JP2009227652A - Biphenylene derivative, its use and process for preparing the same - Google Patents

Abstract

（ここで、置換基Ｒ^１〜Ｒ^８は同一又は異なって、水素原子、フッ素原子、炭素数２〜２０のアルキル基、炭素数２〜２０のアルキニル基、炭素数２〜３０のアルケニル基、又は炭素数４〜２０のアリール基を示し、ｍは１又は２であり、ｎは０〜２の整数を示す。但し、Ｒ^１及びＲ^２は同時に水素原子であることはない。）
【選択図】なしA biphenylene derivative having excellent oxidation resistance and capable of forming a semiconductor active phase by a coating method, an oxidation resistant organic semiconductor material using the same, an organic thin film comprising the same, a light emitting material, and the biphenylene derivative Providing a simple and economical manufacturing method.
A biphenylene derivative represented by the formula (1).

(Here, the substituents R ^{1 to} R ⁸ are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, Or an aryl group having 4 to 20 carbon atoms, m is 1 or 2, and n is an integer of 0 to 2. However, R ¹ and R ² are not simultaneously hydrogen atoms.)
[Selection figure] None

Description

  The present invention relates to a biphenylene derivative that can be developed into an electronic material such as an organic semiconductor, its use, and a production method thereof.

  Organic semiconductor devices typified by organic thin film transistors have recently attracted attention because they have features not found in inorganic semiconductor devices such as energy saving, low cost, and flexibility. An organic thin film transistor is composed of several kinds of materials such as an organic semiconductor active phase, a substrate, an insulating phase, and an electrode. Among them, an organic semiconductor active phase responsible for charge carrier movement has a central role of the device. The semiconductor device performance depends on the carrier mobility of the organic material constituting the organic semiconductor active phase.

  As a method for producing an organic semiconductor active phase, there are generally known a vacuum deposition method in which an organic material is vaporized under a high temperature vacuum, and a coating method in which the organic material is dissolved in an appropriate solvent and applied. ing. Since the coating method can be carried out using a printing technique without using high-temperature and high-vacuum conditions, the manufacturing cost for device fabrication can be greatly reduced, and thus it is an economically preferable process. However, conventionally, there has been a problem that a high-performance material as an organic semiconductor material makes it difficult to form an active phase by coating.

  For example, it has been reported that a crystalline material such as pentacene having a molecular long axis has a carrier mobility as high as that of amorphous silicon and exhibits excellent semiconductor device characteristics (see Non-Patent Document 1, for example). However, pentacene has low solubility due to its strong cohesiveness, and generally an economical coating method cannot be applied. In addition, attempts have been reported to dissolve polyacene such as pentacene to produce a device by a coating method (see, for example, Patent Document 1). However, in order to dissolve polyacenes that are originally hardly soluble, high temperature heating or the like can be used. The application of the coating method has been difficult in terms of process and economy because conditions are required and the solution of pentacene is oxidized very easily by air. Self-assembled materials such as poly- (3-hexylthiophene) are soluble in solvents, and device fabrication by coating has been reported, but the carrier mobility is an order of magnitude lower than that of crystalline low-molecular compounds. (For example, refer nonpatent literature 2) There existed a problem that the characteristic of the obtained organic-semiconductor device was low.

  Under such circumstances, biphenylene is a rigid conjugated condensed ring compound and a compound that can be expected as an organic semiconductor material. However, the biphenylene derivatives reported so far have not been satisfactory as organic semiconductor materials.

  For example, a polysubstituted polycyclic aromatic compound and a method for producing the same describe a compound having a rigid biphenylene structure (see, for example, Patent Documents 2 to 4), but have a substituent other than the molecular major axis direction. Therefore, the crystallinity is lowered, and a uniform film cannot be obtained by a coating method, which is not suitable as a semiconductor material. Moreover, although the structure of a biphenylene derivative is described in the ternary photoinitiator system (for example, refer patent document 5) for cationically polymerizable resin, since the molecular long axis is short, it is not suitable as a semiconductor material.

“Journal of Applied Physics” (USA), 2002, 92, 5259-5263. “Science”, (USA), 1998, 280, 1741-1744. WO2003 / 016599 Pamphlet JP 2004-256497 A JP 2006-156980 A JP 2006-328006 A JP 2005-523348 A

  Therefore, in view of the problems of the above-described conventional technology, the present invention has a biphenylene derivative having excellent oxidation resistance and capable of forming a semiconductor active phase by a coating method, an oxidation resistant organic semiconductor material using the same, and a It is an object to provide an organic thin film, a light emitting material, and a method for easily and economically producing the biphenylene derivative. The present invention further relates to a dihalobiphenyl derivative which is a precursor compound of the biphenylene derivative.

  As a result of intensive studies to solve the above problems, the present inventors have found a novel biphenylene derivative and a dihalobiphenyl derivative which is a precursor. In addition, the present inventors have found an oxidation-resistant organic semiconductor material composed of the biphenylene derivative, an organic thin film composed thereof, and a light emitting material. Furthermore, the inventors have found a production method suitable for producing the biphenylene derivative and have completed the present invention.

The present invention is described in detail below.
(Biphenylene derivative)
The biphenylene derivative of the present invention is represented by the following general formula (1).

（ここで、置換基Ｒ^１〜Ｒ^８は同一又は異なって、水素原子、フッ素原子、炭素数２〜２０のアルキル基、炭素数２〜２０のアルキニル基、炭素数２〜３０のアルケニル基、又は炭素数４〜２０のアリール基を示し、ｍは１又は２であり、ｎは０〜２の整数を示す。但し、Ｒ^１及びＲ^２は同時に水素原子であることはない。）
本発明の一般式（１）の置換基について、述べる。

(Here, the substituents R ^{1 to} R ⁸ are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, Or an aryl group having 4 to 20 carbon atoms, m is 1 or 2, and n is an integer of 0 to 2. However, R ¹ and R ² are not simultaneously hydrogen atoms.)
The substituent of the general formula (1) of the present invention will be described.

The alkyl group having 2 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited. For example, propyl group, butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, isooctyl group, Alkyl groups such as nonyl, decyl, dodecyl, pentadecyl, octadecyl, 2-ethylhexyl; trifluoromethyl, pentafluoroethyl, perfluorooctyl, perfluorodecyl, perfluorododecyl, perfluoro Perfluoroalkyl groups such as fluorooctadecyl group, perfluorocyclohexyl group, perfluorocyclooctyl group; some of trifluoroethyl group, pentadecafluorooctyl group, octadecafluorodecyl group, 2-ethylperfluorohexyl group, etc. C in which hydrogen is replaced by fluorine Genated alkyl groups can be mentioned, preferably an alkyl group having 5 to 20 carbon atoms, more preferably an octyl group, a dodecyl group, an octadecyl group, a perfluorooctyl group, a perfluorododecyl group, a perfluorooctadecyl group, Particularly preferred are dodecyl group and perfluorododecyl group.

The alkynyl group having 2 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited. For example, ethynyl group, methylethynyl group, isopropylethynyl group, tert-butylethynyl group, (octyl) ethynyl group, (decyl) Ethynyl group, (dodecyl) ethynyl group, (octadecyl) ethynyl group, (trifluoromethyl) ethynyl group, (perfluorooctyl) ethynyl group, (perfluorodecyl) ethynyl group, (perfluorododecyl) ethynyl group, phenylethynyl group , {P- (octyl) phenyl} ethynyl group, naphthylethynyl group, anthracenylethynyl group, benzylethynyl group, perfluorophenylethynyl group, {p- (trifluoromethyl) phenyl} ethynyl group, {p- (per Fluorooctyl) phenyl} ethynyl group, etc. Preferably, (octyl) ethynyl group, (decyl) ethynyl group, (dodecyl) ethynyl group, (perfluorooctyl) ethynyl group, (perfluorodecyl) ethynyl group, (perfluorododecyl) ethynyl group, phenylethynyl Group.

The alkenyl group having 2 to 30 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited, and for example, ethenyl group, methyl ethenyl group, isopropyl ethenyl group, tert-butyl ethenyl group, (octyl) ethenyl group, (decyl) ethenyl Group, (dodecyl) ethenyl group, (trifluoromethyl) ethenyl group, phenylethenyl group, {p- (hexyl) phenyl} ethenyl group, {p- (octyl) phenyl} ethenyl group, 2-phenyl-1,2 -Difluoroethenyl group, 2-phenyl-1,2-dimethylethenyl group, diphenylethenyl group, triphenylethenyl group, naphthylethenyl group, anthracenylethenyl group, benzylethenyl group, phenyl (methyl) ethenyl group , (Perfluorophenyl) ethenyl group, {p- (trifluoromethyl) phenyl Ethenyl group, (perfluorooctyl) ethenyl group, (perfluorodecyl) ethenyl group, (perfluorododecyl) ethenyl group, {5- (hexyl) thienyl-2-} ethenyl group, {5- (perfluorohexyl) thienyl -2-} ethenyl group and the like, preferably (octyl) ethenyl group, (decyl) ethenyl group, (dodecyl) ethenyl group, (perfluorooctyl) ethenyl group, (perfluorodecyl) ethenyl group, Perfluorododecyl) ethenyl group, {5- (hexyl) thienyl-2-} ethenyl group, {5- (perfluorohexyl) thienyl-2-} ethenyl group, phenylethenyl group and the like. The alkenyl group having 2 to 30 carbon atoms may be either a trans isomer or a cis isomer, or may be a mixture of any ratio thereof.

The aryl group having 4 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited. For example, a phenyl group, a p-tolyl group, a p- (octyl) phenyl group, an m- (octyl) phenyl group, p- (Decyl) phenyl group, p-fluorophenyl group, pentafluorophenyl group, p- (trifluoromethyl) phenyl group, p- (perfluorooctyl) phenyl group, m- (perfluorooctyl) phenyl group, p- ( (Trifluoromethyl) tetrafluorophenyl group, p-methoxyphenyl group, p-phenoxyphenyl group, 2-thienyl group, 5- (hexyl) -2-thienyl group, 5- (perfluorohexyl) -2-thienyl group, Biphenyl group, perfluorobiphenyl group, 1-naphthyl group, 2-naphthyl group, 1-perfluoronaphthyl group, 2-fluoreni Group, 9,9-dimethyl-2-fluorenyl group, 9-anthracenyl group, etc., preferably phenyl group, p- (octyl) phenyl group, p- (trifluoromethyl) phenyl group, p- (Perfluorooctyl) phenyl group.

As substitution modes of the substituents R ^{1 to} R ⁸ of the biphenylene derivative represented by the general formula (1) of the present invention, R ^{1 to} R ⁴ are the same or different, and are a hydrogen atom, a fluorine atom, or a carbon number of 2 to 20 And at least one group selected from the group consisting of an alkyl group, an alkynyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an aryl group having 4 to 20 carbon atoms, and R ^{5 to} R ^8. Are the same or different and are preferably at least one group selected from the group consisting of a hydrogen atom, a fluorine atom, and an aryl group having 4 to 20 carbon atoms.

Further, the substituents R ^{1 to} R ⁴ are the same or different and are each composed of a hydrogen atom, a fluorine atom, an alkyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an aryl group having 4 to 20 carbon atoms. It is at least one group selected from the group, and R ^{5 to} R ⁸ are the same or different and are at least one group selected from the group consisting of a hydrogen atom and an aryl group having 4 to 20 carbon atoms. Is more preferable.

  The symbol m is 1 or 2, preferably 1. The symbol n represents an integer of 0 to 2, and is preferably 1. The particularly preferred symbols m and n are both 1.

  Among these, the biphenylene derivative represented by the general formula (1) of the present invention exhibits high oxidation resistance and carrier mobility in the biphenylene derivative, the oxidation-resistant organic semiconductor material containing the biphenylene derivative, and the organic thin film thereof. Therefore, the following compounds are preferable,

特に好ましくは

Especially preferably

である。
（ジハロビフェニル誘導体）
次に、本発明の一般式（１）で示されるビフェニレン誘導体の原料として用いられる下記一般式（２）で示されるジハロビフェニル誘導体について述べる。

It is.
(Dihalobiphenyl derivatives)
Next, the dihalobiphenyl derivative represented by the following general formula (2) used as a raw material for the biphenylene derivative represented by the general formula (1) of the present invention will be described.

（ここで、置換基Ｘ^１及びＸ^２は臭素原子、ヨウ素原子又は塩素原子を示し、置換基Ｒ^１〜Ｒ^８、並びに記号ｍ及びｎは、一般式（１）で示される置換基並びに記号と同意義を示す。）
一般式（２）におけるＸ^１及びＸ^２は臭素原子、ヨウ素原子又は塩素原子であり、その中でも好ましくは臭素原子又はヨウ素原子であり、より好ましくは臭素原子である。

(Wherein the substituents X ¹ and X ² represent a bromine atom, an iodine atom or a chlorine atom, the substituents R ^{1 to} R ⁸ , and the symbols m and n are the substituents and symbols represented by the general formula (1)) And the same meaning.)
X ¹ and X ² in the general formula (2) are a bromine atom, an iodine atom or a chlorine atom, preferably a bromine atom or an iodine atom, more preferably a bromine atom.

Preferred examples of the substituents R ¹ and R ² in the general formula (2) of the present invention are a fluorine atom, an alkyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms, and a more preferred example is a fluorine atom. , An alkyl group having 5 to 20 carbon atoms.

Preferred examples of the substituents R ³ and R ⁴ are a hydrogen atom, a fluorine atom, an alkyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms, and more preferred examples are a fluorine atom and 5 to 20 carbon atoms. It is an alkyl group.

Particularly preferred examples of the substituents R ^{5 to} R ⁸ are a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, and an aryl group having 4 to 20 carbon atoms, and a more preferred example is a hydrogen atom.

  As the dihalobiphenyl derivative represented by the general formula (2) of the present invention, the following compounds are preferable,

特に好ましくは

Especially preferably

である。
（ビフェニレン誘導体の製造方法）
次に、本発明の一般式（１）で示されるビフェニレン誘導体の製造方法について述べる。

It is.
(Method for producing biphenylene derivative)
Next, a method for producing the biphenylene derivative represented by the general formula (1) of the present invention will be described.

  The biphenylene derivative represented by the general formula (1) of the present invention can be produced by reacting the dihalobiphenyl derivative represented by the general formula (2) with copper or a copper compound.

  The copper or copper compound used in the reaction is not particularly limited as long as it reacts with iodine or bromine. For example, copper, copper chloride (I), copper bromide (I), copper iodide (I), Examples thereof include copper (II) chloride, copper (II) bromide, and copper (II) iodide, preferably copper and copper (II) chloride. Moreover, even if this copper is an alloy with zinc and / or tin, it can be used without any problem. The shape of the copper and / or copper alloy is preferably powder.

  This reaction with copper or a copper compound can be carried out with or without a solvent. When a solvent is used, examples of the solvent include polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, and dimethyl sulfoxide. In the reaction with such copper or copper compound, the amount of copper or copper compound to be used is preferably 1 to 50 equivalents, particularly preferably 5 to 30 equivalents, relative to 1 equivalent of the dihalobiphenyl derivative represented by the general formula (2). The reaction temperature is preferably 30 to 250 ° C, particularly preferably 50 to 220 ° C, and the reaction time is preferably 1 to 120 minutes, particularly preferably 3 to 80 minutes.

  The reaction is preferably carried out under an inert atmosphere such as nitrogen or argon. The obtained biphenylene derivative represented by the general formula (1) can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

  A more preferable production method of the biphenylene derivative represented by the general formula (1) of the present invention will be described.

As a more preferable production method, there can be mentioned a method in which the dihalobiphenyl derivative represented by the general formula (2) is dilithiated and / or diglynarized and then reacted with a copper compound. Here, dilithiation means that ^two halogens X ¹ and X ² in the general formula (2) are each replaced with lithium, and diglynarization means that ^two halogens in the general formula (2) It means that halogens X ¹ and X ² are each replaced with magnesium halide.

When dilithiating the dihalobiphenyl derivative represented by the general formula (2), the lithiating agent to be used is particularly limited as long as the halogen X ¹ and X ² in the general formula (2) can be substituted with lithium. For example, alkyllithium such as n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, hexyllithium; phenyllithium, p-tert-butylphenyllithium, p-methoxyphenyllithium, p-fluorophenyl Aryl lithium such as lithium; lithium amide such as lithium diisopropylamide and lithium hexamethyldisilazide; lithium metal such as lithium powder can be mentioned, preferably alkyllithium, particularly preferably n-butyllithium, sec- The Butyllithium, it is a tert- butyl lithium.

  The amount of the lithiating agent used is preferably 1.5 to 4 equivalents, more preferably 1.8 to 3 equivalents, particularly preferably 1. to 1 equivalent of the dihalobiphenyl derivative represented by the general formula (2). 9 to 2.6 equivalents.

  The dilithiation reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited. For example, diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, ethylene glycol dimethyl ether and other dialkyl ethers, tetrahydrofuran (hereinafter abbreviated as THF), diglyme. , Dioxane, toluene, pentane, hexane, cyclohexane and the like, preferably dialkyl ethers such as diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, ethylene glycol dimethyl ether, Particularly preferred are diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether. It is an ether. These solvents may be used alone or as a mixture of two or more.

  The dilithiation reaction temperature is preferably -80 to 50 ° C, particularly preferably -30 to 30 ° C. The reaction time is preferably 1 to 240 minutes, particularly preferably 1 to 90 minutes. The progress of the dilithiation reaction can also be monitored by taking out a part of the reaction solution, stopping the reaction with water, and then analyzing by thin layer chromatography or gas chromatography.

  In the method for producing a biphenylene derivative represented by the general formula (1) of the present invention, by carrying out dilithiation in a dialkyl ether, the reaction temperature of dilithiation can be increased to -30 to 30 ° C, It was found that a dihalobiphenyl derivative represented by a low general formula (2) can also be efficiently dilithiated.

  The dilithium salt produced by the dilithiation reaction is then reacted with a copper compound. The reaction with the copper compound includes a method of reacting the reaction mixture containing the dilithium salt generated by the lithiation reaction directly using the copper compound, a method of isolating the generated dilithium salt once, and reacting with the copper compound. Any of them may be used.

  The reaction between the dilithium salt and the copper compound can be carried out using any method of adding a copper compound to the dilithium salt or adding the dilithium salt to a copper compound.

  The copper compound used for the reaction between the dilithium salt and the copper compound is not particularly limited. For example, copper chloride (II), copper bromide (II), copper iodide (II), copper acetate (II), acetylacetonate copper Divalent copper such as (II); monovalent copper such as copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (I) acetate, etc. can be mentioned, preferably divalent Copper, particularly preferably copper (II) chloride and copper (II) bromide. The reaction between the produced dilithium salt and the copper compound is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, ethylene glycol dimethyl ether, diglyme, dioxane and the like, preferably THF and diethyl ether. These solvents may be used alone or as a mixture of two or more. The amount of the copper compound to be used is preferably 0.9 to 5 equivalents, particularly preferably 1.0 to 3.5 equivalents, relative to 1 equivalent of the dihalobiphenyl derivative represented by the general formula (2). The reaction temperature with the copper compound is preferably −90 to 50 ° C., particularly preferably −80 to 30 ° C., and the reaction time is preferably 1 to 30 hours, particularly preferably 1 to 18 hours.

  These copper compounds can be used as they are, or can be used in a state of being mixed with the solvent mentioned in the dilithiation reaction.

  The production of the biphenylene derivative of the general formula (1) of the present invention is preferably carried out under an inert atmosphere such as nitrogen or argon.

  The biphenylene derivative represented by the general formula (1) thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

  When the dihalobiphenyl derivative represented by the general formula (2) is diglynarized, examples of the Grignard agent to be used include alkyl Grignard reagents such as magnesium metal, ethylmagnesium bromide, isopropylmagnesium bromide, and the like. Is magnesium metal. The form of the magnesium metal is not particularly limited, and examples thereof include a cut shape, a ribbon shape, and a granular shape.

  For example, in the case of magnesium metal, the Grignard agent is preferably 1.8 to 10 equivalents with respect to 1 equivalent of the dihalobiphenyl derivative represented by the general formula (2). The Grignard reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include the solvent used in the dilithiation reaction. The temperature of the Grignard reaction is preferably -20 to 80 ° C, and the reaction time is preferably 1 to 120 minutes.

  The magnesium salt produced by the diglynarization reaction is then reacted with a copper compound. The reaction method with the copper compound and the copper compound to be used can be carried out in the same manner as when the dilithium salt produced by the dilithiation reaction is reacted with the copper compound. The reaction atmosphere and the reaction product can be purified in the same manner.

  In the method for producing the biphenylene derivative represented by the general formula (1) of the present invention, the dihalobiphenyl derivative represented by the general formula (2) is dilithiated and / or diglynarized, and then reacted with zinc chloride. It can also be treated with a copper compound.

(Method for producing dihalobiphenyl derivative)
The dihalobiphenyl derivative represented by the general formula (2) is composed of a 2,3-dihaloanthracene derivative represented by the following general formula (3) and a 2,3-dihaloanthracene derivative represented by the following general formula (4). It can be produced by cross-coupling the derived 3-haloanthracenyl metal reagent in the presence of palladium and / or nickel catalyst.

（ここで、置換基Ｒ^１、Ｒ^２、Ｒ^５、Ｒ^６、及びＸ^１、並びに記号ｍは、一般式（２）で示される置換基並びに記号と同意義を示し、置換基Ｘ^３は臭素原子又はヨウ素原子を示す。）

(Here, the substituents R ¹ , R ² , R ⁵ , R ⁶ , and X ¹ , and the symbol m have the same meanings as the substituent and the symbol represented by the general formula (2), and the substituent X ³ is (A bromine atom or an iodine atom is shown.)

（ここで、置換基Ｒ^３、Ｒ^４、Ｒ^７、Ｒ^８、及びＸ^２、並びに記号ｎは、一般式（２）で示される置換基並びに記号と同意義を示し、置換基Ｘ^４は臭素原子又はヨウ素原子を示す。）
置換基Ｘ^３及びＸ^４は臭素原子又はヨウ素原子であり、その中でも好ましくはヨウ素原子である。

(Here, the substituents R ³ , R ⁴ , R ⁷ , R ⁸ , and X ² , and the symbol n have the same meanings as the substituents and symbols represented by the general formula (2), and the substituent X ⁴ is (A bromine atom or an iodine atom is shown.)
The substituents X ³ and X ⁴ are a bromine atom or an iodine atom, and among them, an iodine atom is preferable.

The 3-haloanthracenyl metal reagent is prepared by using a 2,3-dihaloanthracene derivative represented by the general formula (4) as a raw material, a Grignard reagent such as isopropylmagnesium bromide, or an organic lithium such as n-butyllithium. After a halogen / metal exchange reaction with X ⁴ which is a halogen of the general formula (4) with a reagent, zinc chloride, trimethoxyborane, tri (isopropoxy) borane, 2-isopropoxy-4, 4, 5, It can be suitably prepared by reacting with 5-tetramethyl-1,3,2-dioxaborolane or the like. The halogen / metal exchange reaction using the Grignard reagent is, for example, the method described in “Journal of Organic Chemistry”, 2000, Vol. 65, pages 4618-4634, and the halogen / metal exchange reaction using an organolithium reagent is For example, the method of lithiation of halogen at −90 ° C. or lower described in “Journal of Chemical Research Synopsis”, 1981, p. 185 can also be used.

  The catalyst used for the cross-coupling reaction between the 3-haloanthracenyl metal reagent and the 2,3-dihaloanthracene derivative represented by the general formula (3) is not particularly limited as long as it is a palladium and / or nickel catalyst. Zerovalent palladium compounds such as tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium / triphenylphosphine mixture, bis (tri-tert-butylphosphine) palladium; dichlorobis (triphenylphosphine) palladium, palladium acetate / (Tri-tert-butylphosphine) mixture, diacetatobis (triphenylphosphine) palladium, dichloro (1,2-bis (diphenylphosphino) ethane) palladium, dichloro (1,3-bis (diphenylphosphino) propyl Pan) palladium, palladium acetate / triphenylphosphine mixture, palladium acetate / 2- (dicyclohexylphosphino) -1,1′-biphenyl mixture, dichloro (ethylenediamine) palladium, dichloro (N, N, N ′, N′-tetra) Divalent, such as methylethylenediamine) palladium, dichloro (N, N, N ′, N′-tetramethylpropanediamine) palladium, dichloro (N, N, N ′, N′-tetramethylethylenediamine) palladium / triphenylphosphine mixture Palladium compounds: dichlorobis (triphenylphosphine) nickel, dichloro (1,2-bis (diphenylphosphino) ethane) nickel, dichloro (1,3-bis (diphenylphosphino) propane) nickel, dichloro (ethylenediamine) ni Kell, dichloro (N, N, N ', N'-tetramethylethylenediamine) nickel, dichloro (N, N, N', N'-tetramethylpropanediamine) nickel, dichloro (N, N, N ', N' -A tetravalent ethylenediamine) divalent nickel compound such as a nickel / triphenylphosphine mixture; a zerovalent nickel compound such as a bis (1,5-cyclooctadiene) nickel / triphenylphosphine mixture can be mentioned, among which preferable Is a zero-valent or divalent palladium compound, particularly preferably tetrakis (triphenylphosphine) palladium or dichlorobis (triphenylphosphine) palladium.

  The amount of the catalyst used in the coupling reaction is preferably in the range of 0.1 to 20 mol% with respect to the 2,3-dihaloanthracene derivative represented by the general formula (3). Moreover, the usage-amount of the 3-haloanthracenyl metal reagent induced | guided | derived from General formula (4) is 0.6-1 .1 with respect to 1 equivalent of 2,3-dihaloanthracene derivatives shown by General formula (3). 5 equivalent is preferable, More preferably, it is 0.8-1.4 equivalent, Most preferably, it is 0.9-1.2 equivalent.

  The reaction is preferably carried out in a solvent. Examples of the solvent include THF, diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol, N, N-dimethylformamide, N-methylpyrrolidone, diisopropylamine, piperidine, toluene, xylene, Examples include hexane, cyclohexane, ethanol, water, and the like. These solvents may be used alone or as a mixture of two or more. For example, a two-component system such as toluene / water or toluene / ethanol / water can be used.

  The 2,3-dihaloanthracene derivative represented by the general formula (3) and the general formula (4) may be the same compound.

  A base can also be present in the reaction system. There are no particular limitations on the type of base in this case, for example, sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, sodium hydroxide, potassium hydroxide, potassium fluoride. Inorganic bases such as sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, etc .; triethylamine, trimethylamine, tripropylamine, tributylamine, ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, diisopropyl Organic bases such as amine, pyridine and tetrabutylammonium fluoride can be mentioned as suitable ones. The amount of these bases used is preferably 1.5 to 10.0 equivalents, particularly preferably 2.0 to 8.0 equivalents, relative to 1 equivalent of the 2,3-dihaloanthracene derivative represented by the general formula (3). It is. Furthermore, a phase transfer catalyst can be used in combination with these bases. The type of the phase transfer catalyst is not particularly limited, and examples thereof include trioctylmethylammonium chloride, tetrabutylammonium chloride, cetylpyridinium chloride, benzyltrimethylammonium chloride and the like. The amount of these phase transfer catalysts used is preferably 0.1 to 1.5 equivalents, particularly preferably 0.2 to 0.00, per 1 equivalent of the 2,3-dihaloanthracene derivative represented by the general formula (3). 8 equivalents.

  Further, phosphine such as triphenylphosphine can be present in the reaction system. The amount of these phosphines used is preferably 0.9 to 8.0 equivalents, particularly preferably 1.0 to 3.0 equivalents, relative to 1 equivalent of the palladium and / or nickel catalyst.

  The reaction temperature is preferably 10 to 120 ° C, particularly preferably 30 to 100 ° C, and the reaction time is preferably 1 to 48 hours.

  Furthermore, another method for producing the dihalobiphenyl derivative represented by the general formula (2) will be described.

  The dihalobiphenyl derivative represented by the general formula (2), which is a precursor of the biphenylene derivative represented by the general formula (1), can be derived from the 2,3-dihaloanthracene derivative represented by the general formula (3).

  That is, the dihalobiphenyl derivative represented by the general formula (2) is produced by homocoupling the 2,3-dihaloanthracene derivative represented by the general formula (3) using a lithiating agent or a Grignard agent. can do.

The lithiating agent used in the homocoupling reaction of the 2,3-dihaloanthracene derivative is not particularly limited as long as it can lithiate the halogen X ¹ or X ³ in the general formula (3). -Organic lithium reagents such as butyllithium, sec-butyllithium, tert-butyllithium, methyllithium and phenyllithium; Organic lithiumamide reagents such as lithium diisopropylamide and lithium hexamethyldisilazide; An organic lithium reagent is preferred, and n-butyllithium is particularly preferred.

  The lithiation reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane, toluene, pentane, hexane, cyclohexane and the like, and preferably THF. These solvents may be used alone or as a mixture of two or more.

  The lithiating agent is preferably 0.3 to 1.2 equivalents, particularly preferably 0.4 to 0.7 equivalents, relative to 1 equivalent of the 2,3-dihaloanthracene derivative represented by the general formula (3). The temperature of the lithiation reaction is preferably −100 to 40 ° C., particularly preferably −90 to 30 ° C., and the reaction time is preferably 1 to 30 hours, particularly preferably 2 to 20 hours.

On the other hand, the Grignard agent used in the homocoupling reaction of the 2,3-dihaloanthracene derivative represented by the general formula (3) is capable of Grignardizing the halogen X ¹ or X ³ in the general formula (3). As long as it is, there is no particular limitation, and examples thereof include alkyl Grignard reagents such as magnesium metal, ethyl magnesium bromide, isopropyl magnesium bromide, and the like is preferably magnesium metal. The form of the magnesium metal is not particularly limited, and examples thereof include a cutting shape, a ribbon shape, and a granular shape.

  For example, in the case of magnesium metal, the Grignard agent is preferably 0.4 to 0.7 equivalent relative to 1 equivalent of the 2,3-dihaloanthracene derivative represented by the general formula (3). The Grignard reaction is preferably carried out in a solvent. The solvent used is not particularly limited, and examples thereof include the solvent used in the lithiation reaction. The temperature of the Grignard reaction is preferably -20 to 100 ° C, and the reaction time is preferably 1 to 30 hours.

  The production of the dihalobiphenyl derivative represented by the general formula (2) is preferably carried out under an inert atmosphere such as nitrogen or argon.

  The dihalobiphenyl derivative represented by the general formula (2) thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

(Method for producing 2,3-dihaloanthracene derivative)
The 2,3-dihaloanthracene derivative represented by the general formula (3) and the general formula (4) can be obtained from the 2,3-dihaloanthraquinone derivative represented by the following general formula (5) by the following two methods. Can be manufactured.

（ここで、置換基Ｒ^１、Ｒ^２、Ｘ^１、及びＸ^３、並びに記号ｍは、一般式（３）で示される置換基並びに記号と同意義を示す。）。

(Here, the substituents R ¹ , R ² , X ¹ , and X ³ , and the symbol m have the same meaning as the substituent and the symbol represented by the general formula (3)).

(Method 1)
When the substituents R ⁵ and R ⁶ in the 2,3-dihaloanthracene derivative represented by the general formula (3) are hydrogen atoms, the 2,3-dihaloanthraquinone derivative represented by the general formula (5) is reduced by hydride. It can be produced by reducing with an agent and dehydrating with an acid catalyst.

  The hydride reducing agent to be used is not particularly limited as long as it can reduce quinone to a hydroxyl group, and examples thereof include diisobutylaluminum hydride and sodium borohydride. The reduction reaction is preferably carried out using a solvent such as THF, diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, toluene, hexane or the like. The reaction temperature is preferably 0 to 60 ° C., and the reaction time is preferably 1 to 24 hours. As for the usage-amount of a hydride reducing agent, 1-20 equivalent is preferable with respect to 1 equivalent of the 2, 3- dihaloanthraquinone derivative shown by General formula (5).

  Next, the dihydroxyl compound obtained by the hydride reduction is subjected to a dehydration reaction using an acid catalyst. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, toluenesulfonic acid, phosphoric acid and the like. These acid catalysts can also be used as an aqueous solution. The reaction temperature is preferably 10 to 100 ° C., and the reaction time is preferably 1 to 24 hours. The acid catalyst can be added at the end of the reduction reaction using the hydride reducing agent and the dehydration reaction can be carried out as it is. The amount of the acid catalyst used for the dehydration reaction is preferably 5 to 80 equivalents with respect to 1 equivalent of the 2,3-dihaloanthraquinone derivative represented by the general formula (5).

  The process consisting of the hydride reduction reaction and the dehydration reaction is repeated 2 to 4 times, and the 2,3-dihaloanthracene derivative represented by the general formula (3) can be synthesized with good yield.

  The 2,3-dihaloanthraquinone derivative represented by the general formula (5) can be synthesized using an existing method. For example, it is synthesized from 4-bromo-5-iodophthalic anhydride and 1,2-dialkylbenzene with reference to a method described in “Berichite” (Germany), 1933, 66B, pp. 1876-1891. can do.

(Method 2)
The substituents R ⁵ and R ⁶ in the 2,3-dihaloanthracene derivative represented by the general formula (3) are an alkyl group having 2 to 20 carbon atoms, a fluorine atom, an alkynyl group having 2 to 20 carbon atoms, and 2 to 2 carbon atoms. In the case of a 30 alkenyl group or an aryl group having 4 to 20 carbon atoms, a 2,3-dihaloanthraquinone derivative represented by the general formula (5) and the following general formula (6) and / or (7) After reacting with an organometallic reagent, it can be produced by reduction.

R ⁵ M ¹ (6)
R ⁶ M ² (7)
(Here, the substituents R ⁵ and R ⁶ have the same meaning as the substituent represented by the general formula (3), and the substituents M ¹ and M ² represent lithium or magnesium halide.)
The organometallic reagent represented by the general formulas (6) and (7) is not particularly limited as long as it can react with quinone, and examples thereof include an organic lithium reagent and a Grignard reagent. Specific examples of the organic lithium reagent include Alkyl lithium reagents such as octyl lithium, dodecyl lithium, perfluorododecyl lithium; aryl lithium reagents such as phenyl lithium, tolyl lithium, p-octylphenyl lithium, p- (perfluorooctyl) phenyl lithium; ethynyl lithium, 1- Alkynyllithium reagents such as dodecynyllithium, 1- (perfluorododecynyl) lithium, phenylethynyllithium; ethenyllithium, 1-dodecenyllithium, 1- (perfluorododecenyl) lithium, phenyl Arkeni such as ethenyl lithium Examples of the Grignard reagent include alkyl Grignard reagents such as octylmagnesium bromide, dodecylmagnesium bromide, perfluorododecylmagnesium bromide; phenylmagnesium bromide, tolylmagnesium bromide, p-octylphenyl Aryl Grignard reagents such as magnesium bromide and p- (perfluorooctyl) phenylmagnesium bromide; Alkynyl such as ethynylmagnesium bromide, 1-dodecynylmagnesium bromide, 1- (perfluorododecynyl) magnesium bromide and phenylethynylmagnesium bromide Grunard reagent; ethenyl magnesium bromide, 1-dodecenyl magnesium bromide, 1- (perfluorodode Yl) magnesium bromide, alkenyl glutaric Grignard reagent such as phenylethenyl bromide; and the like.

  The reaction between the 2,3-dihaloanthraquinone derivative represented by the general formula (5) and the organometallic reagent represented by the general formulas (6) and (7) is performed by THF, diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, It is preferable to use a solvent such as toluene or hexane. The reaction temperature is preferably −80 to 60 ° C., and the reaction time is preferably 5 to 24 hours. The amount of the organometallic reagent used is preferably 2 to 7 equivalents relative to 1 equivalent of the 2,3-dihaloanthraquinone derivative represented by the general formula (5). Next, the dihydroxyl obtained by the reaction with the organometallic reagent is reduced using a reducing agent. Specific examples of the reducing agent are preferably tin dichloride or sodium hypophosphite / sodium iodide. The reduction reaction is preferably carried out using a solvent such as aqueous hydrochloric acid or acetic acid. The reaction temperature is preferably 20 to 150 ° C., and the reaction time is preferably 1 to 5 hours. The amount of the reducing agent used is preferably 3 to 10 equivalents relative to 1 equivalent of the 2,3-dihaloanthraquinone derivative represented by the general formula (5).

The 2,3-dihaloanthracene derivative represented by the general formula (3) having substituents at the 9- and 10-positions can also be synthesized using an existing method. For example, it can be synthesized from a 2,3-dihaloanthraquinone derivative with reference to the method described in “Sinlet”, pages 217-222, 2005.
(Oxidation-resistant organic semiconductor materials)
Next, the oxidation resistant organic semiconductor material containing the biphenylene derivative represented by the general formula (1) of the present invention will be described. The oxidation-resistant organic semiconductor material is excellent in solubility in a solvent and oxidation resistance, and has suitable coating properties.

  Examples of the solvent used for dissolving the biphenylene derivative represented by the general formula (1) of the present invention include o-dichlorobenzene, chlorobenzene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, and dichloromethane. Halogen solvents; ether solvents such as THF and dioxane; aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate and γ-butyrolactone; N, N-dimethylformamide, N-methylpyrrolidone and the like Amide solvents; among them, aromatic hydrocarbon solvents such as toluene and xylene are preferable from the viewpoint of corrosion of the apparatus. These solvents may be used alone or as a mixture of two or more.

  By mixing and stirring the above-mentioned solvent and the biphenylene derivative represented by the general formula (1), a solution of an oxidation-resistant organic semiconductor containing the biphenylene derivative represented by the general formula (1) can be prepared. In this case, the temperature is preferably 10 to 130 ° C, particularly preferably 20 to 100 ° C. The concentration of the resulting solution can vary depending on the solvent and temperature, and is preferably 0.01 to 10.0% by weight. The solution can be prepared in air, but is preferably prepared in an inert atmosphere such as nitrogen or argon.

  Evaluation of the oxidation resistance of the oxidation-resistant organic semiconductor material containing the biphenylene derivative represented by the general formula (1) can be performed by a method in which the solution is brought into contact with air for a predetermined time. First, the solvent to be used is degassed in advance to remove dissolved oxygen. The contact time with air is preferably 0.5 minutes to 3 hours. The progress of oxidation can be carried out by changing the color of the solution and detecting the oxide by thin layer chromatography, gas chromatography and liquid chromatography analysis.

The solution of the oxidation-resistant organic semiconductor material containing the biphenylene derivative represented by the general formula (1) of the present invention has a relatively high cohesiveness because the biphenylene derivative itself represented by the general formula (1) used has appropriate cohesiveness. Since it can be dissolved in a solvent at a low temperature and has oxidation resistance, it can be suitably applied to the production of an organic thin film by a coating method. That is, since it is not necessary to strictly remove air from the atmosphere, the coating process can be simplified. The coating can be carried out in the air, but is preferably performed under a nitrogen stream in consideration of drying of the solvent. In order to obtain suitable coating properties, the viscosity of the solution of the oxidation-resistant organic semiconductor material containing the biphenylene derivative represented by the general formula (1) of the present invention may be in the range of 0.005 to 20 poise. preferable.
(Organic thin film)
Next, an organic thin film using an oxidation-resistant organic semiconductor material containing a biphenylene derivative represented by the general formula (1) of the present invention will be described. Such an organic thin film can be produced by applying the above-mentioned oxidation-resistant organic semiconductor material solution to a substrate.

  The production of the organic thin film by application to the substrate can be carried out by applying the oxidation-resistant organic semiconductor material solution on the substrate and then evaporating the solvent by a method such as heating, air flow, and natural drying. The concentration of the biphenylene derivative represented by the general formula (1) in the solution is not particularly limited, and is preferably 0.01 to 10.0% by weight, for example. There is no particular limitation on the coating temperature, and for example, it can be suitably carried out between 20 and 130 ° C. The specific method of application is not particularly limited, and for example, spin coating, cast coating, dip coating, or the like can be used. Further, it can be produced by using a printing technique such as screen printing, ink jet printing, or gravure printing. The material of the substrate to be used is not particularly limited, and various crystalline and non-crystalline materials can be used. Further, the substrate may be made of an insulating or dielectric material. Specific examples of the substrate include plastic substrates such as polyethylene terephthalate, polymethyl methacrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, and polyethylene naphthalate; glass, quartz, aluminum oxide, silicon And inorganic material substrates such as silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; and metal substrates such as gold, copper, chromium, and titanium. The surfaces of these substrates can be used even if they are modified with silanes such as octadecyltrichlorosilane, octyltrichlorosilane, and octadecyltrimethoxysilane. Drying of the solvent after coating can be removed at normal pressure or reduced pressure, or may be performed by heating. Furthermore, crystal growth of the biphenylene derivative represented by the general formula (1) of the present invention can be controlled by adjusting the evaporation rate of the solvent. The film thickness of the organic thin film obtained by application | coating to a board | substrate does not have limitation in particular, Preferably it is 1 nm-100 micrometers, Especially preferably, it is 10 nm-20 micrometers. In addition, the thin film obtained in this way can also be arranged more highly by heating at 60-150 degreeC.

(Luminescent material)
The biphenylene derivative represented by the general formula (1) obtained in the present invention can be used as a light emitting material by applying a solution of a biphenylene derivative to a substrate, and in particular, can be used as a material for an organic electroluminescent element. Accordingly, the biphenylene derivative represented by the general formula (1) is expected to be used as an organic EL material.

  The solvent for preparing the solution of the biphenylene derivative represented by the general formula (1) is not particularly limited. For example, o-dichlorobenzene, chlorobenzene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform Halogen solvents such as THF; ether solvents such as THF and dioxane; hydrocarbon solvents of aromatic compounds such as toluene, xylene and mesitylene; ester solvents such as ethyl acetate and γ-butyrolactone; N, N-dimethylformamide, Amide solvents such as N-methylpyrrolidone; and the like. These solvents may be used alone or as a mixture of two or more. Of these, chlorobenzene, toluene and the like are preferable.

  By mixing and stirring the above-mentioned solvent and the biphenylene derivative represented by the general formula (1), a solution of the biphenylene derivative represented by the general formula (1) is obtained. The temperature at the time of mixing and stirring is preferably 10 to 200 ° C, particularly preferably 20 to 150 ° C. The concentration of the biphenylene derivative represented by the general formula (1) when mixing and stirring can be changed depending on the solvent and the temperature, and is preferably 0.01 to 10.0% by weight. The solution can be prepared in air, but is preferably prepared in an inert atmosphere such as nitrogen or argon.

  The application of the solution containing the biphenylene derivative represented by the general formula (1) can be carried out in the air, but is preferably carried out under a nitrogen stream in consideration of drying of the solvent. In order to obtain suitable coating properties, the viscosity of the solution containing the biphenylene derivative represented by the general formula (1) of the present invention is preferably in the range of 0.005 to 20 poise.

  Next, preparation of a light emitting material by applying a solution containing a biphenylene derivative represented by the general formula (1) of the present invention will be described. Such a luminescent material can be produced by applying the above solution to a substrate.

  The production of the light-emitting material by application to the substrate can be carried out by evaporating the solvent by a method such as heating, air flow, and natural drying after applying the solution onto the substrate. The concentration of the biphenylene derivative represented by the general formula (1) in the solution is not particularly limited, and is preferably 0.01 to 10.0% by weight, for example. There is no particular limitation on the coating temperature, and for example, it can be suitably carried out between 20 and 200 ° C, particularly preferably between 30 and 100 ° C. The specific method of application is not particularly limited, and for example, spin coating, cast coating, dip coating, and the like can be used. Further, it can be produced by using a printing technique such as screen printing, ink jet printing, or gravure printing. The material of the substrate to be used is not particularly limited, and various crystalline and non-crystalline materials can be used. Specific examples of the substrate include, for example, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly (diisopropyl fumaric acid), poly (diethyl fumaric acid). ) Plastic substrate; glass, quartz, aluminum oxide, silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide and other inorganic material substrates; gold, copper, chromium, titanium, aluminum and other metal substrates are suitable Can be used. The surfaces of these substrates can be used even if they are modified with silanes such as octadecyltrichlorosilane and octadecyltrimethoxysilane; and silylamines such as hexamethyldisilazane. Further, the substrate may be made of an insulating or dielectric material. Drying of the solvent after coating can be removed under normal pressure or reduced pressure, or it may be dried by heating or a nitrogen stream. Furthermore, the film quality of the biphenylene derivative represented by the general formula (1) can be controlled by adjusting the evaporation rate of the solvent. The film thickness of the light emitting material obtained by coating on the substrate is not particularly limited, and is preferably 1 nm to 100 μm, particularly preferably 10 nm to 20 μm.

In addition, the light-emitting material using the biphenylene derivative represented by the general formula (1) of the present invention can be formed into a thin film by a vacuum deposition method. The thin film by a vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The vacuum degree of the vacuum chamber when forming a thin film by the vacuum evaporation method is 1.3 × 10 ^{−2 to} 1.3 × 10 ⁻⁵ Pascal that can be reached by a diffusion pump, a turbo molecular pump, a cryopump, or the like that is generally used. Is preferred. The deposition rate is preferably 0.005 to 1.0 nm / second, although it depends on the film pressure to be formed.

  The light emission quantum yield of the light emitting material using the biphenylene derivative represented by the general formula (1) of the present invention is preferably 2 to 80%, particularly preferably 3 to 50%.

  Since the biphenylene derivative represented by the general formula (1) of the present invention has a molecular structure with high plane rigidity, it can be expected to give excellent semiconductor characteristics. The biphenylene derivative is dissolved in a solvent such as toluene and is not easily oxidized by air even in a solution state. Therefore, a semiconductor thin film can be easily produced by a coating method. In addition, since the biphenylene derivative represented by the general formula (1) of the present invention has a long conjugated system, it includes an anthracene ring that emits light having a long wavelength from yellow to red, and thus can be expected as a light emitting material. . Accordingly, the biphenylene derivative represented by the general formula (1) of the present invention is used for an active phase of an organic semiconductor in a transistor such as an electronic paper, an organic EL display, a liquid crystal display, or an IC tag, and further, a light emitting material and a host material of an organic EL display. It can be used for organic semiconductor laser materials, organic thin film solar cell materials, light emitting organic transistors, photonic crystal materials, and the like.

  Provided are a biphenylene derivative having excellent oxidation resistance and capable of forming a semiconductor active phase by a coating method and its use. Furthermore, in the production method of the present invention, a biphenylene derivative having a substituent introduced therein can be produced, and a novel organic semiconductor material can be provided.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited only to these Examples.

For identification of the product, ¹ H NMR spectrum and mass spectrum were used. The ¹ H NMR spectrum was measured using JEOL GSX-270WB (270 MHz) manufactured by JEOL. The mass spectrum (MS) is obtained by directly introducing a sample using JEOL JMS-700 manufactured by JEOL, and by electron impact (EI) method (70 electron volts) or FAB method (6 kiloelectron volts, xenon gas, matrix (2- Nitrophenyl octyl ether).

  The progress of the reaction was confirmed using thin layer chromatography, gas chromatography and gas chromatography-mass spectrum (GCMS) analysis.

Gas chromatography analyzer Shimadzu GC14B
Column J & W Scientific, DB-1, 30m
Gas chromatography-mass spectrum analyzer Perkin Elmer Auto System XL (MS part; Turbomass Gold)
Column J & W Scientific, DB-1, 30m
Commercially available products were used as the reaction solvent unless otherwise noted. When a Grignard reagent or an organometallic reagent such as butyl lithium was used, a commercially available dehydrated solvent was used as it was.

  Evaluation as a luminescent material was carried out by measuring a light emission quantum yield and a fluorescence spectrum in a thin film state. The emission quantum yield was measured using C9920-01 manufactured by Hamamatsu Photonics, and the fluorescence spectrum was measured using FP6500 manufactured by JASCO.

Synthesis Example 1 (Synthesis of 4-bromo-5-iodophthalic anhydride)
4-Bromo-5-iodophthalic anhydride was synthesized as follows with reference to “Journal of Organic Chemistry” (USA), 1951, Vol. 16, pp. 1577-1581.

4-Bromophthalimide (Tokyo Chemical Industry Co., Ltd.) 9.95 g (44.0 mmol) was placed in a 50 ml two-necked eggplant flask substituted with nitrogen gas. Subsequently, 5.87 g (23.1 mmol) of iodine and 12 ml of 10% fuming sulfuric acid (manufactured by Yotsuhata Chemical Industry) were added, and the reaction was performed at 90 ° C. for 23 hours. The reaction mixture was cooled to room temperature and poured into ice, and then filtered through a glass filter to obtain 12.8 g of a yellow solid. The obtained solid was dissolved in 35 ml of concentrated sulfuric acid and reacted at 130 ° C. for 5 hours. The reaction mixture was ice-cooled, ice water was added and the precipitated solid was filtered to obtain 13.8 g of a phthalic acid derivative solid. Next, the obtained solid was dissolved in an aqueous solution obtained by dissolving 3.6 g of sodium hydroxide in 18 ml of water at room temperature. Acetic acid was added to this basic aqueous solution to adjust the pH to 3 to 4, and the white precipitate of the monosodium salt of the phthalic acid derivative was filtered. The obtained white solid was suspended in water, the pH was adjusted to 1 or less with concentrated hydrochloric acid, and 4.93 g of a white solid was obtained again as a phthalic acid derivative. This solid was dissolved in 48 ml of toluene, 8.7 g (85.7 mmol) of acetic anhydride was added, and the reaction was performed at 105 ° C. for 4 hours. The reaction solution was concentrated under reduced pressure to obtain 3.79 g of a white solid. A component insoluble in heated toluene was removed from this solid to obtain 5.13 g (14.5 mmol) of the desired 4-bromo-5-iodophthalic anhydride (yield 33%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.51 (s, 1H), 8.23 (s, 1H).
MS m / z: 353 (M ⁺ , 100%), 309 (M ⁺ —CO ₂ , 18%), 282 (M ⁺ —C ₂ O ₃ , 10%), 155 (M ⁺ —C ₂ O ₃ − _{^{I, 16%), 74 (}} M + -C 2 O 3 -I-Br, 32%).

Synthesis Example 2 (Synthesis of 1,2-didodecylbenzene)
1,2-didodecylbenzene was synthesized as follows according to “The Chemical Society of Japan”, 1989, pages 983-987.

2.22 g (15.1 mmol) of 1,2-dichlorobenzene, 131 mg (0.24 mmol) of dichloro [1,3-bis (diphenylphosphino) propane] nickel (Tokyo Chemical Industry), 11.5 ml of dry diethyl ether To the mixed solution, 45 ml (45 mmol) of dodecylmagnesium bromide (manufactured by Sigma-Aldrich, 1.0 mol / l diethyl ether solution) was added dropwise at 0 ° C. in a nitrogen atmosphere. The reaction was carried out at 35 ° C. for 20 hours, the reaction mixture was cooled to 0 ° C., diluted hydrochloric acid was added, and the mixture was extracted with diethyl ether. The diethyl ether solution was washed with water, a saturated aqueous solution of sodium bicarbonate and water in that order and dried over calcium chloride. The resulting liquid was purified by silica gel column chromatography (eluent: hexane) and vacuum distillation to obtain 5.56 g (13.4 mmol) of the desired 1,2-didodecylbenzene (yield 88%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.14-7.09 (m, 4H), 2.59 (t, J = 7.8 Hz, 4H), 1.55 (m, 4H), 1.26 (m, 36H), 0.88 (t, J = 6.8 Hz, 6H).
_{^{MS m / z: 414 (M}} +, 100%), 260 (M + -C 11 H 23, 71%), 106 (M + -C 22 H 46, 98%).

Synthesis Example 3 (Synthesis of 2-bromo-3-iodo-6,7-didodecylanthraquinone) (compound of general formula (5))
2-Bromo-3-iodo-6,7-didodecylanthraquinone was synthesized as follows with reference to “Berichte” (Germany), 1933, 66B, pages 1876-1891.

4-Bromo-5-iodophthalic anhydride 2.82 g (8.00 mmol) obtained in Synthesis Example 1, 3.32 g (8.00 mmol) of 1,2-didodecylbenzene obtained in Synthesis Example 2, tetra To a mixed solution of 5.0 ml of chloroethane, 2.41 g (18.1 mmol) of aluminum chloride was added and reacted at room temperature for 3 hours. Quenched by adding water, further washed with water, and dried under vacuum heating to obtain 6.2 g of a white solid. The obtained solid was dissolved in 44 ml of concentrated sulfuric acid and reacted at 80 ° C. for 1 hour. The reaction mixture was poured into ice, and the precipitated solid was filtered and washed with water. After drying under reduced pressure, the product was purified by silica gel column chromatography (eluent: hexane: methylene chloride = 10: 1) and recrystallization from heptane, and a yellow solid of 2-bromo-3-iodo-6,7-didodecylanthraquinone 4 .20 g (5.60 mmol) was obtained (yield 70%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.73 (s, 1H), 8.45 (s, 1H), 8.05 (s, 2H), 2.75 (m, 4H), 1 .62 (m, 4H), 1.26 (m, 36H), 0.88 (m, 6H).
_{^{MS m / z: 750 (M}} +, 100%), 440 (M + -C 22 H 46, 8%), 313 (M + -C 22 H 46 -I, 2%), 233 (M + -C _{22 H 46 -I-Br, 1} %).

Synthesis Example 4 (Synthesis of 2-bromo-3-iodo-6,7-didodecylanthracene) (compounds of general formulas (3) and (4))
Under a nitrogen atmosphere, 1.10 g (1.47 mmol) of 2-bromo-3-iodo-6,7-didodecylanthraquinone synthesized in Synthesis Example 3 was placed in a 100 ml Schlenk reaction vessel. Next, 17 ml of THF was added, and 4.0 ml (4.0 mmol) of diisobutylaluminum hydride (manufactured by Kanto Chemical Co., 0.99 mol / l, toluene solution) was added as a hydride reducing agent, and a reduction reaction was performed at room temperature for 1.5 hours. Subsequently, 10 ml of 6M hydrochloric acid aqueous solution was added to the reaction mixture as an acid catalyst, and dehydration reaction was performed at 65 ° C. for 3 hours. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The diethyl ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Again, 17 ml of THF was added, 5.5 ml (5.4 mmol) of diisobutylaluminum hydride was added, and a reduction reaction was performed at room temperature for 1.5 hours. Subsequently, 10 ml of 6M hydrochloric acid aqueous solution was added to the reaction mixture, and dehydration reaction was performed for 3 hours. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The diethyl ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (eluent: hexane) gave 629 mg (0.87 mmol) of 2-bromo-3-iodo-6,7-didodecylanthracene as a yellow solid (yield 59%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.55 (s, 1H), 8.27 (s, 1H), 8.16 (s, 1H), 8.15 (s, 1H), 7 .72 (s, 2H), 2.78 (m, 4H), 1.71 (m, 4H), 1.27 (m, 36H) 0.88 (m, 6H).
_{^{MS m / z: 720 (M}} +, 100%), 410 (M + -C 22 H 46, 16%), 283 (M + -C 22 H 46 -I, 4%), 203 (M + -C _{22 H 46 -I-Br, 5} %).

Example 1 (Synthesis of 6,7,6 ′, 7′-tetradodecyl-3,3′-dibromo-2,2′-bianthracenyl) [Synthesis of dihalobiphenyl derivative represented by general formula (2)]
Under a nitrogen atmosphere, 205 mg (0.285 mmol) of 2-bromo-3-iodo-6,7-didodecylanthracene synthesized in Synthesis Example 4 and 8 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −55 ° C., and 0.70 ml (0.57 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.81 M) was added dropwise. After aging for 5 minutes, the mixture was cooled to −78 ° C., and 59.2 mg (0.57 mmol) of trimethoxyborane (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After gradually warming to room temperature, 3M aqueous hydrochloric acid solution was added and stirred for 30 minutes, and then toluene was added for phase separation. The organic phase was concentrated under reduced pressure. To the obtained solid, 210 mg (0.292 mmol) of 2-bromo-3-iodo-6,7-didodecylanthracene synthesized in Synthesis Example 4 and tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 16. 5 mg (0.014 mmol), 5 ml of toluene, and 1.2 ml of ethanol were added. Further, an aqueous solution consisting of 92.8 mg (0.873 mmol) of sodium carbonate and 1.6 ml of water was added, and the reaction was carried out at 60 ° C. for 24 hours. After cooling to room temperature, toluene and water were added for phase separation. The organic phase was concentrated, and the resulting residue was dissolved in 5 ml of toluene, 0.02 ml of 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 2 hours. This toluene solution was washed twice with water and then dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting residue was filtered through a column packed with silica gel (solvent, hexane). The obtained crude solid was recrystallized from heptane to obtain 287 mg of the target yellow solid (yield 85%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.33 (s, 2H), 8.31 (s, 2H), 8.29 (s, 2H), 7.97 (s, 2H), 7 .78 (s, 2H), 7.75 (s, 2H), 2.79 (m, 8H), 1.72 (m, 8H), 1.28 (m, 72H) 0.87 (m, 12H) ).
^{The 1} H NMR spectrum is shown in FIG.
MS m / z: 1185 (M ⁺ , 2%), 592 (M ⁺ / 2, 100).

^{From 1} H NMR and MS measurements, it was confirmed that 6,7,6 ′, 7′-tetradodecyl-3,3′-dibromo-2,2′-bianthracenyl was obtained. Note that. Its structural formula is shown below.

実施例２ （テトラドデシルジナフトビフェニレンの合成）［一般式（１）で示されるビフェニレン誘導体の合成］
窒素雰囲気下、１００ｍｌシュレンク反応容器に実施例１で合成した６，７，６’，７’−テトラドデシル−３，３’−ジブロモ−２，２’−ビアントラセニル２４０ｍｇ（０．２０２ｍｍｏｌ）及びジエチルエーテル７ｍｌを添加した。この混合物を０℃に冷却後、リチオ化剤であるｎ−ブチルリチウム（関東化学製、１．５９Ｍ）のヘキサン溶液０．２８ｍｌ（０．４４ｍｍｏｌ）を滴下した。１時間かけて５℃まで昇温しメタル化の熟成を行った。一方、別の１００ｍｌシュレンク反応容器に塩化銅（ＩＩ）（和光純薬工業製）９５．３ｍｇ（０．７０９ｍｍｏｌ）及びＴＨＦ１０ｍｌを添加し、−７８℃に冷却した。ここへ先のメタル化物のジエチルエーテル溶液をテフロン（登録商標）キャヌラーを用いて移液した。徐々に昇温し、一晩かけて室温まで反応温度を上げた。３Ｍ塩酸水溶液及びトルエンを添加した。分相し、有機相をさらに水で洗浄し、無水硫酸ナトリウムで乾燥した。有機相を濾過し、減圧濃縮し、得られた粗固体をトルエンから再結晶化し、目的物の黄色固体１０８ｍｇを得た（収率５２％）。
^１Ｈ ＮＭＲ（重トルエン，６０℃）：δ＝７．９５（ｓ，４Ｈ），７．６５（ｓ，４Ｈ），７．４０（ｓ，４Ｈ），２．８３（ｔ，Ｊ＝８．５Ｈｚ，８Ｈ），１．７８（ｍ，８Ｈ），１．３１（ｍ，７２Ｈ）０．９２（ｍ，１２Ｈ）。
^１Ｈ ＮＭＲスペクトルを図２に示した。
ＦＡＢＭＳ ｍ／ｚ： １０２６（Ｍ^＋）。

Example 2 (Synthesis of tetradodecyldinaphthobiphenylene) [Synthesis of biphenylene derivative represented by general formula (1)]
Under a nitrogen atmosphere, 240 mg (0.202 mmol) of 6,7,6 ′, 7′-tetradodecyl-3,3′-dibromo-2,2′-bianthracenyl synthesized in Example 1 and diethyl ether in a 100 ml Schlenk reaction vessel 7 ml was added. After cooling the mixture to 0 ° C., 0.28 ml (0.44 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) as a lithiating agent was added dropwise. The temperature was raised to 5 ° C. over 1 hour, and aging of metallization was performed. On the other hand, 95.3 mg (0.709 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 10 ml of THF were added to another 100 ml Schlenk reaction vessel and cooled to -78 ° C. The diethyl ether solution of the metallized product was transferred here using a Teflon (registered trademark) cannula. The temperature was gradually raised, and the reaction temperature was raised to room temperature overnight. 3M aqueous hydrochloric acid and toluene were added. The phases were separated and the organic phase was further washed with water and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting crude solid was recrystallized from toluene to obtain 108 mg of the objective yellow solid (yield 52%).
¹ H NMR (deuterium toluene, 60 ° C.): δ = 7.95 (s, 4H), 7.65 (s, 4H), 7.40 (s, 4H), 2.83 (t, J = 8. 5 Hz, 8H), 1.78 (m, 8H), 1.31 (m, 72H) 0.92 (m, 12H).
^{The 1} H NMR spectrum is shown in FIG.
FABMS m / z: 1026 (M ⁺ ).

^{From 1} H NMR and MS measurements, it was confirmed that tetradodecyldinaphthobiphenylene was obtained. The structural formula is shown below.

合成例５ （２−ブロモ−３−ヨード−６，７−（ドデシル）フルオロアントラセンの合成）（一般式（３）及び（４）の化合物）
合成例２で１，２−ジクロロベンゼンの代わりに、１−クロロ−２−フルオロベンゼン（東京化成工業製）を用いた以外は合成例２と同じ操作を繰り返して１−ドデシル−２−フルオロベンゼンを合成した（収率８０％）。この１−ドデシル−２−フルオロベンゼンと合成例１で得られた４−ブロモ−５−ヨード無水フタル酸を用い、合成例３と同じ操作を繰り返し２−ブロモ−３−ヨード−６，７−（ドデシル）フルオロアントラキノンを得（収率５４％）、さらに合成例４と同じ操作を繰り返して、２−ブロモ−３−ヨード−６，７−（ドデシル）フルオロアントラセンへ変換した（収率６３％）。

Synthesis Example 5 (Synthesis of 2-bromo-3-iodo-6,7- (dodecyl) fluoroanthracene) (compounds of general formulas (3) and (4))
The same operation as in Synthesis Example 2 was repeated except that 1-chloro-2-fluorobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,2-dichlorobenzene in Synthesis Example 2, and 1-dodecyl-2-fluorobenzene was repeated. Was synthesized (yield 80%). Using this 1-dodecyl-2-fluorobenzene and 4-bromo-5-iodophthalic anhydride obtained in Synthesis Example 1, the same operation as in Synthesis Example 3 was repeated and 2-bromo-3-iodo-6,7- (Dodecyl) fluoroanthraquinone was obtained (yield 54%), and further the same operation as in Synthesis Example 4 was repeated to convert to 2-bromo-3-iodo-6,7- (dodecyl) fluoroanthracene (yield 63%). ).

Example 3 (Synthesis of didodecyldifluoro-3,3′-dibromo-2,2′-bianthracenyl) [Synthesis of dihalobiphenyl derivative represented by general formula (2)]
Under a nitrogen atmosphere, 464 mg (0.815 mmol) of 2-bromo-3-iodo-6,7- (dodecyl) fluoroanthracene synthesized in Synthesis Example 5 and 10 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −60 ° C., and 1.3 ml (0.84 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65 M) was added dropwise. After aging for 5 minutes, the mixture was cooled to −78 ° C., and 0.84 ml (0.84 mmol) of a diethyl ether solution of zinc chloride (manufactured by Sigma-Aldrich, 1.0 M) was added dropwise. After gradually raising the temperature to room temperature, the produced slurry was concentrated under reduced pressure. To the obtained solid, 471 mg (0.827 mmol) of 2-bromo-3-iodo-6-dodecyl-7-fluoroanthracene synthesized in Synthesis Example 5 and tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 47 0.1 mg (0.041 mmol) and THF 8 ml were added. The reaction was carried out at 64 ° C. for 8 hours. After cooling to room temperature, toluene and water were added for phase separation. The organic phase was concentrated, and the resulting residue was dissolved in 5 ml of toluene, 0.1 ml of 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 2 hours. The toluene solution was washed twice with water, the organic phase was concentrated under reduced pressure, and saturated brine and toluene were added to the resulting residue. The phases were separated and the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting residue was filtered through a column packed with silica gel (solvent; hexane). The filtrate was concentrated under reduced pressure, and the resulting crude solid was recrystallized from heptane to obtain 440 mg of a yellow solid consisting of a mixture of two isomers of didodecyldifluoro-3,3′-dibromo-2,2′-bianthracenyl. (Yield 61%).
MS m / z: 885 (M ⁺ , 4%), 725 (M ⁺ -2Br, 100).

  From the MS measurement, it was confirmed that didodecyldifluoro-3,3'-dibromo-2,2'-bianthracenyl was obtained. The structural formula is shown below.

実施例４ （ジドデシルジフルオロジナフトビフェニレンの合成）［一般式（１）で示されるビフェニレン誘導体の合成］
窒素雰囲気下、１００ｍｌシュレンク反応容器に、実施例３で合成したジドデシルジフルオロ−３，３’−ジブロモ−２，２’−ビアントラセニル３８８ｍｇ（０．４３８ｍｍｏｌ）及びジエチルエーテル７ｍｌを添加した。この混合物を０℃に冷却し、リチオ化剤であるｎ−ブチルリチウム（関東化学製、１．５９Ｍ）のヘキサン溶液０．６０ｍｌ（０．９５ｍｍｏｌ）を滴下した。０℃で８０分間撹拌した（リチオ化反応）。別の１００ｍｌシュレンク反応容器に、塩化銅（ＩＩ）（和光純薬工業製）１７７ｍｇ（１．３１ｍｍｏｌ）及びＴＨＦ１５ｍｌを添加し、−７８℃に冷却した。ここへ先のジリチオ化物のジエチルエーテル溶液をテフロン（登録商標）キャヌラーを用いて移液した。１５時間かけて室温までゆっくり昇温し、３Ｍ塩酸水溶液を添加した。分相し、有機相をさらに飽和食塩水で洗浄した。懸濁している有機相を濾過し、固体を濾別した。この固体を水及びヘキサンで洗浄し、得られた固体をトルエンから再結晶化し、２種類のジドデシルジフルオロジナフトビフェニレンの２種類の異性体の混合物からなる黄色固体１４６ｍｇを得た（収率４６％）。
ＦＡＢＭＳ ｍ／ｚ： ７２５（Ｍ^＋）。

Example 4 (Synthesis of didodecyldifluorodinaphthobiphenylene) [Synthesis of biphenylene derivative represented by general formula (1)]
Under a nitrogen atmosphere, 388 mg (0.438 mmol) of didodecyldifluoro-3,3′-dibromo-2,2′-bianthracenyl synthesized in Example 3 and 7 ml of diethyl ether were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to 0 ° C., and 0.60 ml (0.95 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) as a lithiating agent was added dropwise. The mixture was stirred at 0 ° C. for 80 minutes (lithiation reaction). To another 100 ml Schlenk reaction vessel, 177 mg (1.31 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 ml of THF were added and cooled to -78 ° C. To this, the diethyl ether solution of the dilithiated compound was transferred using a Teflon (registered trademark) cannula. The temperature was slowly raised to room temperature over 15 hours, and 3M aqueous hydrochloric acid was added. The phases were separated, and the organic phase was further washed with saturated brine. The suspended organic phase was filtered and the solid was filtered off. This solid was washed with water and hexane, and the obtained solid was recrystallized from toluene to obtain 146 mg of a yellow solid composed of a mixture of two kinds of isomers of two kinds of didodecyldifluorodinaphthobiphenylene (yield: 46). %).
FABMS m / z: 725 (M ⁺ ).

  From MS measurement, it was confirmed that didodecyldifluorodinaphthobiphenylene was obtained. The structural formula is shown below.

合成例６ （４−ブロモ−１，２−ジヨードベンゼンの合成）
１００ｍｌシュレンク反応容器に、１，２−ジヨードベンゼン（東京化成工業製）５．５６ｇ（１６．８ｍｍｏｌ）及びジクロロメタン３０ｍｌを添加し、０℃に冷却した。鉄粉（シグマ−アルドリッチ製）６７ｍｇ及びヨウ素１０ｍｇ（０．０４ｍｍｏｌ）を添加後、臭素０．８７ｍｌ（１７ｍｍｏｌ）を滴下した。０℃で８時間撹拌後、亜硫酸水素ナトリウム水溶液を添加し、反応を停止させた。有機相を水で洗浄後、無水硫酸ナトリウムで乾燥した。減圧濃縮し、得られた残渣をＴＨＦ：メタノール＝１：１から２回再結晶化し、４−ブロモ−１，２−ジヨードベンゼン４．９４ｇの白色結晶を得た（収率７２％）。

Synthesis Example 6 (Synthesis of 4-bromo-1,2-diiodobenzene)
To a 100 ml Schlenk reaction vessel, 5.56 g (16.8 mmol) of 1,2-diiodobenzene (manufactured by Tokyo Chemical Industry) and 30 ml of dichloromethane were added and cooled to 0 ° C. After adding 67 mg of iron powder (manufactured by Sigma-Aldrich) and 10 mg (0.04 mmol) of iodine, 0.87 ml (17 mmol) of bromine was added dropwise. After stirring at 0 ° C. for 8 hours, an aqueous sodium hydrogen sulfite solution was added to stop the reaction. The organic phase was washed with water and dried over anhydrous sodium sulfate. The residue was recrystallized twice from THF: methanol = 1: 1 to obtain 4.94 g of 4-bromo-1,2-diiodobenzene as white crystals (yield 72%).

Synthesis Example 7 (Synthesis of 4-bromo-1,2- (perfluorododecyl) benzene)
4-Bromo-1,2- (perfluorododecyl) benzene was synthesized as follows with reference to “Journal of Fluorine Chemistry”, 1989, 43, 207-228.

  In a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, 2.85 g (44.8 mmol) of copper powder (copper bronze) (manufactured by Sigma-Aldrich), 18.4 g (24.6 mmol) of perfluorododecyl iodide (manufactured by Synquest), 4.58 g (11.2 mmol) of 4-bromo-1,2-diiodobenzene synthesized in Synthesis Example 6 and 18 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd., dehydrated product) were added and heated to 125 ° C., The reaction was allowed for 8 hours. After cooling to room temperature, water was added to stop the reaction. Further diethyl ether was added and the mixture was filtered through celite. The filtrate was extracted with diethyl ether, and the combined organic phases were washed with water and dried over anhydrous magnesium sulfate. The residue was purified by silica gel column chromatography (solvent: hexane) to obtain 6.24 g of 4-bromo-1,2- (perfluorododecyl) benzene as a colorless liquid (yield 40). %).

Synthesis Example 8 (Synthesis of 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthraquinone) (Compound of general formula (5))
Under a nitrogen atmosphere, 6.11 g (4.39 mmol) of 4-bromo-1,2- (perfluorododecyl) benzene obtained in Synthesis Example 7 and 80 ml of THF were added to a 300 ml Schlenk reaction vessel. This solution was cooled to −50 ° C., and 6.8 ml (4.4 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65 M) was added dropwise. After aging at −50 ° C. for 30 minutes, a solution consisting of 1.48 g (4.20 mmol) of 4-bromo-5-iodophthalic anhydride synthesized in Synthesis Example 1 and 20 ml of THF was added dropwise thereto. The reaction mixture was allowed to warm to room temperature overnight, then cooled with ice and 3M aqueous hydrochloric acid was added. The mixture was extracted with diethyl ether, and the combined organic phases were washed with saturated brine and dried over anhydrous magnesium sulfate. Concentration under reduced pressure gave 7.00 g of a white solid. Concentrated sulfuric acid (40 ml) was added to the obtained solid and reacted at 80 ° C. for 12 hours. The reaction mixture was poured into ice, and the precipitated solid was filtered and washed with water. After drying, the product was purified by silica gel column chromatography (eluent: hexane: methylene chloride = 15: 1) and recrystallization from heptane, and 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthraquinone was purified. 1.86 g (1.13 mmol) of solid was obtained (27% yield).

Synthesis Example 9 (Synthesis of 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthracene) (Compounds of general formulas (3) and (4))
Under a nitrogen atmosphere, 1.81 g (1.10 mmol) of 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthraquinone synthesized in Synthesis Example 8 was placed in a 100 ml Schlenk reaction vessel. Next, 15 ml of THF was added, and 3.5 ml (3.5 mmol) of diisobutylaluminum hydride (manufactured by Kanto Chemical Co., 0.99 mol / l, toluene solution) as a hydride reducing agent was added, and a reduction reaction was performed at room temperature for 1.5 hours. . Subsequently, 10 ml of 6M hydrochloric acid aqueous solution was added to the reaction mixture as an acid catalyst, and dehydration reaction was performed at 65 ° C. for 3 hours. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The diethyl ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. 15 ml of THF was added again, 3.5 ml (3.5 mmol) of diisobutylaluminum hydride was added, and a reduction reaction was performed at room temperature for 1.5 hours. Subsequently, 10 ml of 6M hydrochloric acid aqueous solution was added to the reaction mixture, and dehydration reaction was performed for 3 hours. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The diethyl ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (eluent: hexane) gave 1.12 g of 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthracene as a yellow solid (yield 63%).

Example 5 (Synthesis of 6,7,6 ′, 7′-tetra (perfluorododecyl) -3,3′-dibromo-2,2′-bianthracenyl) [dihalobiphenyl derivative represented by the general formula (2) Synthesis]
Under a nitrogen atmosphere, 483 mg (0.298 mmol) of 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthracene synthesized in Synthesis Example 9 and 7 ml of THF were added to a 100 ml Schlenk reaction vessel. The solution was cooled to −70 ° C., and 0.46 ml (0.30 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65 M) was added dropwise. After aging for 10 minutes, the mixture was cooled to −78 ° C., and 0.30 ml (0.30 mmol) of zinc chloride (manufactured by Sigma-Aldrich, 1.0 M diethyl ether solution) was added dropwise. The mixture was gradually warmed to room temperature and concentrated under reduced pressure. To the obtained residue, 490 mg (0.303 mmol) of 2-bromo-3-iodo-6,7-di (perfluorododecyl) anthracene synthesized in Synthesis Example 9 and tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 17.3 mg (0.015 mmol) and 8 ml of THF were added, and the reaction was carried out at 64 ° C. for 10 hours. The reaction was stopped by cooling the vessel with water and adding 3 ml of 3M aqueous hydrochloric acid. After adding toluene, the phases were separated, and the organic phase was washed with brine. The organic phase was concentrated under reduced pressure, the solvent was distilled off, and further dried under vacuum. Toluene was added to the obtained residue, 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.06 ml) was added, and the mixture was stirred at room temperature for 2 hours. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (solvent: hexane and hexane: chloroform = 10: 1), and 6,7,6 ′, 7′-tetra (perfluorododecyl) -3,3′-dibromo-2,2 507 mg of a yellow solid of '-bianthracenyl was obtained (yield 57%).
FABMS m / z: 2985 (M ⁺ ).

  From MS measurement, it was confirmed that 6,7,6 ', 7'-tetra (perfluorododecyl) -3,3'-dibromo-2,2'-bianthracenyl was obtained. The structural formula is shown below.

実施例６ （テトラ（パーフルオロドデシル）ジナフトビフェニレンの合成）［一般式（１）で示されるビフェニレン誘導体の合成］
窒素雰囲気下、１００ｍｌシュレンク反応容器に、実施例５で合成した６，７，６’，７’−テトラ（パーフルオロドデシル）−３，３’−ジブロモ−２，２’−ビアントラセニル５００ｍｇ（０．１６７ｍｍｏｌ）及びジエチルエーテル７ｍｌを添加した。この混合物を０℃に冷却し、リチオ化剤であるｎ−ブチルリチウム（関東化学製、１．５９Ｍ）のヘキサン溶液０．２３ｍｌ（０．３７ｍｍｏｌ）を滴下し、０℃で９０分間撹拌した（リチオ化反応）。別の１００ｍｌシュレンク反応容器に、塩化銅（ＩＩ）（和光純薬工業製）６７．４ｍｇ（０．５０１ｍｍｏｌ）及びＴＨＦ１６ｍｌを添加し、−７８℃に冷却した。ここへ先のジリチオ化物のジエチルエーテル溶液をテフロン（登録商標）キャヌラーを用いて移液した。１５時間かけて室温までゆっくり昇温し、３Ｍ塩酸水溶液を添加した。分相し、有機相をさらに飽和食塩水で洗浄した。懸濁している有機相を濾過し、固体を濾別した。この固体を水及びヘキサンで洗浄し、得られた固体をトルエンから再結晶化し、目的物の黄色固体１８４ｍｇを得た（収率３９％）。
ＦＡＢＭＳ ｍ／ｚ： ２８２５（Ｍ^＋）。

Example 6 (Synthesis of tetra (perfluorododecyl) dinaphthobiphenylene) [Synthesis of biphenylene derivative represented by general formula (1)]
In a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, 500 mg (0 .. 6) of 6,7,6 ′, 7′-tetra (perfluorododecyl) -3,3′-dibromo-2,2′-bianthracenyl synthesized in Example 5 was used. 167 mmol) and 7 ml of diethyl ether were added. The mixture was cooled to 0 ° C., 0.23 ml (0.37 mmol) of a hexane solution of n-butyl lithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) as a lithiating agent was added dropwise, and the mixture was stirred at 0 ° C. for 90 minutes ( Lithiation reaction). To another 100 ml Schlenk reaction vessel, 67.4 mg (0.501 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 16 ml of THF were added and cooled to -78 ° C. To this, the diethyl ether solution of the dilithiated compound was transferred using a Teflon (registered trademark) cannula. The temperature was slowly raised to room temperature over 15 hours, and 3M aqueous hydrochloric acid was added. The phases were separated, and the organic phase was further washed with saturated brine. The suspended organic phase was filtered and the solid was filtered off. This solid was washed with water and hexane, and the obtained solid was recrystallized from toluene to obtain 184 mg of the objective yellow solid (yield 39%).
FABMS m / z: 2825 (M ⁺ ).

  From MS measurement, it was confirmed that tetra (perfluorododecyl) dinaphthobiphenylene was obtained. The structural formula is shown below.

合成例１０ （４−ブロモ−１，２−ジフェニルベンゼンの合成）
窒素雰囲気下、２００ｍｌシュレンク反応容器に、合成例６で得られた４−ブロモ−１，２−ジヨードベンゼン２．１５ｇ（５．２５ｍｍｏｌ）にジヒドロキシフェニルボラン（和光純薬工業製）１．４７ｇ（１２．１ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（東京化成工業製）４５８ｍｇ（０．４０ｍｍｏｌ）、炭酸ナトリウム３．３４ｇ（３１．５ｍｍｏｌ）、トルエン４２ｍｌ、エタノール１０．５ｍｌ、水１３．３ｍｌを加え、８０℃で２９時間反応させた。１Ｍ塩酸水溶液を加えて反応をクエンチし、トルエンで抽出した後、有機層を水洗浄して無水硫酸ナトリウムで乾燥した。溶媒を減圧留去し、シリカゲルカラムクロマトグラフィー（溶離液；ヘキサン）で精製して目的の４−ブロモ−１，２−ジフェニルベンゼン１．４６ｇ（４．７２ｍｍｏｌ）を得た（収率９０％）。

Synthesis Example 10 (Synthesis of 4-bromo-1,2-diphenylbenzene)
Under a nitrogen atmosphere, in a 200 ml Schlenk reaction vessel, 2.47 g (5.25 mmol) of 4-bromo-1,2-diiodobenzene obtained in Synthesis Example 6 and 1.47 g of dihydroxyphenylborane (manufactured by Wako Pure Chemical Industries, Ltd.) (12.1 mmol), tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 458 mg (0.40 mmol), sodium carbonate 3.34 g (31.5 mmol), toluene 42 ml, ethanol 10.5 ml, water 13.3 ml. In addition, the mixture was reacted at 80 ° C. for 29 hours. The reaction was quenched with 1M aqueous hydrochloric acid and extracted with toluene. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and purified by silica gel column chromatography (eluent: hexane) to obtain 1.46 g (4.72 mmol) of the desired 4-bromo-1,2-diphenylbenzene (yield 90%). .

Synthesis Example 11 (Synthesis of 2-bromo-3-iodo-6,7-diphenylanthraquinone) (compound of general formula (5))
Under a nitrogen atmosphere, 1.46 g (4.72 mmol) of 4-bromo-1,2-diphenylbenzene obtained in Synthesis Example 10 was placed in a 300 ml Schlenk reaction vessel. Next, 28 ml of THF was added and cooled to −78 ° C., and 3.0 ml (4.77 mmol) of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 mol / l, hexane solution) was added and reacted for 30 minutes. Next, 1.66 g (4.72 mmol) of 4-bromo-5-iodophthalic anhydride synthesized in Synthesis Example 1 was added, and the temperature was raised to room temperature. The solid obtained by quenching by adding water was filtered, washed with water, and dried under heating in vacuum to obtain 3.2 g of a white solid. 26 ml of concentrated sulfuric acid was added to the obtained solid and reacted at 80 ° C. for 1 hour. The reaction mixture was poured into ice, and the precipitated solid was filtered and washed with water. After drying, the residue was purified by silica gel column chromatography (eluent; hexane: methylene chloride = 10: 1) and recrystallization from heptane, and 298 mg (0 of 2-bromo-3-iodo-6,7-diphenylanthraquinone yellow solid) .53 mmol) was obtained (yield 11%).

Synthesis Example 12 (Synthesis of 2-bromo-3-iodo-6,7-diphenylanthracene) (Compounds of general formulas (3) and (4))
Under a nitrogen atmosphere, 243 mg (0.43 mmol) of 2-bromo-3-iodo-6,7-diphenylanthraquinone synthesized in Synthesis Example 11 and 5 ml of THF were added to a 50 ml Schlenk reaction vessel. 1.20 ml (1.20 mmol) of diisobutylaluminum hydride as a hydride reducing agent (manufactured by Kanto Chemical Co., 0.99 mol / l, toluene solution) was added dropwise, and a reduction reaction was performed at room temperature for 1.5 hours. To this reaction mixture, 3 ml of 6M aqueous hydrochloric acid as an acid catalyst was added, and dehydration reaction was performed at 65 ° C. for 3 hours. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The diethyl ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. To the obtained residue, 5 ml of THF was added again, 1.20 ml (1.20 mmol) of diisobutylaluminum hydride (manufactured by Kanto Chemical Co., 0.99 mol / l, toluene solution) was added, and a reduction reaction was performed at room temperature for 1.5 hours. . Subsequently, 3 ml of 6M hydrochloric acid aqueous solution was added to the reaction mixture, and dehydration reaction was performed for 3 hours. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The diethyl ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (eluent: hexane) gave 128 mg (0.239 mmol) of 2-bromo-3-iodo-6,7-diphenylanthracene as a yellow solid (yield 56%).

Example 7 (Synthesis of 6,7,6 ′, 7′-tetraphenyl-3,3′-dibromo-2,2′-bianthracenyl) [Synthesis of dihalobiphenyl derivative represented by general formula (2)]
Under a nitrogen atmosphere, 128 mg (0.239 mmol) of 2-bromo-3-iodo-6,7-diphenylanthracene (a compound of the general formula (3)) synthesized in Synthesis Example 12 and 5 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −70 ° C., and 0.74 ml (0.48 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65 M) was added dropwise. After aging for 20 minutes, the mixture was cooled to −78 ° C., and 49.7 mg (0.48 mmol) of trimethoxyborane (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After gradually warming to room temperature, 3M aqueous hydrochloric acid solution was added and stirred for 30 minutes, and then toluene was added for phase separation. The organic phase was concentrated under reduced pressure. To the obtained residue, 125 mg (0.233 mmol) of 2-bromo-3-iodo-6,7-diphenylanthracene synthesized in Synthesis Example 12 (compound of general formula (4)), tetrakis (triphenylphosphine) palladium ( (Tokyo Chemical Industry Co., Ltd.) 10.3 mg (0.009 mmol), toluene 5 ml, and ethanol 1.2 ml were added. Further, an aqueous solution composed of 78.5 mg (0.741 mmol) of sodium carbonate and 1.6 ml of water was added, and the reaction was carried out at 60 ° C. for 24 hours. After cooling to room temperature, toluene and water were added for phase separation. The organic phase was concentrated under reduced pressure, the solvent was distilled off, and further dried under vacuum. Toluene was added to the obtained residue, 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.03 ml) was added, and the mixture was stirred at room temperature for 2 hours. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (solvent; hexane (eluting anthracene derivative) and hexane: dichloromethane = 10: 1 (eluting the target product)), 6,7,6 ′, 7′-tetraphenyl-3, 87.2 mg of a yellow solid of 3′-dibromo-2,2′-bianthracenyl was obtained (yield 57%).
MS m / z: 817 (M ^<+> , 2%), 657 (M ^<+ > ^- 2Br, 100).

  From the MS measurement, it was confirmed that 6,7,6 ', 7'-tetraphenyl-3,3'-dibromo-2,2'-bianthracenyl was obtained. The structural formula is shown below.

実施例８ （テトラフェニルジナフトビフェニレンの合成）（一般式（１）で示されるビフェニレン誘導体）
窒素雰囲気下、５０ｍｌシュレンク反応容器に、実施例７で合成した６，７，６’，７’−テトラフェニル−３，３’−ジブロモ−２，２’−ビアントラセニル８７．０ｍｇ（０．１０６ｍｍｏｌ）及びジエチルエーテル４ｍｌを添加した。この混合物を０℃に冷却し、リチオ化であるｎ−ブチルリチウム（関東化学製、１．５９Ｍ）のヘキサン溶液０．１６ｍｌ（０．２５ｍｍｏｌ）を滴下し、０℃で９０分間撹拌した（リチオ化反応）。別の１００ｍｌシュレンク反応容器に、塩化銅（ＩＩ）（和光純薬工業製）４７．０ｍｇ（０．３５０ｍｍｏｌ）及びＴＨＦ８ｍｌを添加し、−７８℃に冷却した。ここへ先のジリチオ化物のジエチルエーテル溶液をテフロン（登録商標）キャヌラーを用いて移液した。１５時間かけて室温までゆっくり昇温し、３Ｍ塩酸水溶液を添加した。分相し、有機相をさらに飽和食塩水で洗浄した。懸濁している有機相を濾過し、固体を濾別した。この固体を水及びヘキサンで洗浄し、得られた固体をトルエンから再結晶化し、目的物の黄色固体２７ｍｇを得た（収率３９％）。
ＦＡＢＭＳ ｍ／ｚ： ６５７（Ｍ^＋）。

Example 8 (Synthesis of tetraphenyldinaphthobiphenylene) (biphenylene derivative represented by the general formula (1))
Under a nitrogen atmosphere, 87.0 mg (0.106 mmol) of 6,7,6 ′, 7′-tetraphenyl-3,3′-dibromo-2,2′-bianthracenyl synthesized in Example 7 was placed in a 50 ml Schlenk reaction vessel. And 4 ml of diethyl ether were added. The mixture was cooled to 0 ° C., 0.16 ml (0.25 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) as lithiation was added dropwise, and the mixture was stirred at 0 ° C. for 90 minutes (Lithio). Reaction). In another 100 ml Schlenk reaction vessel, 47.0 mg (0.350 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 8 ml of THF were added and cooled to -78 ° C. To this, the diethyl ether solution of the dilithiated compound was transferred using a Teflon (registered trademark) cannula. The temperature was slowly raised to room temperature over 15 hours, and 3M aqueous hydrochloric acid was added. The phases were separated, and the organic phase was further washed with saturated brine. The suspended organic phase was filtered and the solid was filtered off. This solid was washed with water and hexane, and the resulting solid was recrystallized from toluene to obtain 27 mg of the objective yellow solid (yield 39%).
FABMS m / z: 657 (M ⁺ ).

  From the MS measurement, it was confirmed that tetraphenyldinaphthobiphenylene was obtained. The structural formula is shown below.

合成例１３ （４−ブロモ−１，２−ジ（ドデシン−１−イル）ベンゼンの合成）
窒素雰囲気下、３００ｍｌシュレンク反応容器に、合成例６で得られた４−ブロモ−１，２−ジヨードベンゼン１．８４ｇ（４．５０ｍｍｏｌ）、ヨウ化銅（Ｉ）（和光純薬工業製）９０ｍｇ（０．４７ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（東京化成工業製）２７２ｍｇ（０．２４ｍｍｏｌ）、ＴＨＦ５９ｍｌ、トリエチルアミン２．２９ｇ（２２．２ｍｍｏｌ）、１−ドデシン１．５７ｇ（９．４７ｍｍｏｌ）を加えた。この反応混合物を室温で２６時間反応させた。１Ｍ塩酸水溶液を加えて反応をクエンチし、トルエンで抽出した後、有機相を水洗浄して無水硫酸ナトリウムで乾燥した。溶媒を減圧留去し、シリカゲルカラムクロマトグラフィー（溶離液；ジエチルエーテル：ヘキサン＝１：３０の混合液）で精製して目的の４−ブロモ−１，２−ジ（ドデシン−１−イル）ベンゼン１．５２ｇ（３．１４ｍｍｏｌ）を得た（収率７０％）。

Synthesis Example 13 (Synthesis of 4-bromo-1,2-di (dodecyn-1-yl) benzene)
In a 300 ml Schlenk reaction vessel under a nitrogen atmosphere, 1.84 g (4.50 mmol) of 4-bromo-1,2-diiodobenzene obtained in Synthesis Example 6 and copper (I) iodide (manufactured by Wako Pure Chemical Industries, Ltd.) 90 mg (0.47 mmol), tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry) 272 mg (0.24 mmol), THF 59 ml, triethylamine 2.29 g (22.2 mmol), 1-dodecine 1.57 g (9.47 mmol) Was added. The reaction mixture was reacted at room temperature for 26 hours. The reaction was quenched with 1M aqueous hydrochloric acid and extracted with toluene. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and purified by silica gel column chromatography (eluent; diethyl ether: hexane = 1: 30 mixture) to obtain the desired 4-bromo-1,2-di (dodecin-1-yl) benzene. 1.52 g (3.14 mmol) was obtained (70% yield).

Synthesis Example 14 (Synthesis of 2-bromo-3-iodo-6,7-di (dodecin-1-yl) anthraquinone) (Compound of general formula (5))
Under a nitrogen atmosphere, 1.52 g (3.14 mmol) of 4-bromo-1,2-di (dodecin-1-yl) benzene obtained in Synthesis Example 13 was placed in a 200 ml Schlenk reaction vessel. Next, 19 ml of THF was added and cooled to −78 ° C., and 2.0 ml (3.18 mmol) of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 mol / l, hexane solution) was added and reacted for 30 minutes. Next, 1.10 g (3.14 mmol) of 4-bromo-5-iodophthalic anhydride obtained in Synthesis Example 1 was added, and the temperature was raised to room temperature. The solid obtained by quenching by adding water was filtered, washed with water, and dried under heating in vacuum to obtain 2.3 g (3.1 mmol) of white solid. 17 ml of concentrated sulfuric acid was added to this solid and reacted at 80 ° C. for 1 hour. The reaction mixture was poured into ice, and the precipitated solid was filtered and washed with water. After drying, it was purified by silica gel column chromatography (eluent; hexane: methylene chloride = 10: 1) and recrystallization from heptane, and 2-bromo-3-iodo-6,7-di (dodecin-1-yl) 245 mg (0.33 mmol) of an anthraquinone yellow solid was obtained (yield 11%).

Synthesis Example 15 (Synthesis of 2-bromo-3-iodo-6,7-di (dodecin-1-yl) anthracene) (Compounds of general formulas (3) and (4))
Under a nitrogen atmosphere, 245 mg (0.33 mmol) of 2-bromo-3-iodo-6,7-di (dodecin-1-yl) anthraquinone synthesized in Synthesis Example 14 and 4 ml of THF were added to a 50 ml Schlenk reaction vessel. 0.70 ml (0.70 mmol) of diisobutylaluminum hydride as a hydride reducing agent (manufactured by Kanto Chemical Co., 0.99 mol / l, toluene solution) was added dropwise, and a reduction reaction was performed at room temperature for 1.5 hours. To this reaction mixture, 2 ml of 6M aqueous hydrochloric acid as an acid catalyst was added, and dehydration reaction was performed at 65 ° C. for 3 hours. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The diethyl ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. To the obtained residue, 4 ml of THF was added again, 0.70 ml (0.70 mmol) of diisobutylaluminum hydride was added, and a reduction reaction was performed at room temperature for 1.5 hours. Subsequently, 2 ml of 6M hydrochloric acid aqueous solution was added to the reaction mixture, and dehydration reaction was performed for 3 hours. The reaction mixture was cooled to room temperature and extracted with diethyl ether. The diethyl ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: hexane) to give 102 mg (0.143 mmol) of 2-bromo-3-iodo-6,7-di (dodecin-1-yl) anthracene as a yellow solid. Obtained (yield 42%).

Example 9 (Synthesis of 6,7,6 ′, 7′-tetra (dodecin-1-yl) -3,3′-dibromo-2,2′-bianthracenyl) (dihalo represented by the general formula (2) Biphenyl derivatives)
102 mg (0.143 mmol) of 2-bromo-3-iodo-6,7-di (dodecin-1-yl) anthracene synthesized in Synthesis Example 15 in a 100 ml Schlenk reaction vessel under a nitrogen atmosphere (compound of general formula (3) ) And 5 ml of THF were added. This solution was cooled to −70 ° C., and 0.45 ml (0.29 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65 M) was added dropwise. After aging for 10 minutes, the mixture was cooled to −78 ° C., and 29.7 mg (0.29 mmol) of trimethoxyborane (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After gradually warming to room temperature, 3M aqueous hydrochloric acid solution was added and stirred for 30 minutes, and then toluene was added for phase separation. The organic phase was concentrated under reduced pressure. 99.3 mg (0.140 mmol) of 2-bromo-3-iodo-6,7-di (dodecin-1-yl) anthracene (compound of general formula (4)) synthesized in Synthesis Example 15 was added to the obtained residue. Then, 8.1 mg (0.007 mmol) of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.), 5 ml of toluene, and 1.2 ml of ethanol were added. Further, an aqueous solution consisting of 44.5 mg (0.420 mmol) of sodium carbonate and 1.6 ml of water was added, and the reaction was carried out at 60 ° C. for 24 hours. After cooling to room temperature, toluene was added, phase separation was performed, and the organic phase was washed with brine. The organic phase was concentrated under reduced pressure, the solvent was distilled off, and further dried under vacuum. Toluene was added to the obtained residue, 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.03 ml) was added, and the mixture was stirred at room temperature for 1 hour. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (solvent; hexane (elution of anthracene derivative) and hexane: chloroform = 10: 1 (elution of the desired product)), 6,7,6 ′, 7′-tetra (dodecin-1 -Yl) -3,3′-dibromo-2,2′-bianthracenyl 93.3 mg of yellow solid was obtained (yield 57%).
FABMS m / z: 1169 (M ⁺ , 100%), 1089 (M ⁺ -Br, 7).

  From the MS measurement, it was confirmed that 6,7,6 ', 7'-tetra (dodecin-1-yl) -3,3'-dibromo-2,2'-bianthracenyl was obtained. The structural formula is shown below.

実施例１０ （テトラ（ドデシン−１−イル）ジナフトビフェニレンの合成）（一般式（１）で示されるビフェニレン誘導体）
窒素雰囲気下、５０ｍｌシュレンク反応容器に、実施例９で合成した６，７，６’，７’−テトラ（ドデシン−１−イル）−３，３’−ジブロモ−２，２’−ビアントラセニル９３．０ｍｇ（０．０８０ｍｍｏｌ）及びジエチルエーテル５ｍｌを添加した。この混合物を０℃に冷却し、リチオ化剤であるｎ−ブチルリチウム（関東化学製、１．５９Ｍ）のヘキサン溶液０．２３ｍｌ（０．１３ｍｍｏｌ）を滴下し、０℃で３０分間及び１０℃で６０分間撹拌した（リチオ化反応）。別の１００ｍｌシュレンク反応容器に、塩化銅（ＩＩ）（和光純薬工業製）３５．５ｍｇ（０．２６４ｍｍｏｌ）及びＴＨＦ１０ｍｌを添加し、−７８℃に冷却した。ここへ先のジリチオ化物のジエチルエーテル溶液をテフロン（登録商標）キャヌラーを用いて移液した。１５時間かけて室温までゆっくり昇温し、３Ｍ塩酸水溶液を添加した。分相し、有機相をさらに飽和食塩水で洗浄した。懸濁している有機相を濾過し、固体を濾別した。この固体を水及びヘキサンで洗浄し、得られた固体をトルエンから再結晶化し、目的物の黄色固体２８．１ｍｇを得た（収率３５％）。
ＦＡＢＭＳ ｍ／ｚ： １０１０（Ｍ^＋）。

Example 10 (Synthesis of tetra (dodecin-1-yl) dinaphthobiphenylene) (biphenylene derivative represented by the general formula (1))
In a 50 ml Schlenk reaction vessel under a nitrogen atmosphere, 6,7,6 ′, 7′-tetra (dodecin-1-yl) -3,3′-dibromo-2,2′-bianthracenyl synthesized in Example 9 was obtained. 0 mg (0.080 mmol) and 5 ml of diethyl ether were added. The mixture was cooled to 0 ° C., and 0.23 ml (0.13 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) as a lithiating agent was added dropwise, and at 0 ° C. for 30 minutes and 10 ° C. For 60 minutes (lithiation reaction). To another 100 ml Schlenk reaction vessel, 35.5 mg (0.264 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 10 ml of THF were added and cooled to -78 ° C. To this, the diethyl ether solution of the dilithiated compound was transferred using a Teflon (registered trademark) cannula. The temperature was slowly raised to room temperature over 15 hours, and 3M aqueous hydrochloric acid was added. The phases were separated, and the organic phase was further washed with saturated brine. The suspended organic phase was filtered and the solid was filtered off. This solid was washed with water and hexane, and the obtained solid was recrystallized from toluene to obtain 28.1 mg of the objective yellow solid (yield 35%).
FABMS m / z: 1010 (M ⁺ ).

  From MS measurement, it was confirmed that tetra (dodecin-1-yl) dinaphthobiphenylene was obtained. The structural formula is shown below.

合成例１６ （２−ブロモ−３−ヨード−６，７−ジドデシル−９，１０−ジフェニルアントラセンの合成）（一般式（３）及び（４）の化合物）
窒素雰囲気下、１００ｍｌシュレンク反応容器に合成例３で合成した２−ブロモ−３−ヨード−６，７−ジドデシルアントラキノン５４１ｍｇ（０．７２２ｍｍｏｌ）及びＴＨＦ２０ｍｌを添加した。−７８℃に冷却後、フェニルリチウム（関東化学製、１．０ｍｏｌ／ｌ、シクロヘキサン／ジエチルエーテル溶液）１．５ｍｌ（１．５ｍｍｏｌ）（一般式（６）及び（７）の化合物）を加えた後、一晩かけて室温まで昇温した。次いで反応混合物に３Ｍ塩酸水溶液及びジエチルエーテルを加えた後、分相し、さらにジエチルエーテルで抽出した。ジエチルエーテル溶液を飽和食塩水で洗浄して無水硫酸ナトリウムで乾燥し、減圧濃縮した。得られた残渣に酢酸３０ｍｌ、ヨウ化ナトリウム７４９ｍｇ（５．０ｍｍｏｌ）、及び次亜りん酸ナトリウム・１水和物７２７ｍｇ（６．８６ｍｍｏｌ）を加え、１時間加熱還流下で反応を行った（還元反応）。反応混合物を室温まで冷やし、トルエンで抽出した。トルエン溶液を飽和食塩水で洗浄して無水硫酸ナトリウムで乾燥し、減圧濃縮した。シリカゲルカラムクロマトグラフィー（溶離液；ヘキサン：トルエン＝３０：１）で精製し、２−ブロモ−３−ヨード−６，７−ジドデシル−９，１０−ジフェニルアントラセンの黄色固体４５３ｍｇを得た（収率７２％）。

Synthesis Example 16 (Synthesis of 2-bromo-3-iodo-6,7-didodecyl-9,10-diphenylanthracene) (compounds of general formulas (3) and (4))
Under a nitrogen atmosphere, 541 mg (0.722 mmol) of 2-bromo-3-iodo-6,7-didodecylanthraquinone synthesized in Synthesis Example 3 and 20 ml of THF were added to a 100 ml Schlenk reaction vessel. After cooling to −78 ° C., 1.5 ml (1.5 mmol) of phenyllithium (manufactured by Kanto Chemical Co., 1.0 mol / l, cyclohexane / diethyl ether solution) (compounds of general formulas (6) and (7)) was added. Thereafter, the temperature was raised to room temperature overnight. Next, 3M aqueous hydrochloric acid and diethyl ether were added to the reaction mixture, the phases were separated, and the mixture was further extracted with diethyl ether. The diethyl ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. To the obtained residue, 30 ml of acetic acid, 749 mg (5.0 mmol) of sodium iodide and 727 mg (6.86 mmol) of sodium hypophosphite monohydrate were added, and the reaction was carried out under heating and refluxing for 1 hour (reduction) reaction). The reaction mixture was cooled to room temperature and extracted with toluene. The toluene solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (eluent; hexane: toluene = 30: 1) gave 453 mg of 2-bromo-3-iodo-6,7-didodecyl-9,10-diphenylanthracene as a yellow solid (yield) 72%).

Example 11 (Synthesis of 6,7,6 ′, 7′-tetradodecyl-9,10,9 ′, 10′-tetraphenyl-3,3′-dibromo-2,2′-bianthracenyl) [General formula ( Synthesis of dihalobiphenyl derivative represented by 2)]
Under a nitrogen atmosphere, 205 mg (0.235 mmol) of 2-bromo-3-iodo-6,7-didodecyl-9,10-diphenylanthracene synthesized in Synthesis Example 16 and 6 ml of THF were added to a 100 ml Schlenk reaction vessel. This mixture was cooled to −60 ° C., and 0.58 ml (0.47 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.81M) was added dropwise. After aging for 10 minutes, the mixture was cooled to −78 ° C., and 48.8 mg (0.47 mmol) of trimethoxyborane (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After gradually warming to room temperature, 3M aqueous hydrochloric acid solution was added and stirred for 30 minutes, and then toluene was added for phase separation. The organic phase was concentrated under reduced pressure. To the obtained solid, 210 mg (0.241 mmol) of 2-bromo-3-iodo-6,7-didodecyl-9,10-diphenylanthracene synthesized in Synthesis Example 16, tetrakis (triphenylphosphine) palladium (Tokyo Kasei) 13.9 mg (0.012 mmol), 5 ml of toluene, and 1.2 ml of ethanol were added. Further, an aqueous solution composed of 76.6 mg (0.723 mmol) of sodium carbonate and 1.6 ml of water was added, and the reaction was carried out at 60 ° C. for 24 hours. After cooling to room temperature, toluene and water were added for phase separation. The organic phase was concentrated, and the resulting residue was dissolved in 5 ml of toluene, 0.02 ml of 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 2 hours. The toluene solution was washed twice with water, the organic phase was concentrated under reduced pressure, and saturated brine and toluene were added to the resulting residue. The phases were separated and the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting residue was filtered through a column packed with silica gel (solvent: hexane). The obtained crude solid was recrystallized from heptane to obtain 217 mg of the target yellow solid (yield 62%).
FABMS m / z: 1490 (M ⁺ , 100%), 1419 (M ⁺ -Br, 5).

  From MS measurement, it was confirmed that 6,7,6 ′, 7′-tetradodecyl-9,10,9 ′, 10′-tetraphenyl-3,3′-dibromo-2,2′-bianthracenyl was obtained. did. Note that. Its structural formula is shown below.

実施例１２ （テトラドデシルテトラフェニルジナフトビフェニレンの合成）［一般式（１）で示されるビフェニレン誘導体の合成］
窒素雰囲気下、１００ｍｌシュレンク反応容器に実施例１１で合成した６，７，６’，７’−テトラドデシル−９，１０，９’，１０’−テトラフェニル−３，３’−ジブロモ−２，２’−ビアントラセニル２１０ｍｇ（０．１４１ｍｍｏｌ）及びジエチルエーテル７ｍｌを添加した。この混合物を０℃に冷却後、リチオ化剤であるｎ−ブチルリチウム（関東化学製、１．５９Ｍ）のヘキサン溶液０．２０ｍｌ（０．３１ｍｍｏｌ）を滴下した。１時間かけて５℃まで昇温しメタル化の熟成を行った。別の１００ｍｌシュレンク反応容器に、塩化銅（ＩＩ）（和光純薬工業製）６４．５ｍｇ（０．４７９ｍｍｏｌ）及びＴＨＦ１５ｍｌを添加し、−７８℃に冷却した。ここへ先のジリチオ化物のジエチルエーテル溶液をテフロン（登録商標）キャヌラーを用いて移液した。１５時間かけて室温までゆっくり昇温し、３Ｍ塩酸水溶液を添加した。分相し、有機相をさらに飽和食塩水で洗浄した。懸濁している有機相を濾過し、固体を濾別した。この固体を水及びヘキサンで洗浄し、得られた固体をトルエンから再結晶化し、目的物の黄色固体９７．５ｍｇを得た（収率５２％）。
ＦＡＢＭＳ ｍ／ｚ： １３３０（Ｍ^＋）。

Example 12 (Synthesis of tetradodecyltetraphenyldinaphthobiphenylene) [Synthesis of biphenylene derivative represented by general formula (1)]
Under a nitrogen atmosphere, 6,7,6 ′, 7′-tetradodecyl-9,10,9 ′, 10′-tetraphenyl-3,3′-dibromo-2 synthesized in Example 11 in a 100 ml Schlenk reaction vessel, 210 mg (0.141 mmol) of 2′-bianthracenyl and 7 ml of diethyl ether were added. After cooling this mixture to 0 ° C., 0.20 ml (0.31 mmol) of a hexane solution of n-butyl lithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) as a lithiating agent was added dropwise. The temperature was raised to 5 ° C. over 1 hour, and aging of metallization was performed. To another 100 ml Schlenk reaction vessel, 64.5 mg (0.479 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 ml of THF were added and cooled to -78 ° C. To this, the diethyl ether solution of the dilithiated compound was transferred using a Teflon (registered trademark) cannula. The temperature was slowly raised to room temperature over 15 hours, and 3M aqueous hydrochloric acid was added. The phases were separated, and the organic phase was further washed with saturated brine. The suspended organic phase was filtered and the solid was filtered off. This solid was washed with water and hexane, and the obtained solid was recrystallized from toluene to obtain 97.5 mg of the objective yellow solid (yield 52%).
FABMS m / z: 1330 (M ⁺ ).

  From MS measurement, it was confirmed that tetradodecyltetraphenyldinaphthobiphenylene was obtained. The structural formula is shown below.

合成例１７ （２−ブロモ−３−ヨード−６，７−ジドデシル−９，１０−ビス（フェニルエチニル）アントラセンの合成）（一般式（３）及び（４）の化合物の合成）
窒素雰囲気下、１００ｍｌシュレンク反応容器にフェニルアセチレン（東京化成工業製）１７８ｍｇ（１．７４ｍｍｏｌ）及びＴＨＦ２０ｍｌを添加した。ｎ−ブチルリチウム（関東化学製、１．５９Ｍ）のヘキサン溶液１．０５ｍｌ（１．６７ｍｍｏｌ）を滴下し、２０分間撹拌した。合成例３で合成した２−ブロモ−３−ヨード−６，７−ジドデシルアントラキノン５２３ｍｇ（０．６９７ｍｍｏｌ）を加えた後、混合物を室温で一晩反応させた。次いで反応混合物に３Ｍ塩酸水溶液及びジエチルエーテルを加えた後、分相し、さらにジエチルエーテルで抽出した。ジエチルエーテル溶液を飽和食塩水で洗浄して無水硫酸ナトリウムで乾燥し、減圧濃縮した。得られた残渣に酢酸３０ｍｌ、ヨウ化ナトリウム７４９ｍｇ（５．０ｍｍｏｌ）、及び次亜りん酸ナトリウム・１水和物７２７ｍｇ（６．８６ｍｍｏｌ）を加え、１時間加熱還流下で反応を行った。反応混合物を室温まで冷やし、トルエンで抽出した。トルエン溶液を飽和食塩水で洗浄して無水硫酸ナトリウムで乾燥し、減圧濃縮した。シリカゲルカラムクロマトグラフィー（溶離液；ヘキサン：トルエン＝３０：１の混合液）で精製し、２−ブロモ−３−ヨード−６，７−ジドデシル−９，１０−ビス（フェニルエチニル）アントラセンの黄色固体３９３ｍｇを得た（収率６１％）。

Synthesis Example 17 (Synthesis of 2-bromo-3-iodo-6,7-didodecyl-9,10-bis (phenylethynyl) anthracene) (Synthesis of compounds of general formulas (3) and (4))
Under a nitrogen atmosphere, 178 mg (1.74 mmol) of phenylacetylene (manufactured by Tokyo Chemical Industry) and 20 ml of THF were added to a 100 ml Schlenk reaction vessel. 1.05 ml (1.67 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.59 M) was added dropwise and stirred for 20 minutes. After adding 523 mg (0.697 mmol) of 2-bromo-3-iodo-6,7-didodecylanthraquinone synthesized in Synthesis Example 3, the mixture was reacted at room temperature overnight. Next, 3M aqueous hydrochloric acid and diethyl ether were added to the reaction mixture, the phases were separated, and the mixture was further extracted with diethyl ether. The diethyl ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. To the obtained residue, 30 ml of acetic acid, 749 mg (5.0 mmol) of sodium iodide, and 727 mg (6.86 mmol) of sodium hypophosphite monohydrate were added, and the reaction was carried out with heating under reflux for 1 hour. The reaction mixture was cooled to room temperature and extracted with toluene. The toluene solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (eluent: hexane: toluene = 30: 1 mixture) and yellow solid of 2-bromo-3-iodo-6,7-didodecyl-9,10-bis (phenylethynyl) anthracene 393 mg was obtained (61% yield).

Example 13 (Synthesis of 6,7,6 ′, 7′-tetradodecyl-9,10,9 ′, 10′-tetrakis (phenylethynyl) -3,3′-dibromo-2,2′-bianthracenyl) ( Synthesis of dihalobiphenyl derivative represented by general formula (2))
Under a nitrogen atmosphere, 190 mg (0.206 mmol) of 2-bromo-3-iodo-6,7-didodecyl-9,10-bis (phenylethynyl) anthracene synthesized in Synthesis Example 17 and 6 ml of THF were added to a 100 ml Schlenk reaction vessel. . This mixture was cooled to −60 ° C., and 0.51 ml (0.41 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.81 M) was added dropwise. After aging for 5 minutes, the mixture was cooled to −78 ° C., and 42.6 mg (0.41 mmol) of trimethoxyborane (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After gradually warming to room temperature, 3M hydrochloric acid aqueous solution was added and stirred at room temperature for 30 minutes, and then toluene was added for phase separation. The organic phase was concentrated under reduced pressure, and 195 mg (0.212 mmol) of 2-bromo-3-iodo-6,7-didodecyl-9,10-bis (phenylethynyl) anthracene synthesized in Synthesis Example 17 was added to the obtained solid. , 13.9 mg (0.012 mmol) of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry), 5 ml of toluene, and 1.2 ml of ethanol were added. Further, an aqueous solution composed of 67.4 mg (0.636 mmol) of sodium carbonate and 1.6 ml of water was added, and the reaction was carried out at 60 ° C. for 24 hours. After cooling to room temperature, toluene and water were added for phase separation. The organic phase was concentrated, and the resulting residue was dissolved in 5 ml of toluene, 0.02 ml of 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 2 hours. The toluene solution was washed twice with water, the organic phase was concentrated under reduced pressure, and saturated brine and toluene were added to the resulting residue. The phases were separated and the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting residue was filtered through a column packed with silica gel (solvent: hexane). The resulting crude solid was recrystallized from heptane to obtain 212 mg of the target yellow solid (yield 65%).
MS m / z: 1586 (M ^<+> , 2%), 793 (M ^<+ > / 2, 100).

  From the MS measurement, 6,7,6 ′, 7′-tetradodecyl-9,10,9 ′, 10′-tetrakis (phenylethynyl) -3,3′-dibromo-2,2′-bianthracenyl was obtained. It was confirmed. Note that. Its structural formula is shown below.

実施例１４ （テトラドデシルテトラキス（フェニルエチニル）ジナフトビフェニレンの合成）（一般式（１）で示されるビフェニレン誘導体の合成）
窒素雰囲気下、１００ｍｌシュレンク反応容器に実施例１３で合成した６，７，６’，７’−テトラドデシル−９，１０，９’，１０’−テトラキス（フェニルエチニル）−３，３’−ジブロモ−２，２’−ビアントラセニル２０８ｍｇ（０．１３１ｍｍｏｌ）及びジエチルエーテル７ｍｌを添加した。この混合物を０℃に冷却後、リチオ化剤であるｎ−ブチルリチウム（関東化学製、１．５９Ｍ）のヘキサン溶液０．２０ｍｌ（０．３１ｍｍｏｌ）を滴下した。１時間かけて５℃まで昇温しメタル化の熟成を行った。別の１００ｍｌシュレンク反応容器に、塩化銅（ＩＩ）（和光純薬工業製）６４．５ｍｇ（０．４７９ｍｍｏｌ）及びＴＨＦ１５ｍｌを添加し、−７８℃に冷却した。ここへ先のジリチオ化物のジエチルエーテル溶液をテフロン（登録商標）キャヌラーを用いて移液した。１５時間かけて室温までゆっくり昇温し、３Ｍ塩酸水溶液を添加した。分相し、有機相をさらに飽和食塩水で洗浄した。懸濁している有機相を濾過し、固体を濾別した。この固体を水及びヘキサンで洗浄し、得られた固体をトルエンから再結晶化し、目的物の橙色固体８０．３ｍｇを得た（収率４３％）。
ＦＡＢＭＳ ｍ／ｚ： １４２６（Ｍ^＋）。

Example 14 (Synthesis of tetradodecyltetrakis (phenylethynyl) dinaphthobiphenylene) (Synthesis of biphenylene derivative represented by general formula (1))
6,7,6 ′, 7′-tetradodecyl-9,10,9 ′, 10′-tetrakis (phenylethynyl) -3,3′-dibromo synthesized in Example 13 in a 100 ml Schlenk reaction vessel under nitrogen atmosphere 208 mg (0.131 mmol) of -2,2'-bianthracenyl and 7 ml of diethyl ether were added. After cooling this mixture to 0 ° C., 0.20 ml (0.31 mmol) of a hexane solution of n-butyl lithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) as a lithiating agent was added dropwise. The temperature was raised to 5 ° C. over 1 hour, and aging of metallization was performed. To another 100 ml Schlenk reaction vessel, 64.5 mg (0.479 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 ml of THF were added and cooled to -78 ° C. To this, the diethyl ether solution of the dilithiated compound was transferred using a Teflon (registered trademark) cannula. The temperature was slowly raised to room temperature over 15 hours, and 3M aqueous hydrochloric acid was added. The phases were separated, and the organic phase was further washed with saturated brine. The suspended organic phase was filtered and the solid was filtered off. This solid was washed with water and hexane, and the resulting solid was recrystallized from toluene to obtain 80.3 mg of the objective orange solid (43% yield).
FABMS m / z: 1426 (M ⁺ ).

  From MS measurement, it was confirmed that tetradodecyltetrakis (phenylethynyl) dinaphthobiphenylene was obtained. The structural formula is shown below.

合成例１８ （２−ブロモ−３−ヨード−６，７−ジドデシル−９，１０−ビス（フェニルエテニル）アントラセンの合成）（一般式（３）及び（４）の化合物の合成）
窒素雰囲気下、１００ｍｌシュレンク反応容器にマグネシウム５４．７ｍｇ（２．２５ｍｍｏｌ）及びＴＨＦ２０ｍｌを添加した。ヨウ素５ｍｇを加えた後、β−ブロモスチレン（東京化成工業製）４０ｍｇを添加し、撹拌下マグネシウムを活性化させた。β−ブロモスチレン３５９ｍｇ（１．９６ｍｍｏｌ、計２．１７ｍｍｏｌ）を緩く還流が起こる程度に滴下した。滴下終了後、３０分間撹拌を継続した。合成例３で合成した２−ブロモ−３−ヨード−６，７−ジドデシルアントラキノン６７８ｍｇ（０．９０４ｍｍｏｌ）を加えた後、混合物を室温で一晩反応させた。次いで反応混合物に３Ｍ塩酸水溶液及びジエチルエーテルを加えた後、分相し、さらにジエチルエーテルで抽出した。ジエチルエーテル溶液を飽和食塩水で洗浄して無水硫酸ナトリウムで乾燥し、減圧濃縮した。得られた残渣に酢酸３０ｍｌ、ヨウ化ナトリウム７４９ｍｇ（５．０ｍｍｏｌ）、及び次亜りん酸ナトリウム・１水和物７２７ｍｇ（６．８６ｍｍｏｌ）を加え、１時間加熱還流下で反応を行った。反応混合物を室温まで冷やし、トルエンで抽出した。トルエン溶液を飽和食塩水で洗浄して無水硫酸ナトリウムで乾燥し、減圧濃縮した。シリカゲルカラムクロマトグラフィー（溶離液；ヘキサン：トルエン＝３０：１の混合液）で精製し、２−ブロモ−３−ヨード−６，７−ジドデシル−９，１０−ビス（フェニルエテニル）アントラセンの黄色固体４６８ｍｇを得た（収率５６％）。

Synthesis Example 18 (Synthesis of 2-bromo-3-iodo-6,7-didodecyl-9,10-bis (phenylethenyl) anthracene) (Synthesis of compounds of general formulas (3) and (4))
Under a nitrogen atmosphere, 54.7 mg (2.25 mmol) of magnesium and 20 ml of THF were added to a 100 ml Schlenk reaction vessel. After adding 5 mg of iodine, 40 mg of β-bromostyrene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to activate magnesium under stirring. 359 mg (1.96 mmol, 2.17 mmol in total) of β-bromostyrene was added dropwise to such an extent that reflux occurred slowly. After completion of the dropping, stirring was continued for 30 minutes. After adding 678 mg (0.904 mmol) of 2-bromo-3-iodo-6,7-didodecylanthraquinone synthesized in Synthesis Example 3, the mixture was reacted at room temperature overnight. Next, 3M aqueous hydrochloric acid and diethyl ether were added to the reaction mixture, the phases were separated, and the mixture was further extracted with diethyl ether. The diethyl ether solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. To the obtained residue, 30 ml of acetic acid, 749 mg (5.0 mmol) of sodium iodide, and 727 mg (6.86 mmol) of sodium hypophosphite monohydrate were added, and the reaction was carried out with heating under reflux for 1 hour. The reaction mixture was cooled to room temperature and extracted with toluene. The toluene solution was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (eluent; hexane: toluene = 30: 1 mixture), yellow of 2-bromo-3-iodo-6,7-didodecyl-9,10-bis (phenylethenyl) anthracene 468 mg of solid was obtained (56% yield).

Example 15 (Synthesis of 6,7,6 ′, 7′-tetradodecyl-9,10,9 ′, 10′-tetrakis (phenylethenyl) -3,3′-dibromo-2,2′-bianthracenyl) (Synthesis of dihalobiphenyl derivative represented by general formula (2))
Under a nitrogen atmosphere, 225 mg (0.243 mmol) of 2-bromo-3-iodo-6,7-didodecyl-9,10-bis (phenylethenyl) anthracene synthesized in Synthesis Example 18 and 7 ml of THF were added to a 100 ml Schlenk reaction vessel. did. The mixture was cooled to −60 ° C., and 0.60 ml (0.49 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.81M) was added dropwise. After aging for 5 minutes, the mixture was cooled to −78 ° C., and 50.9 mg (0.490 mmol) of trimethoxyborane (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After gradually warming to room temperature, 3M hydrochloric acid aqueous solution was added and stirred at room temperature for 30 minutes, and then toluene was added for phase separation. The organic phase was concentrated under reduced pressure, and 235 mg (0.254 mmol) of 2-bromo-3-iodo-6,7-didodecyl-9,10-bis (phenylethenyl) anthracene synthesized in Synthesis Example 18 was added to the obtained solid. ), 13.9 mg (0.012 mmol) of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.), 5 ml of toluene, and 1.2 ml of ethanol were added. Further, an aqueous solution consisting of 80.8 mg (0.762 mmol) of sodium carbonate and 1.6 ml of water was added, and the reaction was carried out at 60 ° C. for 24 hours. After cooling to room temperature, toluene and water were added for phase separation. The organic phase was concentrated, and the resulting residue was dissolved in 5 ml of toluene, 0.02 ml of 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 2 hours. The toluene solution was washed twice with water, the organic phase was concentrated under reduced pressure, and saturated brine and toluene were added to the resulting residue. The phases were separated and the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated under reduced pressure, and the resulting residue was filtered through a column packed with silica gel (solvent: hexane). The obtained crude solid was recrystallized from heptane to obtain 259 mg of the target yellow solid (yield 67%).
MS m / z: 1594 (M ⁺ , 2%), 797 (M ⁺ / 2,100).

  From the MS measurement, 6,7,6 ′, 7′-tetradodecyl-9,10,9 ′, 10′-tetrakis (phenylethenyl) -3,3′-dibromo-2,2′-bianthracenyl is obtained. I confirmed that. Note that. Its structural formula is shown below.

実施例１６ （テトラドデシルテトラキス（フェニルエテニル）ジナフトビフェニレンの合成）（一般式（１）で示されるビフェニレン誘導体の合成）
窒素雰囲気下、１００ｍｌシュレンク反応容器に実施例１５で合成した６，７，６’，７’−テトラドデシル−９，１０，９’，１０’−テトラキス（フェニルエテニル）−３，３’−ジブロモ−２，２’−ビアントラセニル２５４ｍｇ（０．１５９ｍｍｏｌ）及びジエチルエーテル７ｍｌを添加した。この混合物を０℃に冷却後、リチオ化剤であるｎ−ブチルリチウム（関東化学製、１．５９Ｍ）のヘキサン溶液０．２２ｍｌ（０．３５ｍｍｏｌ）を滴下した。１時間かけて５℃まで昇温しメタル化の熟成を行った。別の１００ｍｌシュレンク反応容器に、塩化銅（ＩＩ）（和光純薬工業製）６４．１ｍｇ（０．４７７ｍｍｏｌ）及びＴＨＦ１５ｍｌを添加し、−７８℃に冷却した。ここへ先のジリチオ化物のジエチルエーテル溶液をテフロン（登録商標）キャヌラーを用いて移液した。１５時間かけて室温までゆっくり昇温し、３Ｍ塩酸水溶液を添加した。分相し、有機相をさらに飽和食塩水で洗浄した。懸濁している有機相を濾過し、固体を濾別した。この固体を水及びヘキサンで洗浄し、得られた固体をトルエンから再結晶化し、目的物の橙色固体９３．５ｍｇを得た（収率４１％）。

Example 16 (Synthesis of tetradodecyltetrakis (phenylethenyl) dinaphthobiphenylene) (Synthesis of biphenylene derivative represented by general formula (1))
6,7,6 ′, 7′-tetradodecyl-9,10,9 ′, 10′-tetrakis (phenylethenyl) -3,3′- synthesized in Example 15 in a 100 ml Schlenk reaction vessel under nitrogen atmosphere 254 mg (0.159 mmol) of dibromo-2,2′-bianthracenyl and 7 ml of diethyl ether were added. After cooling this mixture to 0 ° C., 0.22 ml (0.35 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) as a lithiating agent was added dropwise. The temperature was raised to 5 ° C. over 1 hour, and aging of metallization was performed. To another 100 ml Schlenk reaction vessel, 64.1 mg (0.477 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries) and 15 ml of THF were added and cooled to -78 ° C. To this, the diethyl ether solution of the dilithiated compound was transferred using a Teflon (registered trademark) cannula. The temperature was slowly raised to room temperature over 15 hours, and 3M aqueous hydrochloric acid was added. The phases were separated, and the organic phase was further washed with saturated brine. The suspended organic phase was filtered and the solid was filtered off. This solid was washed with water and hexane, and the obtained solid was recrystallized from toluene to obtain 93.5 mg of the objective orange solid (yield 41%).

FABMS m / z: 1434 (M ⁺ ).

  From MS measurement, it was confirmed that tetradodecyltetrakis (phenylethenyl) dinaphthobiphenylene was obtained. The structural formula is shown below.

実施例１７ （耐酸化性評価）
窒素雰囲気下、１００ｍｌシュレンク容器にトルエン１０．４ｇを添加し、凍結（液体窒素）−減圧−窒素置換−融解から成るサイクルを３回繰り返すことで溶存酸素を除去した。そこへ実施例２で得られたテトラドデシルジナフトビフェニレンの黄色固体１０．５ｍｇを添加し、１１０℃に加熱溶解させると黄色透明溶液となった。次にこのシュレンク容器の上部の栓を開け、１時間、外気に接触させることで空気を導入し、さらに１１０℃で撹拌した。で酸化に由来する新たなピークの出現はなかった。

Example 17 (Oxidation resistance evaluation)
Under a nitrogen atmosphere, 10.4 g of toluene was added to a 100 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle consisting of freezing (liquid nitrogen) -depressurization-nitrogen replacement-thawing three times. Thereto was added 10.5 mg of a tetradodecyldinaphthobiphenylene yellow solid obtained in Example 2 and dissolved by heating at 110 ° C. to obtain a yellow transparent solution. Next, the stopper at the top of the Schlenk container was opened, air was introduced by contact with outside air for 1 hour, and the mixture was further stirred at 110 ° C. There was no new peak due to oxidation.

  Furthermore, even if this solution was introduced with air at 110 ° C. for 1 hour with stirring, the color of the solution was not changed, and the oxidation resistance was excellent.

Comparative Example 1
Under a nitrogen atmosphere, 28.9 g of toluene was added to a 100 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle of freezing (liquid nitrogen) -depressurization-nitrogen replacement-thawing three times. Thereto was added 3.0 mg of pentacene (manufactured by Tokyo Chemical Industry Co., Ltd.), and when heated to 110 ° C. and dissolved, a reddish purple solution was obtained. Next, when the stopper at the top of the Schlenk container was opened and air was introduced for 1 hour, the color of the solution changed to red pink. The mixture was further stirred at 110 ° C. From gas chromatography and gas chromatography-mass spectrum (GCMS) analysis, it was found that 6,13-pentacenequinone was produced.

  Further, when air was introduced into the solution with stirring at 110 ° C. for 1 hour, the color of the solution changed to yellow.

Example 18 (Preparation of organic thin film)
Under a nitrogen atmosphere, 7.2 mg of tetradodecyldinaphthobiphenylene obtained in Example 2 was mixed with toluene (10.2 g) and stirred at 80 ° C. for 1 hour to prepare a yellow transparent solution of tetradodecyldinaphthobiphenylene. .

  A quartz substrate having a concave surface was heated to 80 ° C. in an air atmosphere, and the above solution was applied onto the substrate using a dropper and dried under normal pressure to produce an organic thin film having a thickness of 420 nm. As a result of analyzing the components of this organic thin film by gas chromatography, there was no peak other than tetradodecyldinaphthobiphenylene, and it was not oxidized. Accordingly, it was found that an organic thin film of tetradodecyldinaphthobiphenylene can be produced without being oxidized in the air.

Example 19 (Preparation of organic thin film, evaluation as light emitting material)
Under a nitrogen atmosphere, 26 mg of tetradodecyl dinaphthobiphenylene obtained in Example 2 was mixed with 5 g of dichloroethane and stirred at 80 ° C. for 1 hour to prepare a yellow solution of tetradodecyl dinaphthobiphenylene.

  In an air atmosphere, the quartz substrate was heated to 70 ° C., and the above solution was applied onto the substrate using a dropper and dried under normal pressure to produce an organic thin film having a thickness of 287 nm. Using this organic thin film, the emission quantum yield and the fluorescence spectrum were measured. The results are shown in Table 1. From these results, tetradodecyldinaphthobiphenylene can be used as a light emitting material.

Example 20 (Production of organic thin film, evaluation as light emitting material)
Under a nitrogen atmosphere, 36 mg of tetradodecyltetraphenyldinaphthobiphenylene obtained in Example 12 was mixed with 5 g of dichloroethane and stirred at 80 ° C. for 1 hour to prepare a yellow solution of tetradodecyltetraphenyldinaphthobiphenylene.

  In an air atmosphere, the quartz substrate was heated to 70 ° C., and the above solution was applied onto the substrate using a dropper and dried under normal pressure to produce an organic thin film having a thickness of 398 nm. Using this organic thin film, the emission quantum yield and the fluorescence spectrum were measured. The results are shown in Table 1. From these results, tetradodecyltetraphenyldinaphthobiphenylene can be used as a light emitting material.

Example 21 (Preparation of organic thin film, evaluation as light emitting material)
Under a nitrogen atmosphere, 36 mg of tetradodecyltetrakis (phenylethynyl) dinaphthobiphenylene obtained in Example 14 was mixed with 5 g of dichloroethane, stirred at 80 ° C. for 1 hour, and an orange solution of tetradodecyltetrakis (phenylethynyl) dinaphthobiphenylene Was prepared.

  In an air atmosphere, the quartz substrate was heated to 70 ° C., and the above solution was applied onto the substrate using a dropper and dried under normal pressure to produce an organic thin film having a thickness of 378 nm. Using this organic thin film, the emission quantum yield and the fluorescence spectrum were measured. The results are shown in Table 1. From these results, tetradodecyltetrakis (phenylethynyl) dinaphthobiphenylene can be used as a light emitting material.

Example 22 (Preparation of organic thin film, evaluation as light emitting material)
Under a nitrogen atmosphere, 32 mg of tetradodecyltetrakis (phenylethenyl) dinaphthobiphenylene obtained in Example 16 was mixed with 5 g of dichloroethane, stirred at 80 ° C. for 1 hour, and tetradodecyltetrakis (phenylethenyl) dinaphthobiphenylene. An orange solution was prepared.

  In an air atmosphere, the quartz substrate was heated to 70 ° C., and the above solution was applied onto the substrate using a dropper and dried under normal pressure to produce an organic thin film having a thickness of 356 nm. Using this organic thin film, the emission quantum yield and the fluorescence spectrum were measured. The results are shown in Table 1. From these results, tetradodecyltetrakis (phenylethenyl) dinaphthobiphenylene can be used as a light emitting material.

比較例２（テトラドデシルジベンゾビフェニレン（本願：ｎ＝ｍ＝０）の合成及び評価）
１） （３，３’−ジブロモ−６，７，６’，７’−テトラドデシル−２，２’−ビナフチルの合成）
窒素雰囲気下、１００ｍｌシュレンク反応容器に２，３−ジブロモ−６，７−ジドデシルナフタレン３８９ｍｇ（０．６２５ｍｍｏｌ）及びＴＨＦ９ｍｌを加えた。−７８℃に冷却し、ｎ−ブチルリチウム（関東化学製、１．５９Ｍ）のヘキサン溶液０．２０ｍｌ（０．３１ｍｍｏｌ）を滴下した。２０分間反応後、冷却用バスを外し、室温で１時間撹拌した。３Ｍ塩酸水溶液及びトルエン添加し分相した。有機相を無水硫酸ナトリウムで乾燥し、減圧濃縮した。残渣をヘプタンから再結晶精製し、白色固体２０４ｍｇを得た（収率６１％）。

Comparative Example 2 (Synthesis and Evaluation of Tetradodecyl Dibenzobiphenylene (Application: n = m = 0))
1) (Synthesis of 3,3′-dibromo-6,7,6 ′, 7′-tetradodecyl-2,2′-binaphthyl)
Under a nitrogen atmosphere, 389 mg (0.625 mmol) of 2,3-dibromo-6,7-didodecylnaphthalene and 9 ml of THF were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to −78 ° C., and 0.20 ml (0.31 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) was added dropwise. After reacting for 20 minutes, the cooling bath was removed and the mixture was stirred at room temperature for 1 hour. 3M hydrochloric acid aqueous solution and toluene were added for phase separation. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was recrystallized and purified from heptane to obtain 204 mg of a white solid (yield 61%).

2) (Synthesis of tetradodecyl dibenzobiphenylene)
Under a nitrogen atmosphere, in a 100 ml Schlenk reaction vessel, 201 mg (0.185 mmol) of 3,3′-dibromo-6,7,6 ′, 7′-tetradodecyl-2,2′-binaphthyl obtained in 1) above and diethyl ether 5 ml was added. After cooling to 0 ° C., 0.25 ml (0.40 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) was added dropwise, and the mixture was stirred at 0 ° C. for 30 minutes and at 10 ° C. for 60 minutes. In a separate 100 ml Schlenk reaction vessel, 74.6 mg (0.555 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 10 ml of THF were charged and cooled to -78 ° C. To this, the diethyl ether solution of the dilithiated compound was transferred using a Teflon (registered trademark) cannula. The temperature was raised to room temperature over 15 hours, and a 3M aqueous hydrochloric acid solution was added to stop the reaction. The phases were separated, and the organic phase was further washed with saturated brine. The suspended organic phase was filtered and the solid was filtered off. This solid was washed with water and hexane, and the obtained solid was recrystallized from toluene to obtain 83.9 mg of a light yellow solid of tetradodecyldibenzobiphenylene (yield 49%).

  The structural formula is shown below.

３）テトラドデシルジベンゾビフェニレンの評価
窒素雰囲気下、１００ｍｌシュレンク容器にトルエン１０．２ｇを添加し、凍結（液体窒素）−減圧−窒素置換−融解から成るサイクルを３回繰り返すことで溶存酸素を除去した。そこへ上記２）で得たテトラドデシルジベンゾビフェニレン７．２ｍｇを添加し、８０℃で１時間撹拌し、テトラドデシルジベンゾビフェニレンの薄黄色透明溶液を調製した。

3) Evaluation of tetradodecyldibenzobiphenylene Under nitrogen atmosphere, 10.2 g of toluene was added to a 100 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle consisting of freezing (liquid nitrogen)-reduced pressure-nitrogen substitution-thawing three times. . Thereto, 7.2 mg of tetradodecyl dibenzobiphenylene obtained in 2) above was added and stirred at 80 ° C. for 1 hour to prepare a pale yellow transparent solution of tetradodecyl dibenzobiphenylene.

  Next, a quartz substrate having a concave surface was heated to 80 ° C. in a nitrogen atmosphere, and the above solution was applied onto the substrate with a dropper and dried under normal pressure. However, there are portions where the material is present and portions where the material is not present, and a uniform film cannot be obtained, and it is difficult to produce a uniform thin film by coating.

¹ H NMR spectrum of 6,7,6 ′, 7′-tetradodecyl-3,3′-dibromo-2,2′-bianthracenyl synthesized in Example 1 ¹ H NMR spectrum of tetradodecyldinaphthobiphenylene synthesized in Example 2

Claims (12)

A biphenylene derivative represented by the following general formula (1):

(Here, the substituents R ^{1 to} R ⁸ are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, Or an aryl group having 4 to 20 carbon atoms, m is 1 or 2, and n is an integer of 0 to 2. However, R ¹ and R ² are not simultaneously hydrogen atoms.) 2. The biphenylene derivative according to claim 1, wherein m and n are 1. An oxidation-resistant organic semiconductor material comprising the biphenylene derivative according to claim 1. An organic thin film comprising the oxidation-resistant organic semiconductor material according to claim 3. A light emitting material comprising the oxidation resistant organic semiconductor material according to claim 3. A dihalobiphenyl derivative represented by the following general formula (2):

(Wherein the substituents X ¹ and X ² represent a bromine atom, an iodine atom or a chlorine atom, the substituents R ^{1 to} R ⁸ , and the symbols m and n are represented by the general formula (1) described in claim 1. And has the same meaning as the substituents and symbols. The dihalobiphenyl derivative according to claim 6, wherein m and n are 1. The method for producing a biphenylene derivative according to claim 1, wherein the dihalobiphenyl derivative according to claim 6 is reacted with a copper compound or copper. The method for producing a biphenylene derivative according to claim 8, wherein the dihalobiphenyl derivative according to claim 6 is dilithiated and / or diglynarized and then reacted with a copper compound. The method for producing a biphenylene derivative according to claim 8 or 9, wherein the copper compound is a divalent copper compound. The method for producing a biphenylene derivative according to any one of claims 8 to 10, wherein the copper compound is copper (II) chloride or copper (II) bromide. The method for producing a biphenylene derivative according to any one of claims 8 to 11, wherein dilithiation is carried out in a dialkyl ether.

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