JP2005132829A - Aromatic compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new aromatic compound having 3 or 4 condensable functional groups or their precursors. <P>SOLUTION: The aromatic compound is expressed by formula (1) or (2). In the formulae, Ar<SP>1</SP>and Ar<SP>3</SP>express each a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic group; Ar<SP>2</SP>expresses a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group; A<SP>1</SP>expresses Z<SP>1</SP>, Z<SP>2</SP>, Z<SP>3</SP>or Z<SP>4</SP>=Z<SP>5</SP>; Z<SP>1</SP>, Z<SP>2</SP>and Z<SP>3</SP>express each O, S or the like; Z<SP>4</SP>and Z<SP>5</SP>express each N, B, P or the like; X<SP>1</SP>, X<SP>2</SP>, X<SP>3</SP>and X<SP>4</SP>express each a halogen atom or the like. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an aromatic compound having three or four condensation-reactive functional groups or precursors thereof, which can be used as a raw material monomer for a branched polymer compound.

High molecular weight light emitting materials (polymer light emitters) have been studied in various ways since they are soluble in solvents and can form a light emitting layer in a light emitting device by a coating method, unlike low molecular weight materials. ,Are known.
An aromatic compound having two condensation-reactive functional groups (for example, WO97 / 05184) is used as a monomer for producing these polymer light emitters.
On the other hand, in recent years, attempts have been made to make branched polymer compounds in order to improve the performance of polymer light emitters, and aromatic compounds having three condensation-reactive functional groups that can be used as monomers are disclosed. (For example, WO96 / 17035). However, in order to create various branched polymer compounds, the types were insufficient.

WO96 / 17035

  The object of the present invention is to provide a novel aromatic compound having three or four condensation-reactive functional groups or precursors thereof.

［式中、Ａｒ¹およびＡｒ³は、それぞれ独立に、４価の芳香族炭化水素基または４価の複素環基を表す。Ａｒ²は、３価の芳香族炭化水素基または３価の複素環基を表し、該
Ａｒ¹、Ａｒ²およびＡｒ³は置換基を有していてもよく、Ａｒ¹およびＡｒ²が置換基を有する場合、それらが結合して環を形成していてもよく、Ａｒ¹およびＡｒ³が置換基を有する場合、それらが結合して環を形成していてもよい。
また、Ａ¹は、−Ｚ¹−、−Ｚ²−Ｚ³−または−Ｚ⁴＝Ｚ⁵−を表し、Ｚ¹、Ｚ²、およびＺ³は、それぞれ独立に、Ｏ、Ｓ、Ｃ（＝Ｏ）、Ｓ（＝Ｏ）、ＳＯ₂、Ｃ（Ｒ¹）（Ｒ²）、Ｓｉ（Ｒ³）（Ｒ⁴）、Ｎ（Ｒ⁵）、Ｂ（Ｒ⁶）、Ｐ（Ｒ⁷）またはＰ（＝Ｏ）（Ｒ⁸）を表し、Ｚ⁴およびＺ⁵は、それぞれ独立に、Ｎ、Ｂ、Ｐ、Ｃ（Ｒ⁹）またはＳｉ(Ｒ¹⁰)
（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹およびＲ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールエチニル基、カルボキシル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アリールアルキルオキシカルボニル基、ヘテロアリールオキシカルボニル基またはシアノ基を表す。ただし、Ｒ¹とＲ²、Ｒ³とＲ⁴は互いに結合して環を形成していてもよい。）を表す。ただし式（１）において、Ａｒ²とＡ¹はＡｒ¹環上の互いに隣接する原子に結合し、Ａｒ¹とＡ¹はＡｒ²環上の互いに隣接する原子隣に結合し、式（２）においてＡｒ³とＡ¹はＡｒ¹環上の互いに隣接する原子に結合し、Ａｒ¹とＡ¹はＡｒ³環の互いに隣接する原子上に結合する。
また、Ｘ¹、Ｘ²、Ｘ³およびＸ⁴は、それぞれ独立にハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル基、−Ｂ（ＯＨ）₂、モノハロゲン化メチル基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、シアノメチル基、ホルミル基、ビニル基、水酸基、アルキルオキシ基、アシルオキシ基、置換シリルオキシ基、アミノ基またはニトロ基を表し、式（１）におけるＸ¹、Ｘ²、およびＸ³の少なくとも一つ並びに式（２）における、Ｘ¹、Ｘ²、Ｘ³およびＸ⁴の少なくとも一つはハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル基、−Ｂ（ＯＨ）₂、モノハロゲン化メチル基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、シアノメチル基、ホルミル基、ビニル基から選ばれる。〕 That is, the present invention provides an aromatic compound represented by the following formula (1) or (2).

[Wherein, Ar ¹ and Ar ³ each independently represents a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic group. Ar ² represents a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and Ar ¹ , Ar ² and Ar ³ may have a substituent, and Ar ¹ and Ar ² are a substituent. When they have, they may combine to form a ring, and when Ar ¹ and Ar ³ have a substituent, they may combine to form a ring.
A ¹ represents -Z ^1- , -Z ² -Z ³ -or -Z ⁴ = Z ^5- , and Z ¹ , Z ² and Z ³ are each independently O, S, C ( = O), S (= O), SO ₂ , C (R ¹ ) (R ² ), Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) Or P (═O) (R ⁸ ), and Z ⁴ and Z ⁵ are each independently N, B, P, C (R ⁹ ) or Si (R ¹⁰ ).
Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group , Alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group Substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, carboxyl group, alkyloxycarbonyl group, Aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycal It represents an alkenyl group, or a cyano group. However, R ¹ and R ^2, R ³ and R ⁴ represents a bond to each other may form a ring.). However, in Formula (1), Ar ² and A ¹ are bonded to adjacent atoms on the Ar ¹ ring, Ar ¹ and A ¹ are bonded to adjacent atoms on the Ar ² ring, and Formula (2) In which Ar ³ and A ¹ are bonded to adjacent atoms on the Ar ¹ ring, and Ar ¹ and A ¹ are bonded to adjacent atoms on the Ar ³ ring.
X ¹ , X ² , X ³ and X ⁴ each independently represent a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, —B (OH) ₂ , monohalogenated methyl Represents a group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group, vinyl group, hydroxyl group, alkyloxy group, acyloxy group, substituted silyloxy group, amino group or nitro group, X in formula (1) ¹ , at least one of X ² and X ³ and at least one of X ¹ , X ² , X ³ and X ⁴ in formula (2) is a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group , Borate group, -B (OH) ₂ , monohalogenated methyl group , Sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group, and vinyl group. ]

〔式中、Ａ¹およびＸ³は、前記と同じ意味を表し、Ａｒ⁴、Ａｒ⁵、Ａｒ⁶およびＡｒ⁷は、それぞれ独立に３価の芳香族炭化水素基または３価の複素環基を表すし、該Ａｒ⁴、Ａｒ⁵、Ａｒ⁶およびＡｒ⁷は置換基を有していてもよく、Ａｒ⁴およびＡｒ⁵が置換基を有する場合、それらが結合して環を形成していてもよい。
Ｘ⁹、Ｘ¹⁰、Ｘ¹¹およびＸ¹²は、それぞれ独立にハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル基、−Ｂ（ＯＨ）₂、モノハロゲン化メチル基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、シアノメチル基、ホルミル基、ビニル基、水酸基、アルキルオキシ基、アシルオキシ基、置換シリルオキシ基、アミノ基またはニトロ基を表し、式（５）におけるＸ⁹、Ｘ¹⁰およびＸ³の少なくとも一つ並びに式（６）における、Ｘ⁹、Ｘ¹⁰、Ｘ¹¹およびＸ¹²の少なくとも一つは、ハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル基、−Ｂ（ＯＨ）₂、モノハロゲン化メチル基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、シアノメチル基、ホルミル基またはビニル基である。〕 The present invention also provides an aromatic compound represented by the following formula (5) or (6).

[Wherein, A ¹ and X ³ represent the same meaning as described above, and Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group. And Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ may have a substituent, and when Ar ⁴ and Ar ⁵ have a substituent, they may combine to form a ring. Good.
X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, —B (OH) ₂ , a monohalogenated methyl group, Represents a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a cyanomethyl group, a formyl group, a vinyl group, a hydroxyl group, an alkyloxy group, an acyloxy group, a substituted silyloxy group, an amino group or a nitro group, and X ⁹ in formula (5), At least one of X ¹⁰ and X ³ and at least one of X ⁹ , X ¹⁰ , X ¹¹ and X ¹² in formula (6) are a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boron Acid ester group, -B (OH) ₂ , monohalogenated methyl group, A sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a cyanomethyl group, a formyl group or a vinyl group. ]

［式中、Ａｒ⁴およびＡｒ⁵は、前記と同じ意味を表し、Ａｒ⁸、Ａｒ⁹およびＡｒ¹⁰はそれぞれ独立にアリーレン基または２価の複素環基を表し、該Ａｒ⁴、Ａｒ⁵、Ａｒ⁸、Ａｒ⁹およびＡｒ¹⁰は置換基を有していてもよく、Ａｒ⁴およびＡｒ⁵が置換基を有する場合、それらが結合して環を形成していてもよく、Ａｒ⁹およびＡｒ¹⁰が置換基を有する場合、それらが結合して環を形成していてもよく、Ａｒ⁹およびＡｒ¹⁰が直接結合して環を形成していてもよい。
Ａ²は、下記式のいずれかで表される。

式中、Ｚ⁶はＢ、ＰまたはＰ（＝Ｏ）を表し、Ｚ⁷はＣ（Ｒ⁹）、Ｓｉ（Ｒ¹⁰）、Ｎ、Ｂ、ＰまたはＰ（＝Ｏ）を表し、Ｚ⁸はＯ、Ｓ、Ｃ（＝Ｏ）、Ｓ（＝Ｏ）、ＳＯ₂、Ｃ（Ｒ¹）（Ｒ²）、Ｓｉ（Ｒ³）（Ｒ⁴）、Ｎ（Ｒ⁵）、Ｂ（Ｒ⁶）、Ｐ（Ｒ⁷）またはＰ（＝Ｏ）（Ｒ⁸）を表し、Ｚ⁹はＣまたはＳｉを表し、Ｚ¹⁰はＮ、Ｂ、Ｐ、Ｃ（Ｒ⁹）またはＳｉ(Ｒ¹⁰)を表す。（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹およびＲ¹⁰は前記と同じ意味を表す。）
Ａ³は、下記式のいずれかで表される。

式中、Ｚ¹¹はＣまたはＳｉを表し、Ｚ¹²はＯ、Ｓ、Ｃ（＝Ｏ）、Ｓ（＝Ｏ）、ＳＯ₂、Ｃ（Ｒ¹）（Ｒ²）、Ｓｉ（Ｒ³）（Ｒ⁴）、Ｎ（Ｒ⁵）、Ｂ（Ｒ⁶）、Ｐ（Ｒ⁷）もしくはＰ（＝Ｏ）（Ｒ⁸）を表し、Ｚ¹³およびＺ¹⁴はそれぞれ独立にＣ（Ｒ⁹）、Ｓｉ（Ｒ¹⁰）、Ｂ、Ｎ、ＰまたはＰ（＝Ｏ）を表す。Ｚ¹⁵およびＺ¹⁶はそれぞれ独立にＣまたはＳｉを表す。（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹およびＲ¹⁰は前記と同じ意味を表す。）
Ａ⁴は、水素原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、置換アミノ基、置換シリル基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基またはアリールエチニル基を表す。ただし、式（９）においてＡｒ⁵とＡ²はＡｒ⁴環の互いに隣接する原子に結合し、Ａｒ⁴とＡ²はＡｒ⁵環の互いに隣接する原子に結合する。
Ｘ¹⁸、Ｘ¹⁹、Ｘ²⁰、Ｘ²¹およびＸ²²は、それぞれ独立にハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル基、−Ｂ（ＯＨ）₂、モノハロゲン化メチル基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、シアノメチル基、ホルミル基、ビニル基、水酸基、アルキルオキシ基、アシルオキシ基、置換シリルオキシ基、アミノ基またはニトロ基を表し、式（９）におけるＸ¹⁸、Ｘ¹⁹およびＸ²⁰の少なくとも一つ、式（１0）におけるＸ¹⁸、Ｘ²¹およびＸ²²の少なくとも一つ、並びに式（１１）におけるＸ¹⁸、Ｘ¹⁹、Ｘ²¹およびＸ²²の少なくとも一つは、ハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル基、−Ｂ（ＯＨ）₂、モノハロゲン化メチル基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、シアノメチル基、ホルミル基、またはビニル基である。］ Furthermore, this invention provides the aromatic compound shown by following formula (9), (10) or (11).

[Wherein Ar ⁴ and Ar ⁵ represent the same meaning as described above, and Ar ⁸ , Ar ⁹ and Ar ¹⁰ each independently represent an arylene group or a divalent heterocyclic group, and the Ar ⁴ , Ar ⁵ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ may have a substituent, and when Ar ⁴ and Ar ⁵ have a substituent, they may be bonded to form a ring, and Ar ⁹ and Ar ¹⁰ are When it has a substituent, they may be bonded to form a ring, or Ar ⁹ and Ar ¹⁰ may be directly bonded to form a ring.
A ² is represented by one of the following formulas.

In the formula, Z ⁶ represents B, P or P (═O), Z ⁷ represents C (R ⁹ ), Si (R ¹⁰ ), N, B, P or P (═O), and Z ⁸ represents O, S, C (= O ), S (= O), SO 2, C (R 1) (R 2), Si (R 3) (R 4), N (R 5), B (R 6) , P (R ⁷ ) or P (═O) (R ⁸ ), Z ⁹ represents C or Si, Z ¹⁰ represents N, B, P, C (R ⁹ ) or Si (R ¹⁰ ). . (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above.)
A ³ is represented by one of the following formulas.

In the formula, Z ¹¹ represents C or Si, and Z ¹² represents O, S, C (═O), S (═O), SO ₂ , C (R ¹ ) (R ² ), Si (R ³ ) ( R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (═O) (R ⁸ ), and Z ¹³ and Z ¹⁴ are each independently C (R ⁹ ), Si (R ¹⁰ ), B, N, P or P (═O) is represented. Z ¹⁵ and Z ¹⁶ each independently represent C or Si. (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above.)
A ⁴ is a hydrogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, substituted silyl group, monovalent group Represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group or an arylethynyl group. However, in Formula (9), Ar ⁵ and A ² are bonded to adjacent atoms of the Ar ⁴ ring, and Ar ⁴ and A ² are bonded to adjacent atoms of the Ar ⁵ ring.
X ¹⁸ , X ¹⁹ , X ²⁰ , X ²¹ and X ²² are each independently a halogen atom, alkyl sulfonate group, aryl sulfonate group, aryl alkyl sulfonate group, borate group, —B (OH) ₂ , monohalogenated Represents a methyl group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group, vinyl group, hydroxyl group, alkyloxy group, acyloxy group, substituted silyloxy group, amino group or nitro group, in formula (9) At least one of X ¹⁸ , X ¹⁹ and X ²⁰ , at least one of X ¹⁸ , X ²¹ and X ²² in formula (10), and at least one of X ¹⁸ , X ¹⁹ , X ²¹ and X ²² in formula (11) One is a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfo group. Over preparative group, borate group, -B (OH) _2, a methyl monohalide group, a sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, a cyanomethyl group, a formyl group or a vinyl group. ]

（式中、Ａｒ⁴、Ａｒ⁵、Ａ¹およびＸ³は、前記と同じ意味を表す。Ａ⁵は、ホウ素原子、アルミニウム原子、ガリウム原子、ケイ素原子、ゲルマニウム原子、窒素原子、リン原子、砒素原子、ａ価の芳香族炭化水素基、ａ価の複素環基または金属錯体構造を有するａ価の基を表す。ａは３または４を表す。複数あるＡｒ⁴、Ａｒ⁵、Ａ¹およびＸ¹⁰は、互いに同一であっても異なっていてもよい。） Moreover, this invention provides the aromatic compound shown by following formula (15).

(Wherein Ar ⁴ , Ar ⁵ , A ¹ and X ³ represent the same meaning as described above. A ⁵ represents a boron atom, an aluminum atom, a gallium atom, a silicon atom, a germanium atom, a nitrogen atom, a phosphorus atom, and arsenic. An atom, an a-valent aromatic hydrocarbon group, an a-valent heterocyclic group or an a-valent group having a metal complex structure, wherein a represents 3 or 4. Plural Ar ⁴ , Ar ⁵ , A ¹ and X ¹⁰ may be the same as or different from each other.

The aromatic compound of the present invention is a novel aromatic compound having three or four condensation-reactive functional groups or precursors thereof, and is useful as a monomer or the like for producing a branched polymer compound.

In the compounds represented by the above formulas (1) and (2), Ar ¹ and Ar ³ each independently represents a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic group. Ar ² represents a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and Ar ¹ , Ar ² and Ar ³ may have a substituent, and Ar ¹ and Ar ² are a substituent. When they have, they may combine to form a ring, and when Ar ¹ and Ar ³ have a substituent, they may combine to form a ring.

  Here, the trivalent aromatic hydrocarbon group and the tetravalent aromatic hydrocarbon group are the remaining atomic groups obtained by removing three and four hydrogen atoms from the aromatic hydrocarbon compound, respectively. -60, preferably 6-20. Note that the aromatic hydrocarbon group may have a substituent, but the carbon number of the aromatic hydrocarbon group does not include the carbon number of the substituent. Substituents include alkyl groups, alkyloxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkyloxy groups, arylalkylthio groups, acyl groups, acyloxy groups, amide groups, and acid imide groups. , Imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, aryl Examples include ethynyl group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group, cyano group and the like. Examples of the aromatic hydrocarbon compound include the following compounds.

Further, the trivalent heterocyclic group and the tetravalent heterocyclic group are the remaining atomic groups obtained by removing 3 and 4 hydrogen atoms from the heterocyclic compound, respectively, and usually have 3 to 60 carbon atoms, preferably 3 carbon atoms. ~ 20. Note that the heterocyclic group may have a substituent, but the carbon number of the heterocyclic group does not include the carbon number of the substituent. Substituents include alkyl groups, alkyloxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkyloxy groups, arylalkylthio groups, acyl groups, acyloxy groups, amide groups, and acid imide groups. , Imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, aryl Examples include ethynyl group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group, cyano group and the like. Examples of the heterocyclic compound include the following compounds.

式中、Ｒはそれぞれ独立に水素原子、アルキル基、アリール基、アリールアルキル基、置換シリル基、アシル基または１価の複素環基を表す。Ｒ’はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アシルオキシ基、置換アミノ基、アミド基、アリールアルケニル基、アリールアルキニル基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基またはシアノ基を表す。

In the formula, each R independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group or a monovalent heterocyclic group. R ′ is independently hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyloxy group, substitution An amino group, an amide group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group, a heteroaryloxy group, a heteroarylthio group, or a cyano group is represented.

Among the substituents that Ar ¹ , Ar ² and Ar ³ may have,
The alkyl group may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl. Group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, A perfluorooctyl group is exemplified.

The alkyloxy group may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyl. Oxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, Examples include perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group and the like.

  The alkylthio group may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexyl. Examples include a thio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, and a trifluoromethylthio group.

The aryl group may have a substituent and usually has about 3 to 60 carbon atoms. Specifically, the aryl group may be a phenyl group or a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ are carbon atoms). indicates a number 1 to 12. the same applies is less.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, pentafluorophenyl group, a pyridyl group, pyridazinyl group, pyrimidyl group , Pyrazyl group, triazyl group and the like.

The aryloxy group may have a substituent on the aromatic ring, and usually has about 3 to 60 carbon atoms. Specifically, the phenoxy group, C _{1 to} C ₁₂ alkoxyphenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group, pyridyloxy group, pyridazinyloxy group, pyrimidyloxy group, pyrazyloxy group, triazyl group is exemplified The

The arylthio group may have a substituent on the aromatic ring, the number of carbon atoms is usually about 3 to 60, specifically, phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group, pyridylthio group, pyridazinylthio group, pyrimidylthio group, pyrazylthio group, etc. Toriajiruchio groups.

The arylalkyl group may have a substituent, the number of carbon atoms is usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl - C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl group exemplified Is done.

The arylalkyloxy group may have a substituent and usually has about 7 to 60 carbon atoms. Specifically, a phenyl-C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkoxyphenyl- C ₁ -C ₁₂ alkoxy groups, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy groups, 1-naphthyl-C ₁ -C ₁₂ alkoxy groups, 2-naphthyl-C ₁ -C ₁₂ alkoxy groups, etc. Is done.

The arylalkylthio group may have a substituent, the number of carbon atoms is usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl - C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio group are exemplified Is done.

Acyl groups usually have about 2 to 20 carbon atoms, and specific examples include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl, and pentafluorobenzoyl groups. Is done.

  The acyloxy group usually has about 2 to 20 carbon atoms. Specifically, the acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group, pentane Examples include a fluorobenzoyloxy group.

  The amide group usually has about 2 to 20 carbon atoms, and specifically includes a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diamide group. Examples include an acetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, a dipentafluorobenzamide group, and the like.

The acid imide group includes a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and usually has about 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms. Specific examples include the following groups.

As the imine residue, an imine compound (refers to an organic compound having —N═C— in the molecule. For example, aldimine, ketimine, and hydrogen atoms on these N are substituted with alkyl groups or the like. And a residue obtained by removing one hydrogen atom from the compound, usually having about 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms. Specific examples include groups represented by the following structural formulas.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The group or the monovalent heterocyclic group may have a substituent.
The number of carbon atoms is usually about 1 to 40. Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group Group, isobutylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctyl amino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ Turkey hydroxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group, phenyl -C ₁ -C ₁₂ alkylamino groups, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino groups, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl-C ₁ -C ₁₂ alkylamino group and the like.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. About 3 to 30 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-i-propylsilyl group, t-butylsilyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, diphenylmethyl Examples include silyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group and the like.

Examples of the substituted silyloxy group include a silyloxy group (H ₃ SiO—) substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The number is usually about 1 to 60, preferably 3 to 30 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tri-n-propylsilyloxy group, tri-i-propylsilyloxy group, t-butylsilyldimethylsilyloxy group, triphenylsilyloxy group, tri- Examples thereof include a p-xylylsilyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a t-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.

As the substituted silylthio group, a silylthio group (H ₃ SiS—) substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group
The number of carbons is usually about 1 to 60, and preferably 3 to 30 carbons. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Examples of the substituted silylthio group include trimethylsilylthio group, triethylsilylthio group, tri-n-propylsilylthio group, tri-i-propylsilylthio group, t-butylsilyldimethylsilylthio group, triphenylsilylthio group, tri- Examples thereof include a p-xylylsilylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a t-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.

Examples of the substituted silylamino group include a silylamino group (H ₃ SiNH— or ((H ₃ Si) ₂ ) substituted with 1 to 6 groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. N-), usually having about 1 to 120 carbon atoms, preferably 3 to 60 carbon atoms, wherein the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group is a substituent. You may have.
Examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tri-n-propylsilylamino group, tri-i-propylsilylamino group, t-butylsilyldimethylsilylamino group, triphenylsilylamino group, tri- p-xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, t-butyldiphenylsilylamino group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group, di (Tri-n-propylsilyl) amino group, di (tri-i-propylsilyl) amino group, di (t-butylsilyldimethylsilyl) amino group, di (triphenylsilyl) amino group, di (tri-p- Xylylsilyl) amino group, di (tribenzylsilyl) Amino group, di (diphenylmethyl silyl) amino, di (t-butyldiphenylsilyl) amino group, di (dimethylphenylsilyl) and amino groups.

The monovalent heterocyclic group refers to a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 2 to 60 carbon atoms. Specifically, a thienyl group, C _{1 to} C Examples include ₁₂ alkylthienyl groups, pyrrolyl groups, furyl groups, pyridyl groups, C ₁ -C ₁₂ alkylpyridyl groups, imidazolyl groups, pyrazolyl groups, triazolyl groups, oxazolyl groups, thiazole groups, thiadiazole groups, and the like.

The heteroaryloxy group refers to a group in which one hydrogen atom is substituted with an oxygen atom from a heterocyclic compound, and is represented by Q ¹ —O—. Q ¹ represents a monovalent heterocyclic group. The number of carbon atoms is usually about 2 to 60, specifically, thienyloxy group, C ₁ -C ₁₂ alkyl thienyl group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C ₁ -C ₁₂ alkyl pyridyl group And imidazolyloxy group, pyrazolyloxy group, triazolyloxy group, oxazolyloxy group, thiazoleoxy group, thiadiazoleoxy group, and the like.

The heteroarylthio group refers to a group obtained by substituting one hydrogen atom with a sulfur atom from a heterocyclic compound, and is represented by Q ² —S—. Q ² represents a monovalent heterocyclic group. The number of carbon atoms is usually about 2 to 60, specifically, thienylmercapto group, C ₁ -C ₁₂ alkyl thienylmercapto group, pyrrolyl mercapto group, a furyl mercapto group, pyridyl mercapto group, C ₁ -C ₁₂ alkyl pyridyl Examples include a mercapto group, an imidazolyl mercapto group, a pyrazolyl mercapto group, a triazolyl mercapto group, an oxazolyl mercapto group, a thiazole mercapto group, and a thiadiazole mercapto group.

The heteroaryloxycarbonyl group refers to a group obtained by substituting one hydrogen atom from a heterocyclic compound with an oxycarbonyl group, and is represented by Q ³ —O (C═O) —. Q ³ represents a monovalent heterocyclic group. The number of carbon atoms is usually about 2 to 60, specifically, thienyl oxycarbonyl group, C ₁ -C ₁₂ alkyl thienyl alkyloxycarbonyl group, pyrrolyl oxycarbonyl group, furyloxy group, pyridyloxy carbonyl group, C ₁ -C ₁₂ alkyl pyridyloxycarbonyl group, imidazolyloxy group, pyrazolyloxy group, benzotriazolyl-oxy group, benzoxazolyl oxycarbonyl group, thiazole oxycarbonyl group, etc. thiadiazoleoxy carbonyl groups.

  Examples of the aryl group in the arylalkenyl group and arylethynyl group include the groups exemplified in the above aryl group. The alkenyl group in the arylalkenyl group usually has about 2 to 20 carbon atoms, and is a vinyl group, 1-propylenyl group, 2-propylenyl group, 3-propylenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl. Group, cyclohexenyl group, 1,3-butadienyl group and the like are exemplified.

A ¹ in formulas (1) and (2) represents -Z ^1- , -Z ² -Z ³ -or -Z ⁴ = Z ^5- , and Z ¹ , Z ² and Z ³ are each independently , O, S, C (═O), S (═O), SO ₂ , C (R ¹ ) (R ² ), Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (═O) (R ⁸ ), and Z ⁴ and Z ⁵ are each independently N, B, P, C (R ⁹ ) or Si (R ¹⁰ ).
Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group , Alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group Substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, carboxyl group, alkyloxycarbonyl group, Aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycal It represents an alkenyl group, or a cyano group. However, R ¹ and R ^2, R ³ and R ⁴ represents a bond to each other may form a ring.).
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group , Arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, The definition and specific examples of the substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group and arylethynyl group are the same as described above.

However, in Formula (1), Ar ² and A ¹ are bonded to adjacent atoms on the Ar ¹ ring, Ar ¹ and A ¹ are bonded to adjacent atoms on the Ar ² ring, and Formula (2) In which Ar ³ and A ¹ are bonded to adjacent atoms on the Ar ¹ ring, and Ar ¹ and A ¹ are bonded to adjacent atoms on the Ar ³ ring.

Specific examples of -Z ^1-in A ¹ include the groups exemplified below.

In A ¹ , examples of —Z ² —Z ³ — include groups exemplified in the following (16), (17), and (18).

（１６）

(16)

In A ¹ , examples of —Z ⁴ = Z ⁵ — include groups exemplified in the following (19) and (20).

In the formulas (1) and (2), X ¹ , X ² , X ³ and X ⁴ are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, a borate ester group, — B (OH) ₂ , monohalogenated methyl group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group, vinyl group, hydroxyl group, alkyloxy group, acyloxy group, substituted silyloxy group, amino group or nitro Represents at least one of X ¹ , X ² , and X ³ in formula (1) is a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate group, or —B (OH) ₂ , Monohalogenated methyl group, sulfonium methyl group, phosphonium methyl group Phosphonate methyl group, cyanomethyl group, selected from a formyl group and a vinyl group, in the formula (2), at least one halogen atom X ^1, X ^2, X ³ and X ^4, alkyl sulfonate group, aryl sulfonate group, an aryl It is selected from an alkyl sulfonate group, a borate group, —B (OH) ₂ , a monohalogenated methyl group, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a cyanomethyl group, a formyl group, and a vinyl group.

  Here, examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably chlorine, bromine and iodine.

  Examples of the alkyl sulfonate group include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. Examples of the aryl alkyl sulfonate group include Examples include a benzyl sulfonate group.

Examples of the borate group include groups represented by the following formula.

Examples of the monohalogenated methyl group include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group.

Examples of the sulfonium methyl group include groups represented by the following formula.
_{-CH2SMe 2 X, -CH2SPh 2 X (} X represents a halogen atom.)

Examples of the phosphonium methyl group include groups represented by the following formula.
-CH2PPh ₃ X (X represents a halogen atom.)

Examples of the phosphonate methyl group include groups represented by the following formula.
-CH2PO (OR ') ₂
(R ′ represents an alkyl group, an aryl group or an arylalkyl group.)

When the compound represented by the above formula (1) or (2) has a condensation-reactive functional group and a condensation-reactive functional group precursor, the condensation-reactive functional group precursor is converted into a functional group after performing the condensation reaction. Furthermore, regioselective substituent introduction and polymerization reaction can be carried out by further conducting a condensation reaction.
Condensation reactive functional groups include halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, boric acid ester groups, -B (OH) ₂ , monohalogenated methyl groups, sulfonium methyl groups, phosphonium methyl groups. Group, phosphonate methyl group, cyanomethyl group, formyl group, or vinyl group, and the condensation-reactive functional group precursor refers to a functional group that can be converted to a condensation-reactive functional group by performing functional group conversion. Specifically, a hydroxyl group, an alkyloxy group, an acyloxy group, a substituted silyloxy group, an amino group or a nitro group can be mentioned.

  In addition, as a method for converting the condensation-reactive functional group precursor into a condensation-reactive functional group, when the condensation-reactive functional group precursor is a hydroxyl group, an alkylsulfonic acid anhydride or an alkylsulfonyl chloride is used in the presence of a base. It can convert into the alkyl sulfonate group by making it react. Similarly, by using a corresponding sulfonic anhydride or sulfonyl chloride, it can be converted into an aryl sulfonate group or an aryl alkyl sulfonate group.

  When the condensation-reactive functional group precursor is an alkyloxy group, it is converted to a hydroxyl group using boron tribromide or the like, and then converted to an alkyl sulfonate group, aryl sulfonate or arylalkyl sulfonate group using the above method. be able to.

  When the condensation-reactive functional group precursor is an acyloxy group, it is converted to a hydroxyl group by hydrolysis or reaction with a reducing agent under basic conditions, and then the alkyl sulfonate group, aryl sulfonate or aryl alkyl sulfonate is used by the above method. Can be converted to a radical.

  When the condensation-reactive functional group precursor is a substituted silyloxy group, it is converted into a hydroxyl group by hydrolysis under acidic conditions, hydrolysis under basic conditions, or reaction with fluoride ions. It can be converted to a sulfonate group, an aryl sulfonate or an arylalkyl sulfonate group.

  When the condensation-reactive functional group precursor is an amino group, it can be converted to a halogen atom by Sandmeyer reaction.

  When the condensation-reactive functional group precursor is a nitro group, it can be converted to an amino group by reaction with a reducing agent, and then converted to a halogen atom using the above method.

When the compound represented by the above formula (1) or (2) has a condensation-reactive functional group and a condensation-reactive functional group precursor, from the viewpoint of light emission intensity when the compound is made into a polymer, A ¹ is , O, C (R ¹ ) (R ² ), N (R ⁵ ) or B (R ⁶ ) is preferred.

Further, from the viewpoint of the emission intensity when it is made into a polymer, it is also preferable that Z ² and Z ³ are different from each other in —Z ² —Z ³ — or that —Z ⁴ = Z ⁵ — is represented. Specific examples include groups exemplified in the above formula (16), (17), (18), (19) or (20).

Among them, A ¹ is OC (═O), OC (R ¹ ) (R ² ), SC (R ¹ ) (R ² ), S (═O) —C (R ¹ ) (R ² ), SO ₂ —C (R ¹ ) (R ² ), N (R ⁵ ) —C (═O) or N═C (R ⁹ ) is more preferred. Specific examples include groups exemplified in the above formulas (18) and (20).

In addition, all of X ¹ , X ² and X ³ in the formula (1) are halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, borate ester groups, —B (OH) ₂ , monohalogenated When selected from a methyl group, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a cyanomethyl group, a formyl group, and a vinyl group, all of X ¹ , X ² , X ³ and X ^{4 in} the formula (2) are halogen atoms, Alkyl sulfonate group, aryl sulfonate group, aryl alkyl sulfonate group, borate ester group, -B (OH) ₂ , monohalogenated methyl group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group, vinyl If it is a compound selected from the group, it is directly subjected to polymerization Preferable to give a branched polymer.

Among them, since the reaction site of the condensation reaction can be controlled, in the formula (1), when at least one of X ¹ , X ² , and X ³ is a different functional group from the others, and in the formula (2), X ¹ , It is preferable that at least one of X ² , X ³ and X ^{4 is} a functional group different from the others.

Of these, X ^1, and at least one halogen atom of ^{X 2, X 3, X 1} , X 2, at least one of X ³ is preferably be a sulfonate group. Here, the sulfonate group represents an alkyl sulfonate group, an aryl sulfonate group or an arylalkyl sulfonate group.

From the viewpoint of emission intensity when the compound is made into a polymer, A ¹ is preferably O, S, S (═O) or SO _2. From the viewpoint of charge transportability when made into a polymer, A ¹ Is C (R ¹ ) (R ² ), Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (═O) (R ⁸ ) Some cases are preferred.

Further, when used as a polymer LED, from the viewpoint of emission intensity when a polymer is used, it is also preferable that -Z ² -Z ³ -or -Z ⁴ = Z ⁵ -is expressed. Specific examples include groups exemplified in the above formula (16), (17), (18), (19) or (20).

Among them, A ¹ is OC (═O), OC (R ¹ ) (R ² ), SC (R ¹ ) (R ² ), S (═O) —C (R ¹ ) (R ² ), SO ₂ —C (R ¹ ) (R ² ), N (R ⁵ ) —C (═O) or N═C (R ⁹ ) is more preferred. Specific examples include the groups exemplified in the above formula (18) or (20).

  Examples of the compound represented by the formula (1) include the following compounds (21) and (22).

  Examples of the compound represented by the formula (2) include the following compounds (23) and (24).

Among them, when Ar ¹ and Ar ² are aromatic hydrocarbons in the above formula (1), or when Ar ¹ and Ar ³ are aromatic hydrocarbons in the above formula (2), it is preferable from the viewpoint of stability of the compound.

  In particular, when represented by the following formula (1-1) or (2-1), it is preferable from the viewpoint of stability of the compound.

式中、Ａ¹、Ｘ¹、Ｘ²、Ｘ³およびＸ⁴は上記と同じ。ベンゼン環上に置換基を有していてもよく、置換基が互いに結合して環を形成していてもよい。置換基としては、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールエチニル基、カルボキシル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アリールアルキルオキシカルボニル基、ヘテロアリールオキシカルボニル基またはシアノ基が挙げられる。

In the formula, A ¹ , X ¹ , X ² , X ³ and X ⁴ are the same as above. The benzene ring may have a substituent, and the substituents may be bonded to each other to form a ring. Substituents include alkyl groups, alkyloxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkyloxy groups, arylalkylthio groups, acyl groups, acyloxy groups, amide groups, and acid imide groups. , Imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, aryl Examples include an ethynyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group, and a cyano group.

上記式（１）または（２）で示される化合物は、上記式（１−２）で示される化合物をハロゲン化する方法などにより製造することができる。Ｘ^1’およびＸ^3’はそれぞれ独立に、ハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル基、−Ｂ（ＯＨ）₂、モノハロゲン化メチル基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、シアノメチル基、ホルミル基もしくはビニル基、またはハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル基、−Ｂ（ＯＨ）₂、モノハロゲン化メチル基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、シアノメチル基、ホルミル基もしくはビニル基に変換可能な官能基を表す。中でも、Ｘ^1’およびＸ³は電子供与基が好ましい。
以下に合成法を例示する。

A method for synthesizing the compound represented by (1) or (2) will be described.

The compound represented by the above formula (1) or (2) can be produced by a method of halogenating the compound represented by the above formula (1-2). X ^{1 ′} and X ^{3 ′} each independently represent a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, —B (OH) ₂ , a monohalogenated methyl group, a sulfonium methyl group, Phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group or vinyl group, or halogen atom, alkyl sulfonate group, aryl sulfonate group, aryl alkyl sulfonate group, borate ester group, -B (OH) ₂ , monohalogenated methyl Represents a functional group which can be converted into a group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group or vinyl group. Among these, X ^{1 ′} and X ³ are preferably electron donating groups.
The synthesis method is illustrated below.

Next, the compound represented by formula (5) or (6) will be described.

In the formula, A ¹ and X ³ represent the same meaning as described above, and Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group. , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ may have a substituent, and when Ar ⁴ and Ar ⁵ have a substituent, they may combine to form a ring.
Here, the definitions, specific examples, etc. of the trivalent aromatic hydrocarbon group, trivalent heterocyclic group, substituents that Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ may have are represented by the formula ( The definitions and specific examples in 1) and (2) are the same.

X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, —B (OH) ₂ , monohalogenated methyl Represents a group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group, vinyl group, hydroxyl group, alkyloxy group, acyloxy group, substituted silyloxy group, amino group or nitro group, X in formula (5) ⁹ , at least one of X ¹⁰ and X ³ is a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, —B (OH) ₂ , a monohalogenated methyl group, a sulfonium methyl group, Phosphonium methyl group, phosphonate methyl Group, cyanomethyl group, selected from a formyl group and a vinyl group, in the formula (6), at least one of X ^9, X ^10, X ¹¹ and X ¹² is a halogen atom, alkyl sulfonate group, aryl sulfonate group, arylalkyl A sulfonate group, a borate group, —B (OH) ₂ , a monohalogenated methyl group, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a cyanomethyl group, a formyl group, and a vinyl group are selected.
Here, in X ⁹ , X ¹⁰ , X ¹¹ and X ¹² , a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, —B (OH) ₂ , a monohalogenated methyl group, The definitions and specific examples of sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, alkyloxy group, acyloxy group, and substituted silyloxy group are the same as those definitions and specific examples in formulas (1) and (2). is there.

When the compound represented by the above formula (5) or (6) has a condensation-reactive functional group and a condensation-reactive functional group precursor, the condensation-reactive functional group precursor is converted into a functional group after performing the condensation reaction. Furthermore, regioselective substituent introduction and polymerization reaction can be carried out by further conducting a condensation reaction.

When the compound represented by the above formula (5) or (6) has a condensation-reactive functional group and a condensation-reactive functional group precursor, from the viewpoint of light emission intensity when the compound is made into a polymer, A ¹ is A case where O, S, S (═O), SO _2, Si (R ³ ) (R ⁴ ), or N (R ⁵ ) is preferable.

Further, -Z ² -Z ³ - or -Z ⁴ = Z ⁵ - is also preferable if represented by. Specific examples include groups exemplified in the above formula (16), (17), (18), (19) or (20).

Among them, A ¹ is O-C (= O), O-C (R 1) (R 2), N (R 5) -C (= O) or a N = C (R ⁹⁾ is preferred.

Further, all of X ¹ , X ² and X ³ in the formula (5) are halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, borate ester groups, —B (OH) ₂ , monohalogenated When selected from a methyl group, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a cyanomethyl group, a formyl group, and a vinyl group, all of X ¹ , X ² , X ³ and X ⁴ in formula (6) are halogen atoms, Alkyl sulfonate group, aryl sulfonate group, aryl alkyl sulfonate group, borate ester group, -B (OH) ₂ , monohalogenated methyl group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group and vinyl When selected from the group, if directly subjected to polymerization It preferred to give Toki polymer.

Among them, since the reaction site of the condensation reaction can be controlled, in the formula (5), when at least one of X ³ , X ⁹ and X ¹⁰ is a different functional group and in the formula (6), X ⁹ , It is preferable that at least one of X ¹⁰ , X ¹¹ and X ^{12 is} a functional group different from the others.

From the viewpoint of the emission intensity when polymerized, it is preferable that A ¹ is O, S, S (═O), SO _2, Si (R ³ ) (R ⁴ ), or N (R ⁵ ).

It is also preferred that -Z ² -Z ³ -or -Z ⁴ = Z ⁵ -is expressed. Specific examples include groups exemplified in the above formula (16), (17), (18), (19) or (20).

Among them, A ¹ is O-C (= O), O-C (R 1) (R 2), N (R 5) -C (= O) or a N = C (R ⁹⁾ is preferred.

  Examples of the compound represented by the formula (5) include compounds exemplified in the following (25) and (26).

  Examples of the compound represented by the formula (6) include compounds exemplified in the following (27) and (28).

Among these, in the above formula (5) or (6), when Ar ⁴ and Ar ⁵ are aromatic hydrocarbons, it is preferable from the viewpoint of the stability of the compound.

In particular, when represented by the following formula (5-1) or (6-1), it is preferable from the viewpoint of stability of the compound.

In the formula, Ar ⁶ , Ar ⁷ , A ¹ , X ³ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are the same as above. The benzene ring may have a substituent, and the substituents may be bonded to each other to form a ring. Substituents include alkyl groups, alkyloxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkyloxy groups, arylalkylthio groups, acyl groups, acyloxy groups, amide groups, and acid imide groups. , Imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, aryl Examples include an ethynyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group, and a cyano group.

上記式（５）で示される化合物は、上記式（５−２）で示される化合物と（５−３）で示される化合物１当量をクロスカップリングさせた後に、Ｘ^3’、Ｘ^9’およびＸ^10’をそれぞれＸ³、Ｘ⁹およびＸ¹⁰へと変換する方法などにより製造することができる。式中、Ａ¹、Ａｒ⁴、Ａｒ⁵およびＡｒ⁶は、上記と同じ意味を表す。Ｘ^3’、Ｘ^9’およびＸ¹⁰はそれぞれ独立にハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル基、−Ｂ（ＯＨ）₂、モノハロゲン化メチル基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、シアノメチル基、ホルミル基もしくはビニル基、またはハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル基、−Ｂ（ＯＨ）₂、モノハロゲン化メチル基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、シアノメチル基、ホルミル基もしくはビニル基に変換可能な官能基を表す。Ｘ³⁰およびＸ³¹は、それぞれ独立にハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、トリアルキルスズ基、ホウ酸エステル基または−Ｂ（ＯＨ）₂を表す。
クロスカップリングの方法としては、Ｓｕｚｕｋｉカップリング、Ｇｒｉｇｎａｒｄカップリング、Ｓｔｉｌｌｅカップリングなどが例示される。Ｘ⁹およびＸ¹⁰に変換可能な官能基としては、例えば、水酸基、アルキルオキシ基、アシルオキシ基、置換シリルオキシ基、アミノ基またはニトロ基などが例示される。官能基変換の方法としては、上記の通りである。以下に合成法を例示する。

Next, a method for synthesizing the compound represented by the formula (5) will be described.

After the compound represented by the above formula (5) is cross-coupled between the compound represented by the above formula (5-2) and 1 equivalent of the compound represented by (5-3), X ^{3 ′} , X ^{9 ′} and It can be produced by a method of converting X ^{10 ′} to X ³ , X ⁹ and X ¹⁰ , respectively. In the formula, A ¹ , Ar ⁴ , Ar ⁵ and Ar ⁶ represent the same meaning as described above. X ^{3 ′} , X ^{9 ′} and X ¹⁰ are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, —B (OH) ₂ , a monohalogenated methyl group, or a sulfonium methyl group. Group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group or vinyl group, or halogen atom, alkyl sulfonate group, aryl sulfonate group, aryl alkyl sulfonate group, boric acid ester group, -B (OH) ₂ , monohalogen Represents a functional group that can be converted into a methyl group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group or vinyl group. X ³⁰ and X ³¹ each independently represent a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a trialkyl tin group, a borate group or —B (OH) ₂ .
Examples of the cross coupling method include Suzuki coupling, Grignard coupling, Stille coupling, and the like. Examples of functional groups that can be converted to X ⁹ and X ¹⁰ include hydroxyl groups, alkyloxy groups, acyloxy groups, substituted silyloxy groups, amino groups, and nitro groups. The functional group conversion method is as described above. The synthesis method is illustrated below.

上記式（６）で示される化合物は、例えば上記式（５−４）で示される化合物と（６−２）で示される化合物をクロスカップリングさせた後に、Ｘ^9’、Ｘ¹⁰、Ｘ¹¹およびＸ¹²をそれぞれＸ⁹、Ｘ¹⁰、Ｘ¹¹およびＸ¹²へと変換する方法などにより製造することができる。クロスカップリングの方法としては、上記と同じ方法が挙げられる。また、（６）で示される化合物は、（５−２）で示される化合物と（５−３）で示される化合物２当量とを反応させた後にＸ^9’およびＸ^10’をそれぞれＸ⁹およびＸ¹⁰変換する方法などによっても製造することができる。

Next, a method for synthesizing the compound represented by the formula (6) will be described.

The compound represented by the above formula (6) is obtained by, for example, cross-coupling the compound represented by the above formula (5-4) with the compound represented by (6-2), and then X ^{9 ′} , X ¹⁰ , X ¹¹ And X ¹² can be produced by a method of converting X ⁹ , X ¹⁰ , X ¹¹ and X ¹² respectively. Examples of the cross coupling method include the same methods as described above. In addition, the compound represented by (6) is obtained by reacting the compound represented by (5-2) with 2 equivalents of the compound represented by (5-3), and then converting X ^{9 ′} and X ^{10 ′} to X ⁹ and it can also be produced by a method of X ¹⁰ conversion.

Next, the compound represented by formula (9), (10) or (11) will be described.

In the formula, Ar ⁴ and Ar ⁵ represent the same meaning as described above, Ar ⁸ , Ar ⁹ and Ar ¹⁰ each independently represent an arylene group or a divalent heterocyclic group, and the Ar ⁴ , Ar ⁵ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ may have a substituent, and when Ar ⁴ and Ar ⁵ have a substituent, they may be bonded to form a ring, and Ar ⁹ and Ar ¹⁰ are substituted. When it has a group, they may be bonded to form a ring, and Ar ⁹ and Ar ¹⁰ may be directly bonded to form a ring.

Here, the arylene group refers to a remaining atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon compound, and usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms. Note that the aromatic hydrocarbon group may have a substituent, but the carbon number of the aromatic hydrocarbon group does not include the carbon number of the substituent. About an aromatic hydrocarbon compound and a substituent, the compound and group illustrated about the trivalent aromatic hydrocarbon group in the said Formula (1) are illustrated.
A bivalent heterocyclic group means the remaining atomic group remove | excluding two hydrogen atoms from the heterocyclic compound, and it is C3-C60 normally, Preferably it is 3-20. In addition, you may have a substituent on the heterocyclic group. Examples of the heterocyclic compound and the substituent include compounds and groups exemplified for the trivalent heterocyclic group in the formula (1).

式中、Ｚ⁶はＢ、ＰまたはＰ（＝Ｏ）を表し、Ｚ⁷はＣ（Ｒ⁹）、Ｓｉ（Ｒ¹⁰）、Ｎ、Ｂ、ＰまたはＰ（＝Ｏ）を表し、Ｚ⁸はＯ、Ｓ、Ｃ（＝Ｏ）、Ｓ（＝Ｏ）、ＳＯ₂、Ｃ（Ｒ¹）（Ｒ²）、Ｓｉ（Ｒ³）（Ｒ⁴）、Ｎ（Ｒ⁵）、Ｂ（Ｒ⁶）、Ｐ（Ｒ⁷）またはＰ（＝Ｏ）（Ｒ⁸）を表し、Ｚ⁹はＣまたはＳｉを表し、Ｚ¹⁰はＮ、Ｂ、Ｐ、Ｃ（Ｒ⁹）またはＳｉ(Ｒ¹⁰)を表す。（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹およびＲ¹⁰は前記と同じ意味を表す。） Where
A ² is represented by one of the following formulas.

In the formula, Z ⁶ represents B, P or P (═O), Z ⁷ represents C (R ⁹ ), Si (R ¹⁰ ), N, B, P or P (═O), and Z ⁸ represents O, S, C (= O ), S (= O), SO 2, C (R 1) (R 2), Si (R 3) (R 4), N (R 5), B (R 6) , P (R ⁷ ) or P (═O) (R ⁸ ), Z ⁹ represents C or Si, Z ¹⁰ represents N, B, P, C (R ⁹ ) or Si (R ¹⁰ ). . (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above.)

式中、Ｚ¹¹はＣまたはＳｉを表し、Ｚ¹²はＯ、Ｓ、Ｃ（＝Ｏ）、Ｓ（＝Ｏ）、ＳＯ₂、Ｃ（Ｒ¹）（Ｒ²）、Ｓｉ（Ｒ³）（Ｒ⁴）、Ｎ（Ｒ⁵）、Ｂ（Ｒ⁶）、Ｐ（Ｒ⁷）もしくはＰ（＝Ｏ）（Ｒ⁸）を表し、Ｚ¹³およびＺ¹⁴はそれぞれ独立にＣ（Ｒ⁹）、Ｓｉ（Ｒ¹⁰）、Ｂ、Ｎ、ＰまたはＰ（＝Ｏ）を表す。Ｚ¹⁵およびＺ¹⁶はそれぞれ独立にＣまたはＳｉを表す。（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹およびＲ¹⁰は前記と同じ意味を表す。） A ³ is represented by one of the following formulas.

In the formula, Z ¹¹ represents C or Si, and Z ¹² represents O, S, C (═O), S (═O), SO ₂ , C (R ¹ ) (R ² ), Si (R ³ ) ( R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (═O) (R ⁸ ), and Z ¹³ and Z ¹⁴ are each independently C (R ⁹ ), Si (R ¹⁰ ), B, N, P or P (═O) is represented. Z ¹⁵ and Z ¹⁶ each independently represent C or Si. (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above.)

A ⁴ is a hydrogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, substituted silyl group, monovalent group Represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group or an arylethynyl group. However, in Formula (9), Ar ⁵ and A ² are bonded to adjacent atoms of the Ar ⁴ ring, and Ar ⁴ and A ² are bonded to adjacent atoms of the Ar ⁵ ring.

In the formula, X ¹⁸ , X ¹⁹ , X ²⁰ , X ²¹ and X ²² are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, a borate ester group, —B (OH) ₂ , Monohalogenated methyl group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group, vinyl group, hydroxyl group, alkyloxy group, acyloxy group, substituted silyloxy group, amino group or nitro group, 9) At least one of X ¹⁸ , X ¹⁹ and X ²⁰ is a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, —B (OH) ₂ , a monohalogenated methyl group, Sulfonium methyl group, phosphonium methyl group, phosphonate Selected from a tomethyl group, a cyanomethyl group, a formyl group, and a vinyl group, and at least one of X ¹⁸ , X ^21, and X ²² in the formula (10) is a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, X ¹⁸ in formula (11) selected from borate group, —B (OH) ₂ , monohalogenated methyl group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group, and vinyl group. , X ¹⁹ , X ²¹ and X ²² are each a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, —B (OH) ₂ , a monohalogenated methyl group, a sulfonium Methyl group, phosphonium methyl group, phosphonate It is selected from a methyl group, a cyanomethyl group, a formyl group, and a vinyl group.

Specific examples of the group represented by A ² include the following groups.

Specific examples of the group represented by A ³ include the following groups.

When the compound represented by the above formula (9), (10) or (11) has a condensation-reactive functional group and a condensation-reactive functional group precursor, a condensation-reactive functional group precursor is obtained after performing a condensation reaction. The functional group can be converted into a functional group and a condensation reaction can be performed to introduce a regioselective substituent or a polymerization reaction.

When the compound represented by the above formula (9), (10) or (11) has a condensation-reactive functional group and a condensation-reactive functional group precursor, and from the viewpoint of emission intensity when converted into a polymer, The case where A ² is B, P or P (═O) is preferred.

式中、Ｚ⁷、Ｚ⁸、Ｚ⁹およびＺ¹⁰は上記と同じ意味を表す。 It is also preferred that A ² is represented by the following formula.

In the formula, Z ⁷ , Z ⁸ , Z ⁹ and Z ¹⁰ represent the same meaning as described above.

In the compound represented by the above formula (10) or (11), A ³ is preferably a tetravalent group shown below from the viewpoint of emission intensity when converted into a polymer.

In the formula (9), X ¹⁸ , X ¹⁹ and X ²⁰ are all halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, borate ester groups, —B (OH) ₂ , monohalogenated methyl Group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group, vinyl group, all of X ¹⁸ , X ²¹ and X ²² in formula (10) are halogen atoms, alkyl sulfonate groups, Aryl sulfonate group, arylalkyl sulfonate group, borate ester group, -B (OH) ₂ , monohalogenated methyl group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group, vinyl group If, X in the formula (11) ^{18, 19,} all of X ²¹ and X ²² is a halogen atom, alkyl sulfonate group, aryl sulfonate group, arylalkyl sulfonate group, borate group, -B (OH) _2, monohalogenated methyl group, a sulfonium methyl group, phosphonium When it is selected from a methyl group, a phosphonate methyl group, a cyanomethyl group, a formyl group, and a vinyl group, it is preferable because it provides a branched polymer when directly subjected to polymerization.

Above all, if because it can control of the reaction site of the condensation reaction, where at least one other different functional groups of X ^18, X ^19, X ²⁰ in (9), X ¹⁸ in (10), It is preferable that at least one of X ²¹ and X ^{22 is} a functional group different from the other and that in the formula (11), at least one of X ¹⁸ , X ¹⁹ , X ²¹ and X ^{22 is} a functional group different from the other. .

Further, from the viewpoint of light emission intensity when a polymer is used, it is preferable that A ² is B, P or P (═O).

式中、Ｚ⁷、Ｚ⁸、Ｚ⁹およびＺ¹⁰は上記と同じ意味を表す。 It is also preferred that A ² is represented by the following formula.

In the formula, Z ⁷ , Z ⁸ , Z ⁹ and Z ¹⁰ represent the same meaning as described above.

In the compound represented by the above formula (10) or (11), A ³ is preferably a tetravalent group shown below from the viewpoint of emission intensity when converted into a polymer.

  Examples of the compound represented by the formula (9) include compounds exemplified in the following (29) and (30).

（２９）

(29)

（３０）

(30)

  Examples of the compound represented by the formula (10) include compounds exemplified in the following (31) and (32).

（３１）

(31)

（３２）

(32)

  Examples of the compound represented by the formula (11) include compounds exemplified in the following (33) and (34).

（３３）

(33)

（３４）

(34)

Among these, when Ar ⁴ and Ar ⁵ are aromatic hydrocarbons in the above formula (9), (10) or (11), it is preferable from the viewpoint of the stability of the compound.

  In particular, when represented by the following formula (9-1), (10-1) or (11-1), it is preferable from the viewpoint of the stability of the compound.

In the formula, Ar ⁸ , Ar ⁹ , Ar ¹⁰ , A ² , A ³ , A ⁴ , X ¹⁸ , X ¹⁹ , X ²⁰ , X ²¹ and X ²² are the same as above. The benzene ring may have a substituent, and the substituents may be bonded to each other to form a ring. Substituents include alkyl groups, alkyloxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkyloxy groups, arylalkylthio groups, acyl groups, acyloxy groups, amide groups, and acid imide groups. , Imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, aryl Examples include an ethynyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group, and a cyano group.

上記式（９）、（１０）または（１１）で示される化合物は、例えば対応する有機リチウム試薬またはＧｒｉｇｎａｒｄ試薬と上記式（９−２）、（１０−２）または（１１−２）とそれぞれ反応させた後、酸触媒存在下に反応させる方法などにより製造することができる。以下に製造方法を例示する。

Next, a method for producing the compound represented by the above formula (9), (10) or (11) will be described.

The compound represented by the above formula (9), (10) or (11) includes, for example, the corresponding organolithium reagent or Grignard reagent and the above formula (9-2), (10-2) or (11-2), respectively. After the reaction, it can be produced by a method of reacting in the presence of an acid catalyst. The production method is illustrated below.

Next, the compound represented by formula (15) will be described.

In the formula, Ar ⁴ , Ar ⁵ , A ¹ and X ³ represent the same meaning as described above. A ⁵ is boron atom, aluminum atom, gallium atom, silicon atom, germanium atom, nitrogen atom, phosphorus atom, arsenic atom, a-valent aromatic hydrocarbon group, a-valent heterocyclic group or metal complex structure a Represents a valent group. a represents 3 or 4. A plurality of Ar ⁴ , Ar ⁵ , A ¹ and X ¹⁰ may be the same or different from each other.

  Here, definitions of a-valent aromatic hydrocarbon group and a-valent heterocyclic group, specific examples are the above-mentioned trivalent aromatic hydrocarbon group, tetravalent aromatic hydrocarbon group, trivalent heterocyclic ring. The definitions and specific examples in the explanation of the group and the tetravalent heterocyclic group are the same.

The a-valent group having a metal complex structure is a remaining a-valent group obtained by removing a hydrogen atom from an organic ligand of a metal complex having an organic ligand. The carbon number of the organic ligand is usually about 4 to 60. For example, 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof. Derivatives, 2-phenyl-benzoxazole and its derivatives, porphyrin and its derivatives and the like.
Examples of the central metal of the complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
Examples of the metal complex having an organic ligand include a low-molecular fluorescent material, a metal complex known as a phosphorescent material, and a triplet light-emitting complex.

Specific examples of the a-valent group having a metal complex structure include the following groups. In addition, you may have a substituent on the avalent group which has a metal complex structure, However, Carbon number of a substituent is not contained in carbon number of a heterocyclic group. Substituents include alkyl groups, alkyloxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkyloxy groups, arylalkylthio groups, acyl groups, acyloxy groups, amide groups, and acid imide groups. , Imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, aryl Examples include an ethynyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group, and a cyano group.
The definition and specific examples of these substituents are the same as described above.

From the viewpoint of light emission intensity when polymerized, A ¹ is O, S, S (═O), SO ₂ , Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ), P (═O) (R ⁸ ),
When —O—C (═O) —, —O—C (R ¹ ) (R ² ) —, —N (R ⁵ ) —C (═O) — or —N═C (R ⁹ ) — Is preferred.

（３５） Examples of the compound represented by the formula (15) include compounds exemplified in the following (35) and (36).

(35)

（３６）

(36)

Among these, when Ar4 and Ar5 are aromatic hydrocarbons in the above formula (15), it is preferable from the viewpoint of the stability of the compound.
In particular, when represented by the following formula (15-1), it is preferable from the viewpoint of the stability of the compound.

In the formula, A ¹ , A ⁵ , X ³ and a are the same as above. The benzene ring may have a substituent, and the substituents may be bonded to each other to form a ring. Substituents include alkyl groups, alkyloxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkyloxy groups, arylalkylthio groups, acyl groups, acyloxy groups, amide groups, and acid imide groups. , Imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, aryl Examples include ethynyl group, carboxyl group, and cyano group.

以下に製造方法を例示する。

Ａ⁵がａ価の芳香族炭化水素基、ａ価の複素環基または金属錯体構造を有するａ価の基である場合、（１５−４）で示される化合物と（１５−５）で示される化合物とのクロスカップリングさせる方法などにより製造することができる。式中、Ａ¹、Ａ⁵、Ａｒ⁴、Ａｒ⁵およびＸ³は上記と同じ。Ｘ³⁴およびＸ³⁵はそれぞれ独立にハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、トリアルキルスズ基、ホウ酸エステル基または−Ｂ（ＯＨ）₂を表す。クロスカップリングの方法としては、Ｓｕｚｕｋｉカップリング、Ｇｒｉｇｎａｒｄカップリング、Ｓｔｉｌｌｅカップリングなどが例示される。

以下に製造方法を例示する。

Next, a method for producing the compound represented by the formula (15) will be described. When A ⁵ is a boron atom, an aluminum atom, a gallium atom, a silicon atom, a germanium atom, a phosphorus atom or an arsenic atom, it is produced by a method of reacting the following formulas (15-2) and (15-3) Can do. In the formula, A ¹ , A ⁵ , Ar ⁴ , Ar ⁵ and X ³ are the same as above. M represents a lithium atom, a sodium atom, a potassium atom, or a magnesium salt. X ³³ represents a halogen atom.

The production method is illustrated below.

When A ⁵ is an a-valent aromatic hydrocarbon group, an a-valent heterocyclic group or an a-valent group having a metal complex structure, the compound represented by (15-4) and (15-5) It can be produced by a method of cross coupling with a compound. In the formula, A ¹ , A ⁵ , Ar ⁴ , Ar ⁵ and X ³ are the same as above. X ³⁴ and X ³⁵ each independently represent a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a trialkyl tin group, a borate group or —B (OH) ₂ . Examples of the cross coupling method include Suzuki coupling, Grignard coupling, Stille coupling, and the like.

The production method is illustrated below.

  Next, the use of the compound of the present invention will be described. The compound of the present invention can be used as a medical / pesticidal intermediate, an organic electronic material, or an intermediate thereof by a condensation reaction of X1 to X22.

As a method for the condensation reaction, in the case of bonding via a vinylene group, it can be produced, for example, by the method described in JP-A-5-202355. When it has two or more condensation-reactive functional groups, it can also be used as a condensation polymerization reaction.
[1] Wittig reaction between a compound having an aldehyde group and a compound having a phosphonium base, [2] Heck reaction between a compound having a vinyl group and a compound having a halogen atom [3] A compound having an aldehyde group and an alkylphosphonate Horner-Wadsworth-Emmons reaction with a compound having a group [4] Knoevenagel reaction between a compound having a formyl group and a compound having a cyano group [5] A method such as McMurry reaction of a compound having two or more formyl groups The
The reactions [1] to [5] are shown by the following formulas.

  A branched oligomer or branched polymer can be produced by subjecting the compound of the present invention to a condensation polymerization reaction.

[1]

[2]

[3]

[4]

[5]

Examples of the condensation reaction method for forming a direct bond include [6] Suzuki coupling reaction, [7] Grignard coupling reaction, and [8] Ni (0) catalyst condensation reaction.
The polymerization methods [6] to [8] are shown by the following formulas.

[6]

[7]

[8]

As a reaction method, the compound of the present invention can be dissolved in an organic solvent as necessary, and reacted, for example, using an alkali or a suitable catalyst at a melting point or higher and a boiling point or lower of the organic solvent. For example, “Organic Reactions”, Vol. 14, pages 270-490, John Wiley & Sons, Inc., 1965, “Organic Reactions”, Vol. 27, 345-390, John Wiley & Sons, Inc., 1982, "Organic Synthesis", Collective Volume VI, 407-411, John Wiley and Sons (407-411). John Wiley & Sons, Inc.), 1988, Chem. Rev., 95, 24. 7 (1995), Journal of Organometallic Chemistry (J. Organomet. Chem.), 576, 147 (1999), Journal of Practical Chemistry (J. Prakt. Chem.), 336, 247 (1994), Macromolecular Chemistry Macromolecular Symposium (Macromol. Chem., Macromol. Symp.), Vol. 12, p. 229 (1987), etc. can be used.

  The organic solvent varies depending on the compound and reaction to be used, but it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction proceeds in an inert atmosphere in order to suppress side reactions. Similarly, it is preferable to perform a dehydration treatment. (However, this is not the case in the case of a two-phase reaction with water such as the Suzuki coupling reaction.)

  In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding. Moreover, it can refine | purify by normal methods, such as reprecipitation refinement | purification and the fractionation by chromatography, after a synthesis | combination.

  More specifically, the reaction conditions will be described. In the case of Wittig reaction, Horner reaction, Knoevengel reaction, etc., the reaction is carried out using an equivalent or more, preferably 1 to 3 equivalents of alkali with respect to the functional group of the monomer. Examples of the alkali include, but are not limited to, metal alcoholates such as potassium tert-butoxide, sodium tert-butoxide, sodium ethylate and lithium methylate, hydride reagents such as sodium hydride, and amides such as sodium amide. Etc. can be used. As the solvent, N, N-dimethylformamide, tetrahydrofuran, dioxane, toluene and the like are used. The reaction can be allowed to proceed at a reaction temperature of usually from room temperature to about 150 ° C. The reaction time is, for example, 5 minutes to 40 hours, but may be any time that allows sufficient polymerization to proceed, and it is not necessary to leave the reaction for a long time after the reaction is completed. is there. If the reaction concentration is too dilute, the reaction efficiency is poor. If the concentration is too high, it becomes difficult to control the reaction. Therefore, the concentration may be appropriately selected within the range of about 0.01 wt% to the maximum concentration to be dissolved. The range is from 1 wt% to 20 wt%. In the case of the Heck reaction, a monomer is reacted using a palladium catalyst in the presence of a base such as triethylamine. A relatively high boiling point solvent such as N, N-dimethylformamide or N-methylpyrrolidone is used, the reaction temperature is about 80 to 160 ° C., and the reaction time is about 1 to 100 hours.

  In the case of the Suzuki coupling reaction, for example, palladium [tetrakis (triphenylphosphine)] or palladium acetate is used as a catalyst, an inorganic base such as potassium carbonate, sodium carbonate, or barium hydroxide; an organic base such as triethylamine; An inorganic salt such as cesium iodide is added in an amount of not less than an equivalent amount, preferably 1 to 10 equivalents, relative to the monomer. An inorganic salt may be used as an aqueous solution and reacted in a two-phase system. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. Although depending on the solvent, a temperature of about 50 to 160 ° C. is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.

  In the case of the Grignard reaction, a halide and metal Mg are reacted in an ether solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane or the like to form a Grignard reagent solution, and a monomer solution prepared separately is mixed with nickel. Alternatively, a method is exemplified in which a palladium catalyst is added while paying attention to excess reaction, and then the reaction is carried out while heating at reflux. The Grignard reagent is used in an equivalent amount or more, preferably 1 to 1.5 equivalents, more preferably 1 to 1.2 equivalents, relative to the monomer. Also in the case of polymerizing by a method other than these, the reaction can be carried out according to a known method.

  The condensation reaction compounds, oligomers, dendrimers and polymer compounds synthesized by the above method can be used as medicines / agrochemicals, organic electronic materials, and intermediates thereof.

  Oligomers, dendrimers, and polymer compounds synthesized by the above methods can also be used as materials for electronic devices. Light emitting materials and charge transport materials for polymer LEDs, organic semiconductors for organic transistors, dyes for lasers, organic solar It can also be used as a battery material.

Next, uses of the oligomer, dendrimer and polymer compound synthesized by the above method will be described. The oligomer, dendrimer, and polymer compound synthesized by the above method have fluorescence or phosphorescence in a solid state, and can be used as a polymer light emitter (high molecular weight light emitting material). Further, the polymer compound has an excellent electron transport ability, and can be suitably used as a polymer LED material or a charge transport material.
The polymer LED using the polymer light emitter is a high-performance polymer LED that can be driven with low voltage and high efficiency.
Therefore, the polymer LED can be preferably used for a backlight of a liquid crystal display, or a device such as a curved or flat light source for illumination, a segment type display element, a dot matrix flat panel display.
In addition, oligomers, dendrimers, and polymer compounds synthesized by the above methods are used for conductive thin films such as laser dyes, organic solar cell materials, organic semiconductors for organic transistors, light-emitting thin films, conductive thin films, and organic semiconductor thin films. It can also be used as a material.

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

化合物Ａ
原料である２，２’，５，５’−テトラメトキシ−１，１’−ビフェニルは、１−ブロモ−２，５−ジメトキシベンゼンからゼロ価ニッケルを用いたカップリング反応にて合成した。
不活性雰囲気下の三つ口フラスコに２，２’，５，５’−テトラメトキシ−１，１’−ビフェニル（7.0g、26mmmol）を入れ、脱水Ｎ，Ｎ−ジメチルホルムアミド（１00ml）に溶解した。フラスコを氷浴で冷却しながら、滴下ロートからＮ−クロロスクシンイミド（6.8g、52mmol）の脱水Ｎ，Ｎ−ジメチルホルムアミド（70ml）を１５分かけて滴下した。滴下終了後ゆっくりと攪拌しながらゆっくりと室温へ戻し、１日攪拌した。
反応液に水（300ml）を加えて、析出した沈殿をろ別回収した。得られた沈殿をトルエン／ヘキサンで再結晶し目的物を得た（収量 5.8g）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ３．７４（ｓ、６Ｈ）、３．８７（ｓ、６Ｈ）、６．８５（ｓ、２Ｈ）、７．０２（ｓ、２Ｈ） Synthesis Example 1 (Synthesis of Compound A)

Compound A
The raw material 2,2 ′, 5,5′-tetramethoxy-1,1′-biphenyl was synthesized from 1-bromo-2,5-dimethoxybenzene by a coupling reaction using zerovalent nickel.
Put 2,2 ', 5,5'-tetramethoxy-1,1'-biphenyl (7.0 g, 26 mmol) in a three-necked flask under inert atmosphere and dissolve in dehydrated N, N-dimethylformamide (100 ml). did. While the flask was cooled in an ice bath, dehydrated N, N-dimethylformamide (70 ml) of N-chlorosuccinimide (6.8 g, 52 mmol) was added dropwise from a dropping funnel over 15 minutes. After the completion of dropping, the mixture was slowly returned to room temperature with stirring and stirred for 1 day.
Water (300 ml) was added to the reaction solution, and the deposited precipitate was collected by filtration. The resulting precipitate was recrystallized from toluene / hexane to obtain the desired product (yield 5.8 g).
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 3.74 (s, 6H), 3.87 (s, 6H), 6.85 (s, 2H), 7.02 (s, 2H)

化合物Ｂ
不活性雰囲気下の三つ口フラスコに化合物Ａ（5.8g、１7mmmol）を入れ、脱水塩化メチレン（１00ml）に溶解した。フラスコを氷浴で冷却しながら、滴下ロートから三臭化ホウ素の塩化メチレン溶液（１mol/Ｌ、50ml）をの３０分かけて滴下した。滴下終了後ゆっくりと攪拌しながらゆっくりと室温へ戻し、一夜攪拌した。
反応液から酢酸エチルで抽出し、有機層を水洗いした後、溶媒を留去して目的物を得た（収量 4.9g）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ６．６４（ｓ、２Ｈ）、６．８２（ｓ、２Ｈ）、８．９〜９．１（ｂｒ、２Ｈ）、９．３７（ｓ、２Ｈ）。 Synthesis Example 2 (Synthesis of Compound B)

Compound B
Compound A (5.8 g, 17 mmol) was placed in a three-necked flask under an inert atmosphere and dissolved in dehydrated methylene chloride (100 ml). While cooling the flask in an ice bath, a solution of boron tribromide in methylene chloride (1 mol / L, 50 ml) was added dropwise from a dropping funnel over 30 minutes. After completion of dropping, the mixture was slowly returned to room temperature while stirring slowly and stirred overnight.
The reaction solution was extracted with ethyl acetate, and the organic layer was washed with water, and then the solvent was distilled off to obtain the desired product (yield 4.9 g).
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 6.64 (s, 2H), 6.82 (s, 2H), 8.9 to 9.1 (br, 2H), 9.37 (s, 2H).

化合物Ｃ
不活性雰囲気下の三つ口フラスコに化合物Ｂ（4.8g、１7mmmol）、ゼオライト（6.7g；Zeolite HSZ 360HUA（Tosoh））およびモレキュラーシーブスで乾燥したｏ−ジクロロベンゼン（１70ml）を加えた。オイルバスで加熱（バス温１80℃）しながら１３時間攪拌した。反応液を室温付近まで冷却し、ヘキサン（200ml）を加えた。析出したろ別し、ヘキサンで洗浄・乾燥した。沈殿から酢酸エチルで抽出し、その溶液をシリカゲルのショートカラムでボトムカットした後、溶媒を留去して、目的物を得た（収量3.5g）。
ＭＳスペクトル：[M-H]^- 267.0 Example 1 (Synthesis of Compound C)

Compound C
Compound B (4.8 g, 17 mmol), zeolite (6.7 g; Zeolite HSZ 360HUA (Tosoh)) and o-dichlorobenzene dried with molecular sieves (170 ml) were added to a three-necked flask under an inert atmosphere. The mixture was stirred for 13 hours while heating in an oil bath (bath temperature of 180 ° C.). The reaction solution was cooled to around room temperature, and hexane (200 ml) was added. The deposited precipitate was separated, washed with hexane and dried. The precipitate was extracted with ethyl acetate, and the solution was bottom-cut with a silica gel short column, and then the solvent was distilled off to obtain the desired product (yield 3.5 g).
MS spectrum: [MH] ^- 267.0

化合物Ｄ
不活性雰囲気下の三つ口フラスコに化合物Ｃ（4.2g）、４−Ｎ，Ｎ−ジメチルアミノピリジン（5.7g）入れ、脱水塩化メチレン（40ml）に溶解した。フラスコを氷浴で冷やしながらトリフルオロメタンスルホン酸無水物（１１g）を30分かけて滴下した。そのままゆっくりと室温まで昇温し５時間攪拌した。トルエンを加えてろ過し、ろ液をシリカゲルのショートカラムでボトムカットした後、溶媒を留去した。得られた固体をトルエン／ヘキサン系で再結晶し目的物を得た（7.6g）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ７．８０（ｓ、２Ｈ）、７．９３（ｓ、２Ｈ）。 Example 2 (Synthesis of Compound D)

Compound D
Compound C (4.2 g) and 4-N, N-dimethylaminopyridine (5.7 g) were placed in a three-necked flask under an inert atmosphere and dissolved in dehydrated methylene chloride (40 ml). While the flask was cooled in an ice bath, trifluoromethanesulfonic anhydride (11 g) was added dropwise over 30 minutes. The mixture was slowly warmed up to room temperature and stirred for 5 hours. Toluene was added for filtration, and the filtrate was bottom cut with a short column of silica gel, and then the solvent was distilled off. The obtained solid was recrystallized from a toluene / hexane system to obtain the desired product (7.6 g).
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.80 (s, 2H), 7.93 (s, 2H).

化合物Ｅ
不活性雰囲気下１ｌの四つ口フラスコに２，８−ジブロモジベンゾチオフェン ７ｇとＴＨＦ ２８０ｍｌを入れ、室温で撹拌、溶かした後、−７８℃まで冷却した。ｎ−ブチルリチウム ２９ｍｌ（１．６モルヘキサン溶液）を滴下した。滴下終了後、温度を保持したまま２時間撹拌し、トリメトキシボロン酸 １３ｇを滴下した。滴下終了後、ゆっくり室温まで戻した。３時間室温で撹拌後、ＴＬＣで原料の消失を確認した。５％硫酸 １００ｍｌを加えて反応を終了させ、室温で１２時間撹拌した。水を加えて洗浄し、有機層を抽出した。溶媒を酢酸エチルに置換した後、３０％過酸化水素水 ５ｍｌを加え、４０℃で５時間撹拌した。その後有機層を抽出し、１０％硫酸アンモニウム鉄（II）水溶液で洗浄後乾燥、溶媒を除去することにより、茶色の固体 ４．４３ｇを得た。
ＭＳ（ＡＰＣＩ（−））：（Ｍ−Ｈ）^- ２１５ Synthesis Example 3 (Synthesis of Compound E)

Compound E
Under an inert atmosphere, 7 g of 2,8-dibromodibenzothiophene and 280 ml of THF were placed in a 1 l four-necked flask, stirred and dissolved at room temperature, and then cooled to -78 ° C. 29 ml of n-butyllithium (1.6 molar hexane solution) was added dropwise. After completion of dropping, the mixture was stirred for 2 hours while maintaining the temperature, and 13 g of trimethoxyboronic acid was added dropwise. After completion of dropping, the temperature was slowly returned to room temperature. After stirring at room temperature for 3 hours, disappearance of the raw material was confirmed by TLC. The reaction was terminated by adding 100 ml of 5% sulfuric acid and stirred at room temperature for 12 hours. Water was added for washing, and the organic layer was extracted. After replacing the solvent with ethyl acetate, 5 ml of 30% aqueous hydrogen peroxide was added and stirred at 40 ° C. for 5 hours. Thereafter, the organic layer was extracted, washed with a 10% aqueous solution of ammonium iron (II) sulfate, dried and the solvent was removed to obtain 4.43 g of a brown solid.
MS (APCI (-)) :( M-H) - 215

化合物Ｆ
不活性雰囲気下で２００ｍｌの三つ口フラスコに化合物Ｅ ４．４３ｇと臭化ｎ−オクチル ２５．１ｇ、および炭酸カリウム １２．５ｇ（２３．５ｍｍｏｌ）を入れ、溶媒としてメチルイソブチルケトン ５０ｍｌを加えて１２５℃で６時間加熱還流した。反応終了後、溶媒を除き、クロロホルムと水で分離、有機層を抽出し、さらに水で２回洗浄した。無水硫酸ナトリウムで乾燥後、シリカゲルカラム（展開溶媒：トルエン／シクロヘキサン＝１／１０）で精製することにより、８．４９ｇの化合物Ｆを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９１（ｔ、６Ｈ）、１．３１〜１．９０（ｍ、２４Ｈ）、４．０８（ｔ、４Ｈ）、７．０７（ｄｄ、２Ｈ）、７．５５（ｄ、２Ｈ）、７．６８（ｄ、２Ｈ） Synthesis Example 4 (Synthesis of Compound F)

Compound F
Under an inert atmosphere, 4.43 g of compound E, 25.1 g of n-octyl bromide, and 12.5 g (23.5 mmol) of potassium carbonate were placed in a 200 ml three-necked flask, and 50 ml of methyl isobutyl ketone was added as a solvent. The mixture was heated to reflux at 125 ° C. for 6 hours. After completion of the reaction, the solvent was removed, the organic layer was extracted with chloroform and water, and further washed twice with water. After drying over anhydrous sodium sulfate, purification was performed with a silica gel column (developing solvent: toluene / cyclohexane = 1/10) to obtain 8.49 g of Compound F.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.91 (t, 6H), 1.31-1.90 (m, 24H), 4.08 (t, 4H), 7.07 (dd, 2H), 7.55 (d, 2H), 7 .68 (d, 2H)

化合物Ｇ
１００ｍｌ三つ口フラスコに化合物Ｆ ６．６７ｇと酢酸 ４０ｍｌを入れ、オイルバスでバス温度１４０℃まで昇温した。続いて、３０％過酸化水素水 １３ｍｌを冷却管から加え、１時間強く撹拌した後、冷水１８０ｍｌに注いで反応を終了させた。クロロホルムで抽出、乾燥後溶媒を除去することによって、６．９６ｇの化合物Ｇを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、６Ｈ）、１．２６〜１．８７（ｍ、２４Ｈ）、４．０６（ｔ、４Ｈ）、７．１９（ｄｄ、２Ｈ）、７．６９（ｄ、２Ｈ）、７．８４（ｄ、２Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ４７３ Synthesis Example 5 (Synthesis of Compound G)

Compound G
A 100 ml three-necked flask was charged with 6.67 g of compound F and 40 ml of acetic acid, and the temperature was raised to 140 ° C. in an oil bath. Subsequently, 13 ml of 30% aqueous hydrogen peroxide was added from the condenser, and after vigorously stirring for 1 hour, the reaction was terminated by pouring into 180 ml of cold water. 6.96 g of compound G was obtained by removing the solvent after extraction with chloroform and drying.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.87 (m, 24H), 4.06 (t, 4H), 7.19 (dd, 2H), 7.69 (d, 2H), 7 .84 (d, 2H)
MS (APCI (+)): (M + H) ^<+> 473

化合物Ｈ
不活性雰囲気下２００ｍｌ四つ口フラスコに化合物Ｇ ３．９６ｇと酢酸／クロロホルム＝１：１混合液 １５ｍｌを加え、７０℃で撹拌し、溶解させた。続いて、臭素 ６．０２ｇを上記の溶媒 ３ｍｌに溶かして加え、３時間撹拌した。チオ硫酸ナトリウム水溶液を加えて未反応の臭素を除き、クロロホルムと水で分離、有機層を抽出、乾燥した。溶媒を除去し、シリカゲルカラム（展開溶媒：クロロホルム／ヘキサン＝１／４）で精製することにより、４．４６ｇの化合物Ｈを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９５（ｔ、６Ｈ）、１．３０〜１．９９（ｍ、２４Ｈ）、４．１９（ｔ、４Ｈ）、７．０４（ｓ、２Ｈ）、７．８９（ｓ、２Ｈ）
ＭＳ（ＦＤ⁺）Ｍ⁺ ６３０ Example 3 (Synthesis of Compound H)

Compound H
Under an inert atmosphere, 3.96 g of Compound G and 15 ml of a mixed solution of acetic acid / chloroform = 1: 1 were added to a 200 ml four-necked flask and stirred at 70 ° C. to dissolve. Subsequently, 6.02 g of bromine was dissolved in 3 ml of the above solvent, and the mixture was stirred for 3 hours. An aqueous sodium thiosulfate solution was added to remove unreacted bromine, and the mixture was separated with chloroform and water, and the organic layer was extracted and dried. The solvent was removed, and purification was performed with a silica gel column (developing solvent: chloroform / hexane = 1/4) to obtain 4.46 g of Compound H.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.95 (t, 6H), 1.30 to 1.99 (m, 24H), 4.19 (t, 4H), 7.04 (s, 2H), 7.89 (s, 2H)
MS (FD ⁺ ) M ⁺ 630

化合物Ｉ
不活性雰囲気下２００ｍｌ三つ口フラスコに化合物Ｈ ３．９ｇとジエチルエーテル ５０ｍｌを入れ、４０℃まで昇温、撹拌した。水素化アルミニウムリチウム １．１７ｇを少量ずつ加え、５時間反応させた。水を少量ずつ加えることによって過剰な水素化アルミニウムリチウムを分解し、３６％塩酸 ５．７ｍｌで洗浄した。クロロホルム、水で分離、有機層を抽出後乾燥した。シリカゲルカラム（展開溶媒：クロロホルム／ヘキサン＝１／５）で精製することにより、１．８ｇの化合物Ｉを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、６Ｈ）、１．２６〜１．９７（ｍ、２４Ｈ）、４．１５（ｔ、４Ｈ）、７．４５（ｓ、２Ｈ）、７．９４（ｓ、２Ｈ）
ＭＳ（ＦＤ⁺）Ｍ⁺ ５９８ Example 4 Synthesis of Compound I

Compound I
Under an inert atmosphere, 3.9 g of Compound H and 50 ml of diethyl ether were placed in a 200 ml three-necked flask, heated to 40 ° C. and stirred. Lithium aluminum hydride 1.17 g was added little by little and allowed to react for 5 hours. Excess lithium aluminum hydride was decomposed by adding water little by little and washed with 5.7 ml of 36% hydrochloric acid. Separated with chloroform and water, the organic layer was extracted and dried. By purification with a silica gel column (developing solvent: chloroform / hexane = 1/5), 1.8 g of Compound I was obtained.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.97 (m, 24H), 4.15 (t, 4H), 7.45 (s, 2H), 7.94 (s, 2H)
MS (FD ⁺ ) M ⁺ 598

化合物Ｊ
化合物Ｉをジクロロメタンに溶解し、三臭化ホウ素を加え攪拌した。反応終了後、水を加え、水相を酢酸エチルで抽出し、溶媒を留去すると化合物Ｊが得られる。 Example 5 (Synthesis of Compound J)

Compound J
Compound I was dissolved in dichloromethane, and boron tribromide was added and stirred. After completion of the reaction, water is added, the aqueous phase is extracted with ethyl acetate, and the solvent is distilled off to obtain compound J.

化合物Ｊ
化合物Ｉをジクロロメタンに溶解し、三臭化ホウ素を加え攪拌した。反応終了後、水を加え、水相を酢酸エチルで抽出し、溶媒を留去すると化合物Ｊが得られる。 Example 6 (Synthesis of Compound K)

Compound J
Compound I was dissolved in dichloromethane, and boron tribromide was added and stirred. After completion of the reaction, water is added, the aqueous phase is extracted with ethyl acetate, and the solvent is distilled off to obtain compound J.

化合物Ｋ
500 ml-3口フラスコをアルゴン置換した後、ジベンゾフラン3.00 gをとり、60 mlの脱水ジエチルエーテルに溶解させ、N,N,N’,N’-テトラメチルエチレンジアミン8.2 mlを加えた。-78 ℃に冷却した後、s-ブチルリチウム54 ml（0.99 Mシクロヘキサン・ヘキサン溶液）を１0分で滴下した。室温まで昇温し、４時間攪拌した後、-78 ℃に冷却し、トリメトキシボラン7.１ mlを一度に加えた。室温まで昇温し、4時間攪拌した。0 ℃まで冷却し、30%過酸化水素水20 mlを30分で滴下した。滴下後、１時間攪拌し、飽和亜硫酸水素ナトリウム水溶液20 mlを20分で滴下した。室温で3時間攪拌した後、１ N塩酸を加え酸性にし、１00 mlのジエチルエーテルで3回抽出した。硫酸ナトリウムで乾燥した後、3.76 gの化合物Ｋを得た。
¹H-NMR（CD3OD, 300MHz）：δ7.46（2H, d）, 7.１8（2H, t）, 6.97（2H,d）
MS（ESI-negative, KCl添加）m/z：１99.１（［M-H］^-） Synthesis Example 6 (Synthesis of Compound K)

Compound K
After replacing the 500 ml three-necked flask with argon, 3.00 g of dibenzofuran was taken and dissolved in 60 ml of dehydrated diethyl ether, and 8.2 ml of N, N, N ′, N′-tetramethylethylenediamine was added. After cooling to −78 ° C., 54 ml of s-butyllithium (0.99 M cyclohexane / hexane solution) was added dropwise over 10 minutes. The mixture was warmed to room temperature, stirred for 4 hours, cooled to −78 ° C., and 7.1 ml of trimethoxyborane was added all at once. The mixture was warmed to room temperature and stirred for 4 hours. The mixture was cooled to 0 ° C., and 20 ml of 30% aqueous hydrogen peroxide was added dropwise over 30 minutes. After the dropwise addition, the mixture was stirred for 1 hour, and 20 ml of a saturated aqueous sodium hydrogen sulfite solution was added dropwise over 20 minutes. The mixture was stirred at room temperature for 3 hours, acidified with 1N hydrochloric acid, and extracted three times with 100 ml of diethyl ether. After drying with sodium sulfate, 3.76 g of compound K was obtained.
¹ H-NMR (CD3OD, 300 MHz): δ 7.46 (2H, d), 7.18 (2H, t), 6.97 (2H, d)
MS (ESI-negative, KCl added) m / z: 199.1 ([MH] ^- )

化合物Ｌ
１00 ml-3口フラスコを窒素置換した後、化合物Ｋ0.50 gをとり、１8 mlの脱水DMFに溶解させ、炭酸カリウム0.80 g、１-ブロモオクタン0.9 mlを加えた。バス温１20 ℃で2時間攪拌した後放冷し、水50 ml加えて50 mlのトルエンで3回抽出した。有機相を合わせ、シリカゲルでろ過した後に溶媒を留去することにより化合物Ｌ 0.90gを得た。
¹H-NMR（CDCl3, 300MHz）δ7.50（2H, d）, 7.22（2H, t）, 6.97（2H, d）, 4.24（4H, t）, １.96〜１.87（4H, m）, １.58〜１.48（4H, m）, １.43〜１.30（１6H, m）, 0.89（6H, t）.
¹³C-NMR（CDCl3, 300MHz）δ１46.0, １45.6, １26.4, １23.6, １１3.0, １１１.3, 69.7, 32.１, 29.7, 29.6, 29.5, 26.3, 23.0, １4.4.
MS（APCI-positive）m/z：425.3（［M+H］⁺）. Synthesis Example 7 (Synthesis of Compound L)

Compound L
After the 100 ml three-necked flask was purged with nitrogen, 0.50 g of compound K was taken and dissolved in 18 ml of dehydrated DMF, and 0.80 g of potassium carbonate and 0.9 ml of 1-bromooctane were added. The mixture was stirred at a bath temperature of 120 ° C. for 2 hours, allowed to cool, added with 50 ml of water, and extracted three times with 50 ml of toluene. The organic phases were combined, filtered through silica gel, and then the solvent was distilled off to obtain 0.90 g of compound L.
¹ H-NMR (CDCl3, 300 MHz) δ 7.50 (2H, d), 7.22 (2H, t), 6.97 (2H, d), 4.24 (4H, t), 1.96 to 1.87 (4H, m ), 1.58 to 1.48 (4H, m), 1.43 to 1.30 (16H, m), 0.89 (6H, t).
¹³ C-NMR (CDCl 3, 300 MHz) δ 146.0, 145.6, 126.4, 123.6, 113.0, 111.3, 69.7, 32.1, 29.7, 29.6, 29.5, 26.3, 23.0, 14 .Four.
MS (APCI-positive) m / z: 425.3 ([M + H] ⁺ ).

化合物Ｍ
１00 ml-3口フラスコをアルゴン置換した後、化合物Ｌ0.83 gをとり、１7 mlの脱水ジエチルエーテルに溶解させ、N,N,N’,N’-テトラメチルエチレンジアミン0.8 mlを加え、-78 ℃に冷却した。s-ブチルリチウム5.１ ml（0.99 Mシクロヘキサン・ヘキサン溶液）を5分間で滴下し、滴下後１0分攪拌した後、冷浴をはずし、室温にて4時間攪拌した後、-78 ℃に冷却した。この溶液に１,2-ジブロモ-１,１,2,2-テトラフルオロエタン0.7 mlを5 mlのジエチルエーテルに溶解した溶液を5分で滴下した。5分攪拌後、冷浴をはずし、室温にて3時間攪拌した。飽和炭酸水素ナトリウム水溶液１0 ml加えて水相を１0 mlのトルエンで2回抽出した。有機相を合わせ、シリカゲルでろ過した後に溶媒を留去することにより化合物Ｍ １.１0 gを得た。
¹H-NMR（CDCl3, 300MHz）：δ 7.47（2H, d）, 7.39（2H, d）, 4.47（4H, t）, １.92〜１.83（4H, m）, １.6１〜１.5１（4H, m）, １.40〜１.25（１6H, m）, 0.89（6H, t）.
¹³C-NMR（CDCl3, 300MHz）：δ１47.7, １42.3, １28.3, １25.9, １１5.3, １１4.１, 74.１, 32.１, 30.5, 29.7, 29.6, 26.3, 23.0, １4.4.
MS（ESI-positive）：m/z：6１9.0, 62１.0, 622.5（［M+H］⁺）. Example 7 (Synthesis of Compound M)

Compound M
After the 100 ml three-necked flask was purged with argon, 0.83 g of compound L was taken and dissolved in 17 ml of dehydrated diethyl ether, 0.8 ml of N, N, N ′, N′-tetramethylethylenediamine was added, and −78 Cooled to ° C. After dropwise addition of 5.1 ml of s-butyllithium (0.99 M cyclohexane / hexane solution) over 5 minutes and stirring for 10 minutes, the cooling bath was removed and the mixture was stirred at room temperature for 4 hours and then cooled to -78 ° C. did. To this solution, a solution prepared by dissolving 0.7 ml of 1,2-dibromo-1,1,2,2-tetrafluoroethane in 5 ml of diethyl ether was added dropwise over 5 minutes. After stirring for 5 minutes, the cold bath was removed and the mixture was stirred at room temperature for 3 hours. A saturated aqueous sodium hydrogen carbonate solution (10 ml) was added, and the aqueous phase was extracted twice with 10 ml of toluene. The organic phases were combined, filtered through silica gel, and then the solvent was distilled off to obtain 1.10 g of compound M.
¹ H-NMR (CDCl 3, 300 MHz): δ 7.47 (2H, d), 7.39 (2H, d), 4.47 (4H, t), 1.92 to 1.83 (4H, m), 1.61 to 1 .51 (4H, m), 1.40 to 1.25 (16H, m), 0.89 (6H, t).
¹³ C-NMR (CDCl 3, 300 MHz): δ 147.7, 142.3, 128.3, 125.9, 115.3, 114.1, 74.1, 32.1, 30.5, 29.7, 29.6, 26.3, 23.0, 14.4.
MS (ESI-positive): m / z: 619.0, 621.0, 622.5 ([M + H] ⁺ ).

化合物Ｎ
実施例５、６と同様の処理をおこなうことにより化合物Ｎを合成することができる。 Example 8 (Synthesis of Compound N)

Compound N
Compound N can be synthesized by the same treatment as in Examples 5 and 6.

化合物Ｏ
500 ml-3口フラスコをアルゴン置換した後、ジベンゾチオフェン5.00 gをとり、１00 mlの脱水ジエチルエーテルに溶解させ、N,N,N’,N’-テトラメチルエチレンジアミン１2.5 mlを加えた。-78 ℃に冷却した後、s-ブチルリチウム82 mlを１0分で滴下した。室温まで昇温し、3時間攪拌した後、-78℃に冷却し、トリメトキシボラン１１ mlを一度に加えた。室温まで昇温し、１.5時間攪拌した。0 ℃まで冷却し、30%過酸化水素水30 mlを20分で滴下した。滴下後、１時間攪拌し、飽和亜硫酸水素ナトリウム水溶液30 mlを１0分で滴下した。室温で3時間攪拌した後、１N塩酸を加え酸性にし、１00 mlのジエチルエーテルで3回抽出した。硫酸ナトリウムで乾燥した後、6.3１ gの粗生成物を得た。トルエン：エタノール＝５：１混合溶媒から２回再結晶することにより化合物Ｏ 0.6１gを得た。
¹H-NMR（CD3OD, 300MHz）δ 7.69（2H, d）, 7.3１（2H, t）, 6.90（2H, d）.
MS（ESI-negative, KCl添加）m/z：2１5.１（［M-H］^-）. Synthesis Example 8 (Synthesis of Compound O)

Compound O
After replacing the 500 ml three-neck flask with argon, 5.00 g of dibenzothiophene was taken and dissolved in 100 ml of dehydrated diethyl ether, and 12.5 ml of N, N, N ′, N′-tetramethylethylenediamine was added. After cooling to −78 ° C., 82 ml of s-butyllithium was added dropwise over 10 minutes. The mixture was warmed to room temperature, stirred for 3 hours, cooled to -78 ° C, and 11 ml of trimethoxyborane was added at once. The mixture was warmed to room temperature and stirred for 1.5 hours. The mixture was cooled to 0 ° C., and 30 ml of 30% hydrogen peroxide was added dropwise over 20 minutes. After dropping, the mixture was stirred for 1 hour, and 30 ml of a saturated aqueous solution of sodium bisulfite was added dropwise over 10 minutes. The mixture was stirred at room temperature for 3 hours, acidified with 1N hydrochloric acid and extracted three times with 100 ml of diethyl ether. After drying with sodium sulfate, 6.31 g of crude product was obtained. Recrystallization from a mixed solvent of toluene: ethanol = 5: 1 twice gave 0.61 g of compound O.
¹ H-NMR (CD3OD, 300 MHz) δ 7.69 (2H, d), 7.31 (2H, t), 6.90 (2H, d).
MS (ESI-negative, KCl added) m / z: 215.1 ([MH] ⁻ ).

化合物Ｐ
１00 ml-3口フラスコを窒素置換した後、化合物Ｏ 0.50gをとり、１4 mlの脱水DMFに溶解させ、炭酸カリウム0.86 g、１-ブロモオクタン0.9 mlを加えた。バス温１20 ℃で2時間攪拌した後放冷し、水50 ml加えて50 mlのトルエンで3回抽出した。有機相を合わせ、シリカゲルでろ過した後に溶媒を留去することにより化合物Ｐ 0.95gを得た。
¹H-NMR（CDCl3, 300MHz）δ 7.69（2H, d）, 7.35（2H, t）, 6.86（2H, d）, 4.１4（4H, t）, １.92〜１.82（4Ｈ, m）, １.54〜１.47（4H, m）, １.42〜１.30（１6Ｈ, m）, 0.89（6H, t）.
¹³C-NMR（CDCl3, 300MHz）δ１54.6, １38.0, １29.2, １25.8, １１4.5, １07.9, 68.9, 32.2, 29.7, 29.6, 26.4, 23.0, １4.5. Synthesis Example 9 (Synthesis of Compound P)

Compound P
The 100 ml three-necked flask was purged with nitrogen, 0.50 g of compound O was taken, dissolved in 14 ml of dehydrated DMF, and 0.86 g of potassium carbonate and 0.9 ml of 1-bromooctane were added. The mixture was stirred at a bath temperature of 120 ° C. for 2 hours and then allowed to cool. The organic phases were combined, filtered through silica gel, and then the solvent was distilled off to obtain 0.95 g of compound P.
¹ H-NMR (CDCl 3, 300 MHz) δ 7.69 (2H, d), 7.35 (2H, t), 6.86 (2H, d), 4.14 (4H, t), 1.92 to 1.82 (4H, m), 1.54 to 1.47 (4H, m), 1.42 to 1.30 (16H, m), 0.89 (6H, t).
¹³ C-NMR (CDCl 3, 300 MHz) δ154.6, 138.0, 129.2, 125.8, 114.5, 107.9, 68.9, 32.2, 29.7, 29.6, 26.4, 23.0, 14.5.

化合物Ｑ
500 ml-3口フラスコをアルゴン置換した後、化合物Ｐ 9.00gをとり、１80 mlの脱水ジエチルエーテルに溶解させ、N,N,N’,N’-テトラメチルエチレンジアミン8.7 mlを加えた。-78 ℃に冷却した後、s-ブチルリチウム57 ml（0.99 Mシクロヘキサン・ヘキサン溶液）を１0分で滴下した。徐々に室温まで昇温した後、5時間還流した後、-78 ℃に冷却し、１,2-ジブロモ-１,１,2,2-テトラフルオロエタン8 mlを40 mlの脱水ジエチルエーテルに溶解した溶液を30分で滴下した。室温まで昇温し、3時間攪拌した。飽和炭酸水素ナトリウム水溶液１00 ml加え、１00 mlのヘキサンで2回抽出した。シリカゲルショートカラムを通した後、溶媒を留去することにより、化合物Ｑ １１.20gを得た。
¹H-NMR（CDCl3, 300MHz）δ 7,62（2H, d）, 7.56（2H, d）, 4.20（4H, t）, １.96〜１.84（4H, m）, １.64〜１.48（4H, m）, １.40〜１.25（１6H, m）, 0.90 （6H, t）.
MS（APPI−positive）ｍ／ｚ：600, 598, 596（［M］⁺）.
Example 9 (Synthesis of Compound Q)

Compound Q
After replacing the 500 ml three-necked flask with argon, 9.00 g of compound P was taken and dissolved in 180 ml of dehydrated diethyl ether, and 8.7 ml of N, N, N ′, N′-tetramethylethylenediamine was added. After cooling to −78 ° C., 57 ml of s-butyllithium (0.99 M cyclohexane / hexane solution) was added dropwise over 10 minutes. After gradually warming to room temperature, refluxed for 5 hours, cooled to -78 ° C, and dissolved 8 ml of 1,2-dibromo-1,1,2,2-tetrafluoroethane in 40 ml of dehydrated diethyl ether The solution was added dropwise over 30 minutes. The mixture was warmed to room temperature and stirred for 3 hours. A saturated aqueous sodium hydrogen carbonate solution (100 ml) was added, and the mixture was extracted twice with 100 ml of hexane. After passing through a silica gel short column, the solvent was distilled off to obtain 11.20 g of Compound Q.
¹ H-NMR (CDCl 3, 300 MHz) δ 7,62 (2H, d), 7.56 (2H, d), 4.20 (4H, t), 1.96 to 1.84 (4H, m), 1.64 to 1.48 (4H, m), 1.40 to 1.25 (16H, m), 0.90 (6H, t).
MS (APPI-positive) m / z: 600, 598, 596 ([M] ⁺ ).

５０ｍｌ２口フラスコを窒素置換した後、化合物Ｒ（特開２００４−１６８９９９に開示）１００ｍｇ（０．１５ｍｍｏｌ）と１，３−ジクロロ−５−ヨードベンゼン１２０ｍｇ（０．４４ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（０）１０ｍｇ（０．０１ｍｍｏｌ）を取り、１ｍｌのトルエンに溶解させた。１Ｍ炭酸カリウム水溶液を１ｍｌ加え、還流下、２０時間攪拌した。分液し、有機相を水、飽和食塩水で洗浄後、溶媒を留去し、粗生成物を得た。
MS（ESI−negative）ｍ／ｚ：７２９（［M+Ｃｌ］^-）.
Example 10 (Synthesis of Compound S)

After replacing the nitrogen in the 50 ml two-necked flask, 100 mg (0.15 mmol) of Compound R (disclosed in JP-A-2004-168999), 120 mg (0.44 mmol) of 1,3-dichloro-5-iodobenzene, tetrakis (triphenylphosphine) 10 mg (0.01 mmol) of palladium (0) was taken and dissolved in 1 ml of toluene. 1 ml of 1M aqueous potassium carbonate solution was added, and the mixture was stirred for 20 hours under reflux. After liquid separation, the organic phase was washed with water and saturated brine, and then the solvent was distilled off to obtain a crude product.
MS (ESI-negative) m / z: 729 ([M + Cl] ^- ).

化合物Ｔ（特開２００４−１６８９９９に開示）をジクロロメタン溶媒中、三臭化ホウ素で処理することにより、化合物Ｕが得られる。化合物Ｕを実施例２と同様の処理をおこない、化合物Ｖを得ることができる。
Example 11 (Synthesis of Compound V)

Compound U (disclosed in JP 2004-168999 A) is treated with boron tribromide in dichloromethane solvent to give compound U. Compound V can be obtained by treating compound U in the same manner as in Example 2.

上記で合成した化合物ＩをＴＨＦ溶媒中、−７８℃で１当量のｎ−ブチルリチウムで処理した後、１／４当量の四塩化ケイ素と反応させることにより化合物Ｗが得られる。



Example 12 (Synthesis of Compound W)

The compound I synthesized above is treated with 1 equivalent of n-butyllithium at −78 ° C. in a THF solvent, and then reacted with 1/4 equivalent of silicon tetrachloride to give compound W.

Claims (7)

An aromatic compound represented by the following formula (1) or (2).

[Wherein, Ar ¹ and Ar ³ each independently represents a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic group. Ar ² represents a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and Ar ¹ , Ar ² and Ar ³ may have a substituent, and Ar ¹ and Ar ² are a substituent. When they have, they may combine to form a ring, and when Ar ¹ and Ar ³ have a substituent, they may combine to form a ring.
A ¹ represents -Z ^1- , -Z ² -Z ³ -or -Z ⁴ = Z ^5- , and Z ¹ , Z ² and Z ³ are each independently O, S, C ( = O), S (= O), SO ₂ , C (R ¹ ) (R ² ), Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) Or P (═O) (R ⁸ ), and Z ⁴ and Z ⁵ are each independently N, B, P, C (R ⁹ ) or Si (R ¹⁰ ).
Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group , Alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group Substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, carboxyl group, alkyloxycarbonyl group, Aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycal It represents an alkenyl group, or a cyano group. However, R ¹ and R ^2, R ³ and R ⁴ represents a bond to each other may form a ring.). However, in Formula (1), Ar ² and A ¹ are bonded to adjacent atoms on the Ar ¹ ring, Ar ¹ and A ¹ are bonded to adjacent atoms on the Ar ² ring, and in Formula (2), Ar ³ and A ¹ are bonded to adjacent atoms on the Ar ¹ ring, and Ar ¹ and A ¹ are bonded to adjacent atoms on the Ar ³ ring.
X ¹ , X ² , X ³ and X ⁴ are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, —B (OH) ₂ , or a monohalogenated methyl Represents a group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group, vinyl group, hydroxyl group, alkyloxy group, acyloxy group, substituted silyloxy group, amino group or nitro group, X in formula (1) ¹ , at least one of X ² and X ³ and at least one of X ¹ , X ² , X ³ and X ⁴ in formula (2) is a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group , borate group, -B (OH) _2, methyl monohalide group Sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, selected from cyanomethyl group, a formyl group and a vinyl group. ] All of X ¹ , X ² and X ³ in formula (1) and all of X ¹ , X ² , X ³ and X ⁴ in formula (2) are halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups. , Boric acid ester group, —B (OH) ₂ , monohalogenated methyl group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, cyanomethyl group, formyl group and vinyl group, The aromatic compound described. An aromatic compound represented by the following formula (5) or (6).

[Wherein, A ¹ and X ³ represent the same meaning as described above, and Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group. The Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ may have a substituent, and when Ar ⁴ and Ar ⁵ have a substituent, they may be bonded to form a ring. .
X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, —B (OH) ₂ , a monohalogenated methyl group, Represents a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a cyanomethyl group, a formyl group, a vinyl group, a hydroxyl group, an alkyloxy group, an acyloxy group, a substituted silyloxy group, an amino group or a nitro group, and X ⁹ in formula (5), At least one of X ¹⁰ and X ³ and at least one of X ⁹ , X ¹⁰ , X ¹¹ and X ¹² in formula (6) are a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boron Acid ester group, -B (OH) ₂ , monohalogenated methyl group, A sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a cyanomethyl group, a formyl group or a vinyl group. ] All of X ⁹ , X ¹⁰ and X ³ in formula (5) and all of X ⁹ , X ¹⁰ , X ¹¹ and X ¹² in formula (6) are a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl It is selected from alkylsulfonate groups, borate groups, -B (OH) ₂ , monohalogenated methyl groups, sulfonium methyl groups, phosphonium methyl groups, phosphonate methyl groups, cyanomethyl groups, formyl groups and vinyl groups. The aromatic compound according to claim 3. An aromatic compound represented by the following formula (9), (10) or (11).

[Wherein Ar ⁴ and Ar ⁵ represent the same meaning as described above, and Ar ⁸ , Ar ⁹ and Ar ¹⁰ each independently represent an arylene group or a divalent heterocyclic group, and the Ar ⁴ , Ar ⁵ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ may have a substituent, and when Ar ⁴ and Ar ⁵ have a substituent, they may be bonded to form a ring, and Ar ⁹ and Ar ¹⁰ are When it has a substituent, they may be bonded to form a ring, or Ar ⁹ and Ar ¹⁰ may be directly bonded to form a ring.
A ² is the following formula:

(Wherein Z ⁶ represents B, P or P (═O), Z ⁷ represents C (R ⁹ ), Si (R ¹⁰ ), N, B, P or P (═O); Z ⁸ Are O, S, C (═O), S (═O), SO ₂ , C (R ¹ ) (R ² ), Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (═O) (R ⁸ ), Z ⁹ represents C or Si, Z ¹⁰ represents N, B, P, C (R ⁹ ) or Si (R ¹⁰ ). R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above.)
Represents one of the following:
A ³ is the following formula

(In the formula, Z ¹¹ represents C or Si, and Z ¹² represents O, S, C (═O), S (═O), SO ₂ , C (R ¹ ) (R ² ), Si (R ³ ). (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (═O) (R ⁸ ), and Z ¹³ and Z ¹⁴ are each independently C (R ⁹ ), Represents Si (R ¹⁰ ), B, N, P or P (═O), Z ¹⁵ and Z ¹⁶ each independently represent C or Si, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above.)
Represents one of the following:
A ⁴ is a hydrogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, substituted silyl group, monovalent group Represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group or an arylethynyl group. However, in Formula (9), Ar ⁵ and A ² are bonded to adjacent atoms of the Ar ⁴ ring, and Ar ⁴ and A ² are bonded to adjacent atoms of the Ar ⁵ ring.
X ¹⁸ , X ¹⁹ , X ²⁰ , X ²¹ and X ²² are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, a borate group, —B (OH) ₂ , mono A halogenated methyl group, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a cyanomethyl group, a formyl group, a vinyl group, a hydroxyl group, an alkyloxy group, an acyloxy group, a substituted silyloxy group, an amino group or a nitro group, ) At least one of X ¹⁸ , X ¹⁹ and X ²⁰ , at least one of X ¹⁸ , X ²¹ and X ²² in formula (10), and X ¹⁸ , X ¹⁹ , X ²¹ and X ²² in formula (11) At least one of a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl A sulfonate group, a borate group, —B (OH) ₂ , a monohalogenated methyl group, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a cyanomethyl group, a formyl group, and a vinyl group are selected. ] All of X ¹⁸ , X ¹⁹ and X ²⁰ in Formula (9), and all of X ¹⁸ , X ²¹ and X ²² in Formula (10) and X ¹⁸ , X ¹⁹ , X ²¹ and X ²² in Formula (11) All are halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, borate ester groups, -B (OH) ₂ , monohalogenated methyl groups, sulfonium methyl groups, phosphonium methyl groups, phosphonate methyl groups, cyanomethyl 6. The aromatic compound according to claim 5, which is a group, a formyl group or a vinyl group. An aromatic compound represented by the following formula (15).

(Wherein Ar ⁴ , Ar ⁵ , A ¹ and X ³ represent the same meaning as described above. A ⁵ represents a boron atom, an aluminum atom, a gallium atom, a silicon atom, a germanium atom, a nitrogen atom, a phosphorus atom, and arsenic. An atom, an a-valent aromatic hydrocarbon group, an a-valent heterocyclic group or an a-valent group having a metal complex structure, wherein a represents 3 or 4. Plural Ar ⁴ , Ar ⁵ , A ¹ and X ¹⁰ may be the same as or different from each other.