8 mmol (1897.4 mg) of 2-bromo-9,9′-spirobi[9H-fluorene] was used instead of 4-bromo-4′-t-butylbiphenyl. The reaction and post-treatment were carried out to obtain 1.88 g of the desired product (yield 98%).
¹ H NMR (500.13 MHz, Acetone): δ = 6.39 (brs, 2H), 6.62 (dd, J = 7.5, 1.0 Hz, 2H), 6.73 (dd, J = 7.5, 1.0 Hz, 4H), 7.05-7.09 (m, 4H), 7.16 (td, J = 7.5, 1.0 Hz, 4 H), 7.36 (td, J = 7.5, 1.0 Hz, 2H), 7.40 (td, J = 7.5, 1.0 Hz, 4 H), 7.82 (s, 2H), 7.89 (brdd, 4 H) 7.97 (brd, J = 7.5, 4 H)
¹³ C NMR (125.77 MHz, Acetone): δ = 66.9, 99.0, 114.6, 118.0, 120.5, 121.1, 121.5, 124.5, 124.8, 125.1, 127.9, 128.6, 128.88, 136.9, 141.2, 142.7, 142.8, 142.9, 145.8, 149.4, 149.9, 151.0
¹⁹ F NMR (470.45 MHz, Acetone): δ = -152.3 (brd, 4F), -143.2 (m, 4F)
IR (neat): ν~ = 3391 (w), 3063 (w), 3042 (w), 3015 (w), 1653 (m), 1614 (m), 1488 (s), 1446 (s), 1346 ( w), 1299 (m), 1290 (m), 1284 (m), 1267 (m), 1215 (m), 1167 (w), 1153 (w), 1120 (m), 1089 (m), 1078 ( m), 979 (m), 967 (m), 851 (w), 821 (m), 750 (s), 735 (s), 725 (s), 717 (s), 636 (m)
HRMS (ESI): Calcd for C ₆₂ H ₃₂ F ₈ N ₂ (M+H) ⁺ 956.2438, found 812.4212.

[Example 1-30]

In a 100 mL reaction flask equipped with a reflux tower, Pd(dppf)Cl ₂ 0.45 mmol (367.5 mg), potassium acetate 45 mmol (4416.3 mg), 3-bromo-N-phenylcarbazole 15 mmol (4823.2 mg), 11 mmol (4190.0 mg) of bis(pinacolato)diborone was weighed in and the system was replaced with nitrogen. After adding thereto 150 mL of N,N-dimethylformamide, the mixture was stirred for 5 minutes and then heated and stirred for 3 hours in a bath at 90°C. The reaction was traced by a chromatography (TLC) method using a minute amount of the reaction mixture collected from the system.
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 washed with 50 mL of ion-exchanged water in a separatory funnel, and then 50 mL of chloroform was added for extraction. The organic layer was collected from the separatory funnel. Then, the collected organic layer was dried over magnesium sulfate.
Magnesium sulfate was removed by filtration, the obtained filtrate was concentrated, and the obtained concentrate was subjected to column chromatography (developing solvent: hexane/ethyl acetate=100/0→96/4) to obtain the desired product. The containing fraction was collected.
Finally, the solvent was removed from the fractions collected under reduced pressure to obtain 4.21 g of pinacolato N-phenylcarbazol-3-yl-boronic acid (yield 76%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 1.41(s, 12H), 7.29 (ddd, J = 7.9, 6.0, 2.0 Hz, 1H), 7.37 (brd, J = 8.2 Hz, 1H), 7.40 ( m, 2H), 7.48 (t, J = 7.5 Hz, 1H), 7.55 (m, 2H), 7.61 (m, 2H), 8.76 (dd, J = 8.2, 1.2 Hz, 2H), 8.18 (d, J = 7.6 Hz, 1H), 8.64 (s, 1H)

Reaction flask fitted with a reflux column _{50mL, Pd (PPh 3) 4} 0.09mmol (104.1mg), sodium hydroxide 9mmol (359.9mg), N- phenyl-carbazol-3-yl - boronic acid pinacolato 3 mmol ( 1107.8 mg) and 4-bromo-4'-iodobiphenyl 3.3 mmol (1184.7 mg) were weighed in and the system was replaced with nitrogen. 13.5 mL of a mixed solvent (2/1 (v/v)) of tetrahydrofuran and water was added thereto, and the mixture was stirred for 5 minutes and then heated and stirred in a bath at 50°C for 5 hours. The reaction was traced by a chromatography (TLC) method using a minute amount of the reaction mixture collected from the system.
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 washed with 50 mL of ion-exchanged water in a separating funnel, and then 50 mL of tetrahydrofuran was added for extraction. The organic layer was collected from the separatory funnel. Then, the collected organic layer was dried over magnesium sulfate.
Magnesium sulfate was removed by filtration, the obtained filtrate was concentrated, and the obtained concentrate was subjected to column chromatography (developing solvent: hexane/ethyl acetate=100/0→96/4) to obtain the desired product. The containing fraction was collected.
Finally, the solvent was removed from the fractions collected under reduced pressure to obtain 810 mg of 4-bromo-4′-(N-phenylcarbazol-3-yl)-biphenyl (yield 57%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 7.30-7.33 (m, 1H), 7.43 (m, 2H), 7.50 (m, 4H), 7.57-7.70 (m, 9H), 7.79 (d, J = 8.5 Hz, 2H), 8.20 (d, J = 7.9 Hz, 1H), 8.39 (brs, 1H)

In a 30 mL reaction flask equipped with a reflux tower, Pd(DBA) ₂ 0.5 mmol (28.8 mg), RuPhos 0.75 mmol (35.0 mg), 4,4′-diaminooctafluorobiphenyl 0.5 mmol (164.1 mg). ) Was weighed in and the system was replaced with nitrogen. 8 mL of dioxane was added thereto, 1.05 mmol (498.1 mg) of 4-bromo-4′-(N-phenylcarbazol-3-yl)-biphenyl was added thereto, and the mixture was stirred for 5 minutes, and then LHMDS 1.3 mol/L tetrahydrofuran. 0.923 mL (1.2 mmol) of the solution was added, and the mixture was heated and stirred in a bath at 110°C for 5 hours (internal temperature 92°C). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→90/10) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the target substance was fractionated. ..
Finally, the solvent was removed from the fractions collected under reduced pressure at 80°C to obtain 457 mg of the desired product (yield 82%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 5.94 (brs, 2H), 7.11 (brd, 2H), 7.32 (brquin, 1H), 7.43 (brd, 2H), 7.48-7.51 (m, 2H), 7.60-7.66 (m, 6H), 7.70-7.72 (brm, 3H), 7.80-7.82 (m, 3H), 8.21 (brd, 2H), 8.41 (brs, 1H)

[Example 1-31]

In a 100 mL reaction flask equipped with a reflux tower, Pd(dppf)Cl ₂ 0.45 mmol (367.5 mg), potassium acetate 45 mmol (4416.3 mg), 2-bromo-9,9′-spirobi[9H-fluorene]. 15 mmol (5929.5 mg) and bis(pinacolato)diboron 16.5 mmol (4190.0 mg) were weighed in and the system was replaced with nitrogen. After adding thereto 150 mL of N,N-dimethylformamide, the mixture was stirred for 5 minutes and then heated and stirred for 3 hours in a bath at 90°C. The reaction was traced by a chromatography (TLC) method using a minute amount of the reaction mixture collected from the system.
After cooling the reaction mixture to room temperature, the solvent was removed from the cooled reaction mixture under reduced pressure and the mixture was concentrated. The concentrate was washed with 50 mL of deionized water in a separating funnel, and then 50 mL of chloroform was added for extraction. The organic layer was collected from the liquid funnel. Then, the collected organic layer was dried over magnesium sulfate.
Magnesium sulfate was removed by filtration, the obtained filtrate was concentrated, and the obtained concentrate was subjected to column chromatography (developing solvent: hexane/ethyl acetate=100/0→96/4) to obtain the desired product. The containing fraction was collected.
Finally, the solvent was removed from the fractions collected under reduced pressure to obtain 1.85 g of 9,9'-spirobi[9H-fluoren]-2-yl-boronic acid pinacolato (yield 28%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 1.25 (s, 12H), 6.68 (brd, J = 7.5 Hz 1H), 6.71 (brd, J = 7.5 Hz, 2H), 7.09 (dt, J = 7.5 , 1.1 Hz 2H), 7.11 (dt, J = 7.5, 1.1 Hz 1H), 7.18 (brs, 1H), 7.35 (dt, J = 7.5, 1.1 Hz 1H), 7.36 (dt, J = 7.5, 1.1 Hz 2H) ), 7.33-7.37 (m, 5H)

Reaction flask fitted with a reflux column _{50mL, Pd (PPh 3) 4} 0.09mmol (104.1mg), sodium hydroxide 9mmol (359.9mg), 9,9'- spirobi [9H-fluoren] -2 3 mmol (1327.1 mg) of yl-boronic acid pinacolato and 3.3 mmol (1184.7 mg) of 4-bromo-4'-iodobiphenyl were weighed in and the system was replaced with nitrogen. 13.5 mL of a mixed solvent of tetrahydrofuran and water (2/1 (v/v)) was added thereto, and the mixture was stirred for 5 minutes and then heated and stirred in a bath at 50° C. for 5 hours. The reaction was followed by chromatography (TLC) method using the reaction mixture.
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 washed with 50 mL of ion-exchanged water in a separating funnel, and then 50 mL of tetrahydrofuran was added for extraction. The organic layer was collected from the separatory funnel. Then, the collected organic layer was dried over magnesium sulfate.
Magnesium sulfate was removed by filtration, the obtained filtrate was concentrated, and the obtained concentrate was subjected to column chromatography (developing solvent: hexane/ethyl acetate=100/0→96/4) to obtain the desired product. The containing fraction was collected.
Finally, the solvent was removed from the fractions collected under reduced pressure to obtain 836.4 mg of 2-(4'-bromobiphenyl-4-yl)-9,9'-spirobi[9H-fluorene] (yield 51 %).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 6.73 (d, J = 7.6 Hz, 1H), 6.78 (d, J = 7.6 Hz, 2H), 6.97 (s, 1H), 7.12 (brt, 3H) , 7.36-7.42 (m, 5 H), 7.49 (s, 4H), 7.53 (d,2H), 7.66 (dd, J = 7.9, 1.8 Hz, 1H), 7.86 (d, J = 7.6 Hz, 2 H ), 7.87 (d, J = 7.6 Hz, 1 H), 7.92 (d, J = 7.9 Hz, 1H)

In a 30 mL reaction flask equipped with a reflux tower, Pd(DBA) ₂ 0.5 mmol (28.8 mg), RuPhos 0.75 mmol (35.0 mg), 4,4′-diaminooctafluorobiphenyl 0.5 mmol (164.1 mg). ) Was weighed in and the system was replaced with nitrogen. Dioxane (8 mL) was added thereto, and 2-(4'-bromobiphenyl-4-yl)-9,9'-spirobi[9H-fluorene] 1.05 mmol (574.9 mg) was added thereto, followed by stirring for 5 minutes. LHMDS 1.3 mol/L tetrahydrofuran solution 0.923 mL (corresponding to LHMDS 1.2 mmol) was added, and the mixture was heated and stirred in a 110° C. bath for 5 hours (internal temperature 92° C.). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→90/10) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the target substance was fractionated. ..
Finally, the solvent was removed from the fractions collected under reduced pressure at 80°C to obtain 532 mg of the desired product (yield 86%).
¹ H NMR (500.13 MHz, CDCl ₃ ): δ = 6.78 (brd, 2H), 6.83 (brd, 4H), 7.05 (brm, 6H), 7.15 (brt, 6H), 7.41 (brt, 6H), 7.54 ( brm, 12H), 7.70 (brd, 2H), 7.90 (brd, 6H), 7.95 (brd, 2H),
¹³ C NMR (125.77 MHz, CDCl ₃ ): δ = 118.7, 120.2, 120.3, 120.5, 122.8, 124.3, 124.4, 126.9, 127.1, 127.6, 127.8, 128.0, 128.1, 135.5, 139.4, 139.7, 140.4, 140.6, 141.3. , 141.6, 142.0, 18.9, 149.4, 149.8
¹⁹ F NMR (470.45 MHz, CDCl ₃ ): δ = -151.41 (brd, 4F), -140.63 (m, 4F)
IR (neat): ν~ = 3387.0 (w), 3059.1 (w), 3030.2 (w), 2953.0 (w), 2926.0 (w), 2856.6 (w), 1653.0 (m), 1606.7 (m), 1485.2 ( s), 1446.6 (s), 1236.4 (m), 1085.9 (m), 975.98 (m), 813.96 (s), 750.31 (s), 727.16 (s)

Table 4 shows a summary of Examples 1-21 to 1-31.

(4) Reaction of pentafluoroaniline with 4,4'-dibromobiphenyl

[Example 1-32]
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 into a 30 mL reaction flask equipped with a reflux tower. The system was replaced with nitrogen. 8 mL of dioxane and 2.4 mmol (439.3 mg) of pentafluoroaniline were added thereto, and the mixture was stirred for 5 minutes. The mixture was heated and stirred for 5 hours (internal temperature 92°C). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separating funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 30 mL of ethyl acetate for extraction. The organic layer was left in the separating funnel and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 20 mL of ethyl acetate for extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. Column chromatography (developing solvent: hexane/ethyl acetate=100/0→90/10) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the target substance was fractionated. ..
Finally, the solvent was removed from the fractions collected under reduced pressure at 80°C to obtain 451.7 mg of the desired product (yield 58%).
¹ H NMR (500.13 MHz, DMSO): δ = 6.86 (brd, J = 8.1 Hz, 4H), 7.45 (brd, J = 8.1 Hz, 4H), 8.32 (brs, 2H)
¹³ C NMR (125.77 MHz, DMSO): δ =116.1, 118.1, 126.9, 132.4, 137.0, 138.3, 142.3, 142.7
¹⁹ F NMR (470.45 MHz, DMSO): δ = -165.04 (brt, 2F), -163.81 (brt, 4F), -148.47 (brd, 4H)
IR (neat): ν~ = 3410 (m), 3029 (w), 1611 (m), 1577 (w), 1517 (s), 1502 (s), 1482 (s) 1446 (s), 1327 (m ), 1277 (m), 1238 (m), 1183 (m), 1159 (m), 1136 (m), 977 (s), 817 (s), 779 (m), 727 (m), 710 (m ); HRMS (ESI)

(5) Reaction of pentafluoroaniline with bromobenzene: influence of base

[Example 1-33]
Reaction and post-treatment were carried out in the same manner as in Example 1-11, except that pentafluoroaniline (1 mmol), bromobenzene (2.4 mmol), and LHMDS 1.3 mol/L tetrahydrofuran solution 1.85 mL (equivalent to LHMDS 2.4 mmol) were used. The desired product (179.8 mg) was obtained (yield 69%).

[Example 1-34]
Reaction and post-treatment were carried out in the same manner as in Example 1-11 except that pentafluoroaniline (2.4 mmol), bromobenzene (1 mmol), and LHMDS 1.3 mol/L tetrahydrofuran solution 1.85 mL (equivalent to LHMDS 2.4 mmol) were used. The desired product (193.6 mg) was obtained (yield 75%).

Table 5 shows a summary of Examples 1-33 and 1-34. From these results, it can be seen that the yield tends to decrease when an excess amount of base is present in the system.

(6) Synthesis of polymer

[Example 2-1]
In a 30 mL reaction flask equipped with a reflux tower, Pd(DBA) ₂ 0.08 mmol (46.0 mg), RuPhos 0.12 mmol (56.0 mg), 4,4′-diaminooctafluorobiphenyl 4.2 mmol (1378.3 mg). ) Was weighed in and the system was replaced with nitrogen. 8 mL of dioxane and 10 mmol of 1,4-dibromobenzene (943.6 mg) were added thereto, and the mixture was stirred for 5 minutes, then, LHMDS 1.3 mol/L tetrahydrofuran solution 7.1 mL (equivalent to LHMDS 9.2 mmol)) was added, and a bath at 110°C was added. The mixture was heated and stirred for 5 hours (internal temperature: 92°C). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separatory funnel together with 100 mL of a saturated aqueous solution of ammonium chloride and 50 mL of ethyl acetate for extraction, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 30 mL of ethyl acetate to perform extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. The solution obtained by dissolving the obtained residue in 10 mL of tetrahydrofuran was added dropwise to 500 mL of a mixed solvent of hexane and toluene (2/1 (v/v)), the resulting solid was collected by filtration, and the obtained solid was obtained. The product was dried at 80° C. under reduced pressure to obtain 0.47 g of the desired product.
¹ H NMR (500.13 MHz, DMSO): δ = 7.08 (brd, J = 7.7 Hz, 4H), 7.56 (brd, J = 7.7 Hz, 4H), 8.68 (brs, 2H)
¹³ C NMR (125.77 MHz, DMSO): δ = 97.2, 117.6, 123.9, 126.1, 127.8, 128.5, 132.9, 140.0, 140.7, 144.2.
¹⁹ F NMR (470.45 MHz, DMSO): δ = -148.76 (d, J = 17.3 Hz, 4F), -140.67 (s, 4F)
IR (neat): ν~ = 3421 (w), 3398 (w), 3030 (w), 1652 (m), 1610 (m), 1575 (w), 1482 (s), 1410 (m), 1394 ( m), 1291 (m), 1261 (s), 1234 (s), 1183 (m), 1118 (m), 1085 (s), 995 (s), 973 (s), 938 (m), 812 ( s), 721 (s)

[Example 2-2]
Reaction and post-treatment were carried out in the same manner as in Example 2-1, except that 0.4 mmol (230.0 mg) of Pd(DBA) ₂ and 0.6 mmol (280.0 mg) of RuPhos were used, and thus 1.60 g of the desired product was obtained. It was

Table 6 shows a summary of Example 2-1 and Example 2-2. As shown in Table 6, it is understood that the molecular weight of the obtained polymer can be controlled by changing the catalyst amount.

[Example 2-3]

In a 30 mL reaction flask equipped with a reflux tower, Pd(DBA) ₂ 0.5 mmol (287.5 mg), 0.75 mmol (350.0 mg), 4,4′-diaminooctafluorobiphenyl 2.5 mmol (820.4 mg). ) And 4,4'-dibromobiphenyl (2.38 mmol, 742.9 mg) were weighed in and the system was replaced with nitrogen. After adding 8 mL of dioxane thereto and stirring for 5 minutes, 7.1 mL of LHMDS 1.3 mol/L tetrahydrofuran solution (corresponding to 9.2 mmol of LHMDS) was added, and the mixture was heated with stirring in a 110° C. bath for 5 hours (internal temperature 92° C.). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separatory funnel together with 100 mL of a saturated aqueous solution of ammonium chloride and 50 mL of ethyl acetate for extraction, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 30 mL of ethyl acetate to perform extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. The solution obtained by dissolving the obtained residue in 10 mL of tetrahydrofuran was added dropwise to 500 mL of a mixed solvent of hexane and toluene (2/1 (v/v)), the resulting solid was collected by filtration, and the obtained solid was obtained. The product was dried at 80° C. under reduced pressure to obtain 1.01 g of the desired product. The obtained polymer had Mw=32,000, Mn=15,000 and Mw/Mn=2.13, and ΔT5 was 321.6° C., and Tg was not observed.

[Example 2-4]

In a 30 mL reaction flask equipped with a reflux tower, Pd(DBA) ₂ 0.3 mmol (172.5 mg), RuPhos 0.45 mmol (210.0 mg), 4,4′-diaminooctafluorobiphenyl 1.5 mmol (492.3 mg). ), and 1.43 mmol (572.3 mg) of 3,6-dibromo-9-phenylcarbazole were weighed in and the system was replaced with nitrogen. After 8 mL of dioxane was added thereto and stirred for 5 minutes, 2.54 mL of LHMDS 1.3 mol/L tetrahydrofuran solution (equivalent to LHMDS 3.3 mmol) was added, and the mixture was heated and stirred for 5 hours in a 110° C. bath (internal temperature 92° C.). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separatory funnel together with 100 mL of a saturated aqueous solution of ammonium chloride and 50 mL of ethyl acetate for extraction, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 30 mL of ethyl acetate to perform extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. The solution obtained by dissolving the obtained residue in 10 mL of tetrahydrofuran was added dropwise to 500 mL of a mixed solvent of hexane and toluene (2/1 (v/v)), and the resulting solid was collected by filtration, and the obtained filtrate was obtained. Was dried at 80° C. under reduced pressure to obtain 928 mg of the desired product. The obtained polymer had Mw=12,000, Mn=7,000, and Mw/Mn=1.71, and ΔT5 was 340.1° C., and Tg was not observed.
¹ H NMR (500.13 MHz, THF): δ = 5.39 (d, J = 8.5 Hz, 2H), 5.52 (d, J = 8.5 Hz, 2H), 5.62 (brs, H), 5.80 (brs, 4H), 6.07 (d, 2H), 7.62 (brd, J = 8.0 Hz, 2H), 8.06 (brs, 2H)
¹³ C NMR (125.77 MHz, THF): δ = 96.7, 110.8, 113.5, 121.4, 124.6, 126.2, 127.7, 127.8, 128.2, 129.1, 129.8, 130.9, 136.0, 139.1, 139.4, 140.2, 146.3.
¹⁹ F NMR (470.45 MHz, THF): δ = -151.34 (brd, 4F), -145.89 (brd, 4F)
IR (neat): ν~ = 3403 (w), 3029 (w), 2927 (w), 1651 (m), 1597 (w), 1483 (s), 1460 (s), 1364 (w), 1328 ( w), 1291 (w), 1282 (w), 1211 (m), 1166 (w), 1121 (w), 1080 (m), 1027 (w), 994 (m), 976 (s), 951 ( m), 939 (m), 925 (w), 863 (w), 757 (m), 723 (s)

[Example 2-5]

In a 30 mL reaction flask equipped with a reflux tower, Pd(DBA) ₂ 0.4 mmol (230.0 mg), RuPhos 0.6 mmol (280.0 mg), 4,4′-diaminooctafluorobiphenyl 2 mmol (656.3 mg), 1.90 mmol (670.6 mg) of 2,7-dibromo-9,9-dimethylfluorene was weighed in and the system was replaced with nitrogen. After 8 mL of dioxane was added thereto and stirred for 5 minutes, 3.2 mL of LHMDS 1.3 mol/L tetrahydrofuran solution (corresponding to 4.2 mmol of LHMDS) was added, and the mixture was heated and stirred in a 110° C. bath for 5 hours (internal temperature 92° C.). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separatory funnel together with 100 mL of a saturated aqueous solution of ammonium chloride and 50 mL of ethyl acetate for extraction, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 30 mL of ethyl acetate to perform extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. The solution obtained by dissolving the obtained residue in 10 mL of tetrahydrofuran was added dropwise to 500 mL of a mixed solvent of hexane and toluene (2/1 (v/v)), and the resulting solid was collected by filtration, and then at 80°C. It was dried under reduced pressure to obtain 926 mg of the desired product. The obtained polymer had Mw=20,000, Mn=11,000 and Mw/Mn=1.82, and ΔT5 was 340.1° C., and Tg was not observed.
¹ H NMR (500.13 MHz, THF): δ = 1.52 (s, 6H), 7.02 (brd, J = 8.0 Hz, 2H), 7.18 (s, 2H), 7.62 (brd, J = 8.0 Hz, 2H), 8.06 (brs, 2H)
¹³ C NMR (125.77 MHz, THF): δ = 26.6, 46.5, 97.1, 113.1, 117.4, 119.3, 125.0, 127.9, 128.7, 133.8, 139.9, 140.7, 145.1, 154.3
¹⁹ F NMR (470.45 MHz, THF): δ = -151.76 (brd, 4F), -142.20 (brd, 4F)
IR (neat): ν~ = 3423 (w), 2958 (w), 2925 (w), 2859 (w), 1651 (m), 1613 (w), 1587 (w), 1518 (m), 1485 ( s), 1464 (s), 1417 (m), 1295 (m), 1259 (w), 1239 (m), 1220 (w), 1195 (w), 1089 (m), 995 (m), 979 ( s), 971 (s), 809 (m), 724 (m), 718 (m)

[Example 2-6]

In a 30 mL reaction flask equipped with a reflux tower, Pd(DBA) ₂ 0.3 mmol (172.5 mg), RuPhos 0.45 mmol (210.0 mg), 4,4′-diaminooctafluorobiphenyl 1.5 mmol (492.3 mg). ), 9,10-dibromoanthracene 1.43 mmol (480 mg) were weighed in and the system was replaced with nitrogen. After 8 mL of dioxane was added thereto and stirred for 5 minutes, 2.54 mL of LHMDS 1.3 mol/L tetrahydrofuran solution (equivalent to LHMDS 3.3 mmol) was added, and the mixture was heated and stirred for 5 hours in a 110° C. bath (internal temperature 92° C.). During the process, a small amount of the solution in the flask was sampled and the reaction was traced using liquid chromatography. The area of the peak that can be attributed to the target substance increased as the area of the peak that can be attributed to the raw material decreased. At that time, no prominent peak corresponding to a by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was put into a separatory funnel together with 100 mL of a saturated aqueous solution of ammonium chloride and 50 mL of ethyl acetate for extraction, the organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated saline was put in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were respectively collected. Then, put all the collected aqueous layers together into a separating funnel, and add 30 mL of ethyl acetate to perform extraction, collect the organic layers, combine all the collected organic layers, and dry them with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate with a rotary evaporator. The solution obtained by dissolving the obtained residue in 10 mL of tetrahydrofuran was added dropwise to 500 mL of a mixed solvent of hexane and toluene (2/1 (v/v)), the resulting solid was collected by filtration, and the filtrate was collected. It was dried at 80° C. under reduced pressure to obtain 928 mg of the desired product. The polymer obtained had Mw=18,000, Mn=8,100 and Mw/Mn=2.22.
¹ H NMR (500.13 MHz, DMSO): δ = 7.60 (brs, 2H), 8.31 (brs, 2H), 9.30 (brs, 1H)
¹³ C NMR (125.77 MHz, CDCl ₃ ): δ = 123.9, 126.4, 128.7, 129.3, 131.3, 135.8, 137.7, 143.5, 145.5.
¹⁹ F NMR (470.53 MHz, CDCl ₃ ): δ = -160.0 (brs, 4F), -143.2 (brs, 4F)
IR (neat): ν~ = 3361.9 (w), 1651.1 (m), 1485.1 (s), 1435.0 (m), 1377.2 (m), 12771.1 (w), 1178.5 (w), 1134.1 (w), 1111.0 ( w), 1045.4 (w), 970.2 (s), 950.9 (m), 763.8 (s), 723.3 (s)

[2] Preparation of charge transporting composition and charge transporting thin film [Example 3-1]
35.9 mg of a fluorinated arylamine compound having a naphthyl group represented by the following formula (H1) synthesized in Example 1-24 in a sample bottle (10 mL) and an arylsulfonic acid compound 56 represented by the following formula (D2). 0.2 mg was weighed, 3 g of tetrahydrofurfuryl alcohol was added, and the mixture was stirred at room temperature until uniform, to obtain a solution having a solid content of 3% by mass. This solution was applied onto an ITO substrate using a spin coater, dried in the atmosphere at 80° C. for 1 minute, and then baked at 230° C. for 15 minutes to form a thin film having a thickness of 50 nm. As the ITO substrate, a glass substrate on the surface of which indium tin oxide (ITO) was formed with a film thickness of 50 nm was used. An aluminum thin film was formed on this thin film using a vapor deposition apparatus (vacuum degree 4.0×10 ⁻⁵ Pa) to obtain a single layer element. The vapor deposition was performed under the conditions of a vapor deposition rate of 0.2 nm/sec. The thickness of the aluminum thin film was 80 nm. The aryl sulfonic acid compound represented by the following formula (D2) was synthesized according to the method described in WO 2006/025342.

[Example 3-2]
44 mg of a fluorinated arylamine compound having a triphenylamine group represented by the following formula (H2) synthesized in Example 1-26 in a sample bottle (10 mL) and 49 mg of the arylsulfonic acid compound represented by the above formula (D2). Was weighed out, 3 g of tetrahydrofurfuryl alcohol was added, and the mixture was stirred at room temperature until uniform, to obtain a solution having a solid content of 3% by mass. A single-layer element was produced in the same manner as in Example 3-1, except that this solution was used.

[Example 3-3]
21.6 mg of a fluoroarylamine copolymer having a biphenyl skeleton represented by the following formula (H3) synthesized in Example 2-3 in a sample bottle (10 mL) and the arylsulfonic acid represented by the above formula (D2) 40 mg of the compound was weighed out, 3 g of tetrahydrofurfuryl alcohol was added, and the mixture was stirred at room temperature until uniform, to obtain a solution having a solid content of 2% by mass. A single-layer element was produced in the same manner as in Example 3-1, except that this solution was used.

[Example 3-4]
36 mg of a fluoroarylamine copolymer having a phenylcarbazole group represented by the following formula (H4) synthesized in Example 2-4 in a sample bottle (10 mL), and an arylsulfonic acid represented by the above formula (D2) 57 mg of the compound was weighed out, 3 g of tetrahydrofurfuryl alcohol was added, and the mixture was stirred at room temperature until uniform, to obtain a solution having a solid content of 3% by mass. A single-layer element was produced in the same manner as in Example 3-1, except that this solution was used.

[Example 3-5]
In a sample bottle (10 mL), 34 mg of a fluoroarylamine copolymer having a 9,9-dimethylfluorene group represented by the following formula (H5) synthesized in Example 2-5 and the above formula (D2) were represented. 59 mg of the aryl sulfonic acid compound was weighed out, 3 g of tetrahydrofurfuryl alcohol was added, and the mixture was stirred at room temperature until uniform, to obtain a solution having a solid content of 3% by mass. A single-layer element was produced in the same manner as in Example 3-1, except that this solution was used.

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

As shown in Table 7, it is understood that the thin film containing the fluorinated arylamine compound or polymer of the present invention as the charge transporting substance exhibits good conductivity.

Claims (30)

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. A method for producing a fluorinated aromatic secondary amine compound,
The catalyst comprises a palladium zero-valent complex of dibenzylideneacetone,
The method for producing a fluorinated aromatic secondary amine compound, wherein the ligand contains a biphenylphosphine compound represented by the following formula (L).

(In the formula, each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ^{2 to} R ⁵ each independently represent a hydrogen atom or a carbon number. Represents an alkyl group having 1 to 20 or an alkoxy group having 1 to 20 carbon atoms, and R ^{6 to} R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. , or an NR ⁹ ₂ group, R ⁹ each independently represent an alkyl group having 1 to 20 carbon atoms.) The catalyst is a palladium zero-valent complex of dibenzylideneacetone,
The method for producing a fluorinated aromatic secondary amine compound according to claim 1, wherein the ligand is a biphenylphosphine compound represented by the formula (L). The R ¹ is each independently a branched chain alkyl group having 3 to 20 carbon atoms or a cyclic alkyl group in which the carbon atom bonded to the phosphorus atom is a secondary or tertiary carbon atom. 2. The method for producing a fluorinated aromatic secondary amine according to 2. The method for producing a fluorinated aromatic secondary amine according to claim 3, wherein both R ¹ are a cyclohexyl group or a t-butyl group. R ² and R ⁵ each independently represent a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, R ³ and R ⁴ are both hydrogen atoms, and R ^{6 to} R ⁸ are respectively The method for producing a fluorinated aromatic secondary amine according to any one of claims 1 to 4, which independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. .. The fluorinated aroma according to any one of claims 1 to 5, wherein the biphenylphosphine compound represented by the formula (L) is a biphenylphosphine compound represented by any of the following formulas (L1) to (L4). For producing a secondary amine of group C.

(In the formula, Me means a methyl group, i-Pr means an isopropyl group, Cy means a cyclohexyl group, and t-Bu means a t-butyl group.) The method for producing a fluorinated aromatic secondary amine according to claim 1, wherein the palladium zero-valent complex of dibenzylideneacetone is bis(dibenzylideneacetone)palladium(0). The fluorinated aromatic primary amine compound is a fluorinated aromatic primary monoamine compound or diamine compound having two or more fluorine atoms in the molecule, according to any one of claims 1 to 7. Process for producing aromatic secondary amine. 9. The chlorinated, brominated or iodinated aromatic hydrocarbon is a mono or dichloro aromatic hydrocarbon, a mono or dibromo aromatic hydrocarbon, or a mono or diiodo aromatic hydrocarbon. Item 6. A method for producing a fluorinated aromatic secondary amine according to the item. A fluorine-containing aniline derivative represented by the formula (T1) or (T2) (however, the compounds represented by the following formulas [1] to [13] are excluded).

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

(In the formula, L ⁰¹ is —S—, —O—, —CO—, —CH ₂ —, —(CH ₂ ) ₂ —, —C(CH ₃ ) ₂ —, —CF ₂ —, —(CF _{2) 2 -, - C (} CF 3) 2 -, 9,9-diyl group, -NH- or -NZ ¹⁰ - represents,
L ⁰² and L ⁰³ are each independently hydrogen atom, Z ¹¹ alkyl group carbon atoms which may be have 1 to 20 substituents, alkenyl group optionally having 2 to 20 carbon atoms optionally substituted by Z ¹¹ Or represents an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² .
L ⁰⁴ represents a hydrogen atom, optionally substituted alkenyl group or Z ¹² alkyl group, optionally 2 to 20 carbon atoms optionally substituted by Z ¹¹ of carbon atoms which may be have 1-20 substituted with Z ¹¹ Represents an aryl group having 6 to 20 carbon atoms,
Z 'represents a substituent of the aromatic ring, each independently, an alkyl group having carbon atoms which may be have 1-20 replaced by Z ^11, Z ¹¹ which may be 2-20 carbons substituted with Represents an alkenyl group or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² .
Z ^{01 to} Z ⁰⁹ represent a substituent of an aromatic ring, and each independently represent a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹¹ , Represents an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z ¹¹ or an aryl group having 6 to 20 carbon atoms which may be substituted by Z ¹² .
Z ¹⁰ represents an alkyl group having carbon atoms which may be have 1-20 replaced by Z ^11, which may be substituted with alkenyl or Z ¹² good 2 to 20 carbon atoms optionally substituted by Z ¹¹ carbon Represents an aryl group of the number 6 to 20,
Z ^11's each independently represent a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³ .
Z ¹² are each independently a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, optionally substituted with an alkyl group or Z ¹³ of carbon atoms which may be have 1-20 substituted with Z ¹³ Represents a good alkenyl group 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,
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 are substituted with an aromatic ring. Represents the number of fluorine atoms
a ¹² , a ¹⁴ , a ²² , a ²⁴ , a ³² , a ³⁴ , a ⁴² , a ⁵² , a ⁶² , a ⁷² , a ⁷⁴ , a ⁸² , a ⁸⁴ , a ⁹² and a ⁹⁴ are substituted with an aromatic ring. Represents the number of Z ^{01 to} Z ⁰⁹
a ⁷⁵ and a ⁷⁶ represent the number of Z′ substituting the aromatic ring,
a ¹¹ is an integer of 2 to 4, a ¹² is an integer of 0 to 2 and satisfies a ¹¹ +a ¹² ≦4,
a ¹³ is an integer of 2 to 4, a ¹⁴ is an integer of 0 to 2 and satisfies a ¹³ +a ¹⁴ ≦4,
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 Satisfies ²⁴ ≤ 4,
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. Satisfies ³⁴ ≤ 4,
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,
a ⁵¹ is an integer of 1 to 8, a ⁵² is an integer of 0 to 7 and a ⁵¹ +a ⁵² ≦8 is satisfied,
a ⁶¹ is an integer of 1 to 8, a ⁶² is an integer of 0 to 7 and a ⁶¹ +a ⁶² ≦8 is satisfied,
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 a ⁷¹ +a ⁷² ≦3 and a ⁷³ +a ⁷⁴ ≦3 is satisfied, and a ⁷⁵ and a ⁷⁶ are each independently an integer of 0 to 4,
a ⁸¹ and a ⁸³ are each independently an integer of 1 to 3, a ⁸² and a ⁸⁴ are each independently an integer of 0 to 2, and a ⁸¹ +a ⁸² ≦3 and a ⁸³ +a ^{Satisfying 84} ≦3,
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 a ⁹¹ +a ⁹² ≦3 and a ⁹³ +a ⁹⁴ ≦3 is satisfied. )
Y ²¹¹ and Y ²¹² each independently represent a monovalent group represented by any of formulas (B01) to (B21),

(In the formula, L ¹¹ is —S—, —O—, —CO—, —CH ₂ —, —(CH ₂ ) ₂ —, —C(CH ₃ ) ₂ —, —CF ₂ —, —(CF _{2) 2 -, - C (} CF 3) 2 -, 9,9-diyl group, -NH- or -NZ ¹⁰⁰ - represents,
L ¹² represents a hydrogen atom, optionally substituted alkenyl group or Z ¹³¹ of is an alkyl group having 1 to 20 carbon atoms also be good 2-20 carbon atoms substituted with Z ¹³⁰ substituted with Z ¹³⁰ Represents an aryl group having 6 to 20 carbon atoms,
L ¹³ and L ¹⁴ are each independently a hydrogen atom, Z ¹³⁰ with an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ¹³⁰ Or represents an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³¹ ,
Z ¹⁰⁰ represents an alkyl group with carbon atoms which may have 1 to 20 substituted by Z ^130, which may be substituted with alkenyl or Z ¹³¹ good 2 to 20 carbon atoms optionally substituted by Z ¹³⁰ carbon Represents an aryl group of the number 6 to 20,
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, or a C 1-20 optionally substituted with Z ^130. Represents an alkyl group having 2 to 20 carbon atoms, which may be substituted with Z ¹³⁰ , or an aryl group having 6 to 20 carbon atoms, which may be substituted with Z ¹³¹ .
Z ¹⁰⁸ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having carbon atoms which may be have 1-20 substituted with Z ^130, is substituted with Z ¹³⁰ Represents an alkenyl group having 2 to 20 carbon atoms which may be present or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³¹ , and Z ¹⁰⁸ existing on different benzene rings are bonded to each other to form a ring. May be formed,
Z ^{130 s} each independently represent a fluorine atom, a chlorine atom, a bromine atom or an aryl group having 6 to 20 carbon atoms, which may be substituted with Z ¹³² .
Z ¹³¹ are each independently a fluorine atom, a chlorine atom, a bromine atom, an alkyl group or Z ¹³² carbon atoms which may be have 2-20 substituted with 1 to 20 carbon atoms which may be substituted with Z ¹³² Represents an alkenyl group of
Z ¹³² represents a fluorine atom, a chlorine atom or a bromine atom,
Ar ^1's each independently represent an aryl group having 6 to 20 carbon atoms,
Ar ² represents a single bond or an arylene group having 6 to 20 carbon atoms. )
X ²²¹ and X ²²² each independently represent a monovalent group represented by any of formulas (C01) to (C09),

(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 are aromatic rings. Represents the number of fluorine atoms to be substituted,
b ¹² , b ²² , b ²⁴ , b ³² , b ³⁴ , b ⁴² , b ⁵² , b ⁶² , b ⁷² , b ⁷⁴ , b ⁸² , b ⁸⁴ , b ⁹² and b ⁹⁴ are substituted with an aromatic ring Z ⁰¹ ~ Represents the number of Z ⁰⁹ ,
b ⁷⁵ and b ⁷⁶ represent the number of Z′ substituting the aromatic ring,
b ¹¹ is an integer of 2 to 5, b ¹² is an integer of 0 to 3 and satisfies b ¹¹ +b ¹² ≦5,
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 satisfying b ²¹ +b ²² ≦4 and b ²³ +b ²⁴ ≦5,
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 are satisfied,
b ⁴¹ is an integer of 1 to 7, b ⁴² is an integer of 0 to 6, and b ⁴¹ +b ⁴² ≦7 is satisfied,
b ⁵¹ is an integer of 1 to 9, b ⁵² is an integer of 0 to 8 and satisfies b ⁵¹ +b ⁵² ≦9,
b ⁶¹ is an integer of 1 to 9, b ⁶² is an integer of 0 to 8 and satisfies b ⁶¹ +b ⁶² ≦9,
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 are satisfied, and b ⁷⁵ and b ⁷⁶ are each independently an integer of 0 to 4,
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,
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 b ⁹¹ +b ⁹² ≤3 and b ⁹³ +b ⁹⁴ ≤4 are satisfied,
L ^{01 to} L ⁰⁴ , Z′ and Z ^{01 to} Z ⁰⁷ have the same meanings as described above. )
Y ²²¹ represents a divalent group represented by any of formulas (D01-1) to (D21).

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

The fluorine-containing aniline derivative according to claim 10, wherein X ²¹¹ is a divalent group represented by the formula (A02). The fluorine-containing aniline derivative according to claim 11, wherein X ²¹¹ is a divalent group represented by the following formula (A02-1).

(In the formula, a ^{21 to} a ²⁴ and Z ⁰² have the same meanings as described above.) The fluorine-containing aniline derivative according to claim 10, wherein Y ²¹¹ and Y ²¹² are the same monovalent group. 14. The fluorine-containing group according to claim 13, wherein both Y ²¹¹ and Y ²¹² are a monovalent group represented by any of the formulas (B01), (B02), (B04), (B08) and (B18). Aniline derivative. The fluorinated aniline derivative according to claim 10, wherein Y ²²¹ is a divalent group represented by the formula (D02). The fluorine-containing aniline derivative according to claim 15, wherein Y ²²¹ is a divalent group represented by the following formula (D02-1).

The fluorine-containing aniline derivative according to claim 10, 15 or 16, wherein X ²²¹ and X ²²² are the same monovalent group. The fluorine-containing aniline derivative according to claim 17, wherein both X ²²¹ and X ²²² are a monovalent group represented by the formula (C01). A polymer containing a repeating unit represented by the following formula (P1-2).

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

(In the formula, L ⁰¹ is —S—, —O—, —CO—, —CH ₂ —, —(CH ₂ ) ₂ —, —C(CH ₃ ) ₂ —, —CF ₂ —, —(CF _{2) 2 -, - C (} CF 3) 2 -, 9,9-diyl group, -NH- or -NZ ¹⁰ - represents,
L ⁰² and L ⁰³ are each independently hydrogen atom, Z ¹¹ alkyl group carbon atoms which may be have 1 to 20 substituents, alkenyl group optionally having 2 to 20 carbon atoms optionally substituted by Z ¹¹ Or represents an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² .
L ⁰⁴ represents a hydrogen atom, optionally substituted alkenyl group or Z ¹² alkyl group, optionally 2 to 20 carbon atoms optionally substituted by Z ¹¹ of carbon atoms which may be have 1-20 substituted with Z ¹¹ Represents an aryl group having 6 to 20 carbon atoms,
Z 'represents a substituent of the aromatic ring, each independently, an alkyl group having carbon atoms which may be have 1-20 replaced by Z ^11, Z ¹¹ which may be 2-20 carbons substituted with Represents an alkenyl group or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² .
Z ^{01 to} Z ⁰⁹ represent a substituent of an aromatic ring, and each independently represent a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹¹ , Represents an alkenyl group having 2 to 20 carbon atoms which may be substituted by Z ¹¹ or an aryl group having 6 to 20 carbon atoms which may be substituted by Z ¹² .
Z ¹⁰ represents an alkyl group having carbon atoms which may be have 1-20 replaced by Z ^11, which may be substituted with alkenyl or Z ¹² good 2 to 20 carbon atoms optionally substituted by Z ¹¹ carbon Represents an aryl group of the number 6 to 20,
Z ^11's each independently represent a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³ .
Z ¹² are each independently a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, optionally substituted with an alkyl group or Z ¹³ of carbon atoms which may be have 1-20 substituted with Z ¹³ Represents a good alkenyl group 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,
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 are substituted with an aromatic ring. Represents the number of fluorine atoms
a ¹² , a ¹⁴ , a ²² , a ²⁴ , a ³² , a ³⁴ , a ⁴² , a ⁵² , a ⁶² , a ⁷² , a ⁷⁴ , a ⁸² , a ⁸⁴ , a ⁹² and a ⁹⁴ are substituted with an aromatic ring. Represents the number of Z ^{01 to} Z ⁰⁹
a ⁷⁵ and a ⁷⁶ represent the number of Z′ substituting the aromatic ring,
a ¹¹ is an integer of 2 to 4, a ¹² is an integer of 0 to 2 and satisfies a ¹¹ +a ¹² ≦4,
a ¹³ is an integer of 2 to 4, a ¹⁴ is an integer of 0 to 2 and satisfies a ¹³ +a ¹⁴ ≦4,
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 Satisfies ²⁴ ≤ 4,
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. Satisfies ³⁴ ≤ 4,
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,
a ⁵¹ is an integer of 1 to 8, a ⁵² is an integer of 0 to 7 and a ⁵¹ +a ⁵² ≦8 is satisfied,
a ⁶¹ is an integer of 1 to 8, a ⁶² is an integer of 0 to 7 and a ⁶¹ +a ⁶² ≦8 is satisfied,
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 a ⁷¹ +a ⁷² ≦3 and a ⁷³ +a ⁷⁴ ≦3 is satisfied, and a ⁷⁵ and a ⁷⁶ are each independently an integer of 0 to 4,
a ⁸¹ and a ⁸³ are each independently an integer of 1 to 3, a ⁸² and a ⁸⁴ are each independently an integer of 0 to 2, and a ⁸¹ +a ⁸² ≦3 and a ⁸³ +a ^{Satisfying 84} ≦3,
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 a ⁹¹ +a ⁹² ≦3 and a ⁹³ +a ⁹⁴ ≦3 is satisfied. )
Y ²²¹ represents a divalent group represented by any of formulas (D01-1) to (D21).

(In the formula, L ¹¹ is —S—, —O—, —CO—, —CH ₂ —, —(CH ₂ ) ₂ —, —C(CH ₃ ) ₂ —, —CF ₂ —, —(CF _{2) 2 -, - C (} CF 3) 2 -, 9,9-diyl group, -NH- or -NZ ⁰² - represents,
L ¹² represents a hydrogen atom, optionally substituted alkenyl group or Z ¹³¹ of is an alkyl group having 1 to 20 carbon atoms also be good 2-20 carbon atoms substituted with Z ¹³⁰ substituted with Z ¹³⁰ Represents an aryl group having 6 to 20 carbon atoms,
L ¹³ and L ¹⁴ are each independently a hydrogen atom, Z ¹³⁰ with an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group which may C2-20 optionally substituted by Z ¹³⁰ Or represents an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³¹ ,
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, or a C 1-20 optionally substituted with Z ^130. Represents an alkyl group having 2 to 20 carbon atoms, which may be substituted with Z ¹³⁰ , or an aryl group having 6 to 20 carbon atoms, which may be substituted with Z ¹³¹ .
Z ¹⁰⁸ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkyl group having carbon atoms which may be have 1-20 substituted with Z ^130, is substituted with Z ¹³⁰ Represents an alkenyl group having 2 to 20 carbon atoms which may be present or an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³¹ , and Z ¹⁰⁸ existing on different benzene rings are bonded to each other to form a ring. May be formed,
Z ^{130 s} each independently represent a fluorine atom, a chlorine atom, a bromine atom or an aryl group having 6 to 20 carbon atoms, which may be substituted with Z ¹³² .
Z ¹³¹ are each independently a fluorine atom, a chlorine atom, a bromine atom, an alkyl group or Z ¹³² carbon atoms which may be have 2-20 substituted with 1 to 20 carbon atoms which may be substituted with Z ¹³² Represents an alkenyl group of
Z ¹³² represents a fluorine atom, a chlorine atom or a bromine atom,
Ar ^1's each independently represent an aryl group having 6 to 20 carbon atoms,
Ar ^3's each independently represent an arylene group having 6 to 20 carbon atoms. )] The polymer according to claim 19, wherein the X ²¹¹ is a divalent group represented by the formula (A02). 21. The polymer according to claim 20, wherein X ²¹¹ is a divalent group represented by the following formula (A02-1).

(In the formula, a ^{21 to} a ²⁴ and Z ⁰² have the same meanings as described above.) 22. The polymer according to claim 19, wherein Y ²²¹ is a divalent group represented by any of the formulas (D02), (D17) and (D19). A charge-transporting substance comprising the aniline derivative according to any one of claims 10 to 18. A charge-transporting substance comprising the polymer according to any one of claims 19 to 22. A charge-transporting composition comprising the charge-transporting substance according to claim 23 or 24 and an organic solvent. The charge transporting composition according to claim 25, comprising a dopant substance. A charge-transporting thin film obtained from the charge-transporting composition according to claim 25 or 26. An electronic device comprising the charge transporting thin film according to claim 27. An organic electroluminescence device comprising the charge transporting thin film according to claim 27. 30. The organic electroluminescence device according to claim 29, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.