JP2007308421A - Spirobi(hetero fluorene) derivative, application of the same, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a spirobi(hetero fluorene) derivative having excellent oxidation resistance and capable of forming a semiconductor active phase by a coating method, a method for producing the same, and an oxidation-resistant organic semiconductor material and an organic thin film using the spirobi(hetero fluorene) derivative. <P>SOLUTION: The spirobi(hetero fluorene) has a general formula represented by (1), where Ψ is a silicon atom, a germanium atom or a tin atom, substituents R<SP>1</SP>-R<SP>4</SP>are similarly or differently a hydrogen atom, a fluorine atom, a 5-20C alkyl group, a 1-20C halogenated alkyl group, a 4-30C aryl group, a 2-20C alkynyl group or a 2-30C alkenyl group, provided that substituents of at least one group of the substituent group of R<SP>1</SP>, R<SP>2</SP>and the substituent group of R<SP>3</SP>, R<SP>4</SP>are bonded with one another to form a ring, and substituents R<SP>5</SP>-R<SP>8</SP>are similarly or differently a hydrogen atom, or a fluorine atom. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a spirobi (heterofluorene) 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 the higher the performance of the organic semiconductor material, the more difficult it is to form an active phase by a coating method.

  For example, it has been reported that a crystalline material such as pentacene having a rigid structure has a carrier mobility as high as that of amorphous silicon and exhibits excellent semiconductor device characteristics (see Non-Patent Document 1). 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 Patent Document 1). However, in order to dissolve polyacenes that are originally hardly soluble, conditions such as high temperature heating are required. Further, since the solution of pentacene is very easily oxidized by air, the application of the coating method has been difficult in terms of process and economy. 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 one order of magnitude lower than crystalline compounds (non- There is a problem that the characteristics of the obtained organic semiconductor device are low.

  Furthermore, spirobi (heterofluorene) derivatives have been reported as compounds that can be expected as organic semiconductor materials (see Patent Documents 2 and 3 and Non-Patent Document 3). However, none of these reports have been satisfactory as an organic semiconductor material and a manufacturing method thereof.

“Journal of Applied Physics” (USA), 2002, 92, 5259-5263. “Science”, (USA), 1998, 280, 1741-1744. “Organometallics” (USA), 2003, 22, 5589-5592 WO2003 / 016599 Special table flat 10-509996 WO00 / 02886

  Accordingly, in view of the problems of the above-described conventional technology, the present invention has a superior oxidation resistance and a spirobi (heterofluorene) derivative capable of forming a semiconductor active phase by a coating method, and a manufacturing method excellent in its economic efficiency. Another object of the present invention is to provide an oxidation-resistant organic semiconductor material and an organic thin film using a spirobi (heterofluorene) derivative.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a novel spirobi (heterofluorene) derivative and a method for producing it in a high yield. In addition, the inventors have found an oxidation-resistant organic semiconductor material composed of a spirobi (heterofluorene) derivative and a thin film thereof, and have completed the present invention.

The present invention is described in detail below.
(Spirobi (heterofluorene) derivatives)
The spirobi (heterofluorene) derivative of the present invention is a spirobi (heterofluorene) derivative represented by the following general formula (1).

（ここで、Ψはケイ素原子、ゲルマニウム原子、又はスズ原子を示し、置換基Ｒ^１〜Ｒ^４は同一又は異なって、水素原子、フッ素原子、炭素数５〜２０のアルキル基、炭素数１〜２０のハロゲン化アルキル基、炭素数４〜３０のアリール基、炭素数２〜２０のアルキニル基、又は炭素数２〜３０のアルケニル基を示す。但し、置換基群（Ｒ^１とＲ^２）及び置換基群（Ｒ^３とＲ^４）のうち少なくとも１つの群における置換基は互いに結合し環を形成する。置換基Ｒ^５〜Ｒ^８は同一又は異なって、水素原子又はフッ素原子を示す。）
本発明の一般式（１）の置換基について、さらに述べる。

(Here, Ψ represents a silicon atom, a germanium atom, or a tin atom, and the substituents R ^{1 to} R ⁴ are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group having 5 to 20 carbon atoms, 20 represents a halogenated alkyl group, an aryl group having 4 to 30 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, provided that the substituent group (R ¹ and R ² ) and The substituents in at least one of the substituent groups (R ³ and R ⁴ ) are bonded to each other to form a ring, and the substituents R ^{5 to} R ⁸ are the same or different and represent a hydrogen atom or a fluorine atom.)
The substituent of the general formula (1) of the present invention will be further described.

  The substituent Ψ is preferably a silicon atom.

In the substituents R ¹ to R ^4, an alkyl group having 5 to 20 carbon atoms is not particularly limited, and examples thereof include pentyl, neopentyl, hexyl, octyl, dodecyl group and the like.

The halogenated alkyl group having 1 to 20 carbon atoms in the substituents R ^{1 to} R ⁴ is not particularly limited, and examples thereof include a trifluoromethyl group, a trifluoroethyl group, and a perfluorohexyl group.

The aryl group having 4 to 30 carbon atoms in the substituents R ^{1 to} R ⁴ is not particularly limited, and examples thereof include a phenyl group, a p-tolyl group, a p- (n-octyl) phenyl group, and m- (n-octyl) phenyl. Group, p-fluorophenyl group, pentafluorophenyl group, p- (trifluoromethyl) phenyl group, p-methoxyphenyl group, p-phenoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 1-biphenyleno group, 2-biphenyleno group, biphenyl group, perfluorobiphenyl group, terphenyl group, 2-thienyl group, 2,2′-bithienyl-5 group, 5 '-(N-octyl) -2,2'-bithienyl-5-group, 2-pyridyl group, 3-pyridyl group, 2,2'-bipyridyl-6-group, tetrafluoropyri Zyl group, 2-thienyl group, 3-thienyl group, 5- (n-hexyl) -2-thienyl group, 2,2′-bithienyl-5-group, quinolyl group, (diphenylamino) phenyl group, (diphenylamino) ) Biphenyl group and the like can be mentioned, and preferred are phenyl group, p- (trifluoromethyl) phenyl group, pentafluorophenyl group and the like.

The alkynyl group having 2 to 20 carbon atoms in the substituents R ^{1 to} R ⁴ is not particularly limited, and for example, an ethynyl group, a methylethynyl group, an isopropylethynyl group, a tert-butylethynyl group, a (n-octyl) ethynyl group, ( Trifluoromethyl) ethynyl group, (n-perfluorooctyl) ethynyl, phenylethynyl group, {p- (n-octyl) phenyl} ethynyl group, naphthylethynyl group, anthracenylethynyl group, biphenylenoethynyl group, biphenylethynyl Group, terphenylethynyl group, benzylethynyl group, perfluorophenylethynyl group, {p- (trifluoromethyl) phenyl} ethynyl group, {p- (n-perfluorooctyl) phenyl} ethynyl group, etc. , Preferably an (n-octyl) ethynyl group, (trifluoromethyl Le) ethynyl group, phenylethynyl group, a {p-(trifluoromethyl) phenyl} ethynyl group, {p-(n-perfluorooctyl) phenyl} ethynyl group, a biphenyl ethynyl group, terphenyl ethynyl group.

The alkenyl group having 2 to 30 carbon atoms in the substituents R ^{1 to} R ⁴ is not particularly limited. For example, ethenyl group, methylethenyl group, isopropylethenyl group, tert-butylethenyl group, (n-octyl) ethenyl group, (tri Fluoromethyl) ethenyl group, phenylethenyl group, 1,2-difluoro-2-phenylethenyl group, 1,2-dimethyl-2-phenylethenyl group, diphenylethenyl group, triphenylethenyl group, naphthylethenyl group , Anthracenylethenyl group, biphenylenoethenyl group, biphenylethenyl group, terphenylethenyl group, benzylethenyl group, phenyl (methyl) ethenyl group, perfluorophenylethenyl group, {p- (trifluoromethyl ) Phenyl} ethenyl group, (n-perfluorooctyl) ethenyl group, etc. Rukoto can. (N-octyl) ethenyl group, phenylethenyl group and biphenylethenyl group are preferred. The alkenyl group having 2 to 20 carbon atoms may be a trans isomer or a cis isomer, or may be a mixture of any proportion thereof.

The substituents R ^{1 to} R ⁴ are preferably the same or different, and are an alkyl group having 5 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 4 to 30 carbon atoms, or 2 to 2 carbon atoms. 20 is an alkynyl group, particularly preferably an aryl group having 4 to 30 carbon atoms and an alkynyl group having 2 to 20 carbon atoms.

The substituent group (R ¹ and R ² ) and the substituent group (R ³ and R ⁴ ) can be bonded to each other to form a ring. The ring is formed in any one substituent group or in both substituent groups, preferably in both substituent groups. Examples of the ring formed include a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, a triphenylene ring which may have a substituent, and a substituent. Benzocyclobutene ring, which may have a substituent, thiophene ring which may have a substituent, and benzothiophene ring which may have a substituent, preferably having a substituent And a benzene ring which may have a substituent, and more preferably a benzene ring which may have a substituent.

  Examples of the benzene ring that may have a substituent include a benzene ring, a dimethylbenzene ring, a di (trifluoromethyl) benzene ring, and a diphenylbenzene ring, and a diphenylbenzene ring is preferable. The naphthalene ring which may have a substituent is, for example, a naphthalene ring, a dimethylnaphthalene ring, a diphenylnaphthalene ring, and the like, and preferably a naphthalene ring. The triphenylene ring which may have a substituent is, for example, a triphenylene ring, a decamethyltriphenylene ring, a diphenyltriphenylene ring or the like, and a triphenylene ring is preferable. Examples of the benzocyclobutene ring which may have a substituent include a benzocyclobutene ring, a dimethylbenzocyclobutene ring, and a diphenylbenzocyclobutene ring, and a benzocyclobutene ring is preferable. Examples of the thiophene ring that may have a substituent include a thiophene ring, a methylthiophene ring, and a phenylthiophene ring, and a methylthiophene ring is preferable. Examples of the benzothiophene ring that may have a substituent include a benzothiophene ring, a methylbenzothiophene ring, and a phenylbenzothiophene ring, and a methylthiophene ring is preferable.

One or more of the substituents R ^{5 to} R ⁸ are preferably a hydrogen atom.

  Examples of the spirobi (heterofluorene) derivative represented by the general formula (1) of the present invention include the following compounds.

（耐酸化性有機半導体材料）
次に、本発明の下記一般式（２）で示されるスピロビ（ヘテロフルオレン）誘導体を含む耐酸化性有機半導体材料について述べる。該耐酸化性有機半導体材料は溶剤への溶解性、耐酸化性に優れ、好適な塗布性を有する。

(Oxidation-resistant organic semiconductor materials)
Next, an oxidation resistant organic semiconductor material containing a spirobi (heterofluorene) derivative represented by the following general formula (2) 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.

（ここで、Ψはケイ素原子、ゲルマニウム原子、又はスズ原子を示し、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５〜２０のアルキル基、炭素数１〜２０のハロゲン化アルキル基、炭素数４〜３０のアリール基、炭素数２〜２０のアルキニル基、又は炭素数２〜３０のアルケニル基を示す。なお、置換基群（Ｒ^１とＲ^２）及び／又は置換基群（Ｒ^３とＲ^４）における置換基は互いに結合し環を形成することができる。）
本発明の一般式（２）の置換基について、さらに述べる。

(Here, Ψ represents a silicon atom, a germanium atom, or a tin atom, and the substituents R ^{1 to} R ⁸ are the same or different, and are a hydrogen atom, a fluorine atom, an alkyl group having 5 to 20 carbon atoms, 20 represents a halogenated alkyl group, an aryl group having 4 to 30 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, wherein the substituent group (R ¹ and R ² ) and (The substituents in the substituent group (R ³ and R ⁴ ) can be bonded to each other to form a ring.)
The substituent of the general formula (2) of the present invention will be further described.

  The substituent Ψ is preferably a silicon atom.

The alkyl group having 5 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited, and examples thereof include those exemplified for the substituents R ^{1 to} R ⁴ in the general formula (1).

The halogenated alkyl group having 1 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited, and examples thereof include those exemplified for the substituents R ^{1 to} R ⁴ in the general formula (1).

The aryl group having 4 to 30 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited, and examples thereof include those exemplified for the substituents R ^{1 to} R ⁴ in the general formula (1).

The alkynyl group having 2 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited, and examples thereof include those exemplified for the substituents R ^{1 to} R ⁴ in the general formula (1).

The alkenyl group having 2 to 30 carbon atoms in the substituents R ^{1 to} R ⁸ is not particularly limited, and examples thereof include those exemplified for the substituents R ^{1 to} R ⁴ in the general formula (1).

The substituents R ^{1 to} R ⁴ are preferably the same or different and are an alkyl group having 5 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 4 to 30 carbon atoms, or 2 carbon atoms. -20 alkynyl group, particularly preferably an aryl group having 4 to 30 carbon atoms or an alkynyl group having 2 to 20 carbon atoms.

The substituent group (R ¹ and R ² ) and the substituent group (R ³ and R ⁴ ) can be bonded to each other to form a ring. The ring is formed in any one substituent group or in both substituent groups, preferably in both substituent groups. The ring thus formed is not particularly limited, and examples thereof include the rings listed in the general formula (1).

The substituents R ^{5 to} R ⁸ are preferably the same or different and are a hydrogen atom or a fluorine atom, and more preferably one or more of the substituents R ^{5 to} R ⁸ are a hydrogen atom.

  Examples of the spirobi (heterofluorene) derivative represented by the general formula (2) in the oxidation-resistant organic semiconductor material of the present invention include examples of the spirobi (heterofluorene) derivative represented by the general formula (1) of the present invention. The same compounds as those obtained and the following compounds can be mentioned.

なお、本発明の下記一般式（２）で示されるスピロビ（ヘテロフルオレン）誘導体を含む耐酸化性有機半導体材料は、一般式（２）で示されるスピロビ（ヘテロフルオレン）誘導体の代わりに一般式（１）で示されるスピロビ（ヘテロフルオレン）誘導体を用いても製造することができる。従って、以下「一般式（２）等」と標記した場合は一般式（２）及び／又は一般式（１）で示されるスピロビ（ヘテロフルオレン）誘導体を表す。

In addition, the oxidation-resistant organic semiconductor material containing the spirobi (heterofluorene) derivative represented by the following general formula (2) of the present invention has the general formula (2) instead of the spirobi (heterofluorene) derivative represented by the general formula (2). It can also be produced using the spirobi (heterofluorene) derivative represented by 1). Therefore, hereinafter, “general formula (2) etc.” represents a spirobi (heterofluorene) derivative represented by general formula (2) and / or general formula (1).

  The solvent used for dissolving the spirobi (heterofluorene) derivative represented by the general formula (2) or the like is preferably a halogen solvent containing halogen such as chlorine, for example, o-dichlorobenzene, chlorobenzene, 1,2-dichloroethane, 1 , 1,2,2-tetrachloroethane, chloroform; ether solvents containing 1 to 2 oxygens such as THF, dioxane; hydrocarbon solvents of aromatic compounds such as toluene, xylene; ester solvents such as acetic acid Ethyl, γ-butyrolactone; amide solvents such as N, N-dimethylformamide, N-methylpyrrolidone; and the like. These solvents may be used alone or as a mixture of two or more. Among them, preferred is toluene or o-dichlorobenzene.

  An oxidation-resistant organic semiconductor containing the spirobi (heterofluorene) derivative represented by the general formula (2) by mixing and stirring the solvent listed above and the spirobi (heterofluorene) derivative represented by the general formula (2) Can be prepared. The temperature of mixing and stirring is 10 to 200 ° C, preferably 20 to 190 ° C. If it is lower than 10 ° C., the concentration becomes too low to make it difficult to obtain a good thin film, which is not preferred. The concentration of the solution can be changed depending on the type of solvent and the temperature, but 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 evaluation of the oxidation resistance of the oxidation-resistant organic semiconductor material containing the spirobi (heterofluorene) derivative represented by the general formula (2) or the like can be performed by a method in which the solution is brought into contact with air for a predetermined time. The solvent used for the evaluation is degassed in advance to remove dissolved oxygen. The contact time with air is suitably 0.5 minutes to 3 hours. The progress of oxidation can be achieved by changing the color of the solution and / or detecting the oxide by gas chromatography and gas chromatography-mass spectrum (GCMS) analysis.

The solution of the oxidation-resistant organic semiconductor material containing the spirobi (heterofluorene) derivative represented by the general formula (2) or the like of the present invention is suitable for the spirobi (heterofluorene) derivative itself represented by the general formula (2) or the like used. Therefore, it can be dissolved in a solvent at a relatively low temperature and has oxidation resistance, so that 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 spirobi (heterofluorene) derivative represented by the general formula (2) of the present invention is 0.005 to 20 poise. It is preferable to be in the range.
(Organic thin film)
Next, an organic thin film using an oxidation-resistant organic semiconductor material containing a spirobi (heterofluorene) derivative represented by the general formula (2) 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 a thin film by coating on a substrate can be carried out by vaporizing the solvent by a method such as heating, air flow, and natural drying after the oxidation-resistant organic semiconductor material solution is coated on the substrate. The concentration of the compound such as the general formula (2) in the solution is not particularly limited, and is preferably 0.01 to 10.0% by weight, for example. The application temperature is not particularly limited, and can be preferably carried out between 20 ° C. and 200 ° C., for example. The specific method of application is not particularly limited, and known methods such as spin coating, cast coating, and dip coating can be used. Furthermore, it can also be produced by using printing techniques such as screen printing, gravure printing, and ink jet 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 include plastic substrates such as polyethylene terephthalate, polymethyl methacrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol; glass, quartz, aluminum oxide, silicon, silicon oxide, tantalum dioxide, An inorganic material substrate such as tantalum pentoxide or indium tin oxide; a metal substrate such as gold, copper, chromium, or titanium can be preferably used. Further, the surfaces of these substrates can be used even if they are modified with silanes such as octadecyltrichlorosilane and octadecyltrimethoxysilane or hexamethyldisilazane. The applied solvent can be removed by drying under normal pressure or reduced pressure, or may be dried by heating in a nitrogen stream. Furthermore, crystal growth of the spirobi (heterofluorene) derivative represented by the general formula (2) of the present invention can be controlled by adjusting the evaporation rate of the solvent. Although the film thickness of the thin film obtained by application | coating to a board | substrate is not specifically limited, Preferably it is 1 nm-100 micrometers, Most preferably, it is 10 nm-10 micrometers.

  Moreover, the organic thin film using the oxidation-resistant organic-semiconductor material containing the spirobi (heterofluorene) derivative shown by General formula (2) etc. of this invention can also be produced on a board | substrate by a vacuum evaporation method.

The spirobi (heterofluorene) derivative represented by the general formula (2) of the present invention can be expected to give excellent semiconductor characteristics. The spirobi (heterofluorene) 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 formed by a coating method. The oxidation-resistant organic semiconductor material containing the spirobi (heterofluorene) derivative represented by the general formula (1) of the present invention and the spirobi (heterofluorene) derivative represented by the general formula (2) is an electronic paper, an organic electroluminescence display It can be used for organic semiconductor active phase applications of transistors such as liquid crystal displays or IC tags, and further for organic semiconductor laser materials, organic thin film solar cell materials, photonic crystal materials, and the like.
(Method for producing spirobi (heterofluorene) derivative)
Next, the manufacturing method of the spirobi (heterofluorene) derivative shown by General formula (2) is described. In addition, the spirobi (heterofluorene) derivative shown by General formula (1) can also be manufactured by the same method.

  A spirobi (heterofluorene) derivative represented by the general formula (2) is obtained by dilithiating and / or digrinarizing a dihalobiphenyl derivative represented by the following general formula (3) in a dialkyl ether solvent, It can be produced by reacting with a germanium compound or a tin compound.

（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は、一般式（２）で示される置換基と同意義を示す。）
なお、一般式（１）及び／又は（２）で示されるスピロビ（ヘテロフルオレン）誘導体を以下「一般式（２）等」と標記する。

(Here, the substituents X ¹ and X ² represent a bromine atom, an iodine atom or a chlorine atom, and the substituents R ^{1 to} R ⁸ have the same meaning as the substituent represented by the general formula (2).)
The spirobi (heterofluorene) derivative represented by the general formula (1) and / or (2) is hereinafter referred to as “general formula (2) etc.”.

The substituents X ¹ and X ² are preferably a bromine atom and an iodine atom.

When the dihalobiphenyl derivative represented by the general formula (3) is dilithiated, as long as the lithiating agent to be used is capable of substituting the halogen X ¹ and / or X ² in the general formula (3) with lithium. It does not specifically limit, For example, an organic lithium reagent, an organic lithium amide reagent, and a lithium metal can be mentioned. Examples of the organolithium reagent include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, phenyllithium, etc .; examples of the organolithium amide reagent include lithium diisopropylamide, lithium hexamethyldiethyl. Examples thereof include silazide. Such a lithiating agent is preferably n-butyllithium.

Here, dilithiation means that ^two halogens X ¹ and X ² in the general formula (3) are each replaced with lithium.

  The dilithiation reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited. For example, a non-cyclic ring having two or more oxygen atoms such as dialkyl ether such as diethyl ether, di (n-butyl) ether, methyl-tert-butyl ether, ethylene glycol dimethyl ether, trimethylene glycol dimethyl ether or the like. Hydrocarbons such as ether, toluene, hexane, cyclohexane, etc. are preferred, dialkyl ethers are preferred, and diethyl ether is particularly preferred. These solvents may be used alone or as a mixture of two or more.

  The dilithiating agent is used in an amount of 1.5 to 3.0 equivalents, preferably 1.8 to 2.5 equivalents, relative to the dihalobiphenyl derivative represented by the general formula (3). The temperature of the dilithiation reaction is -80 to 60 ° C, preferably -40 to 40 ° C, and the reaction time is 1 to 360 minutes, preferably 3 to 60 minutes.

When the dihalobiphenyl derivative of the general formula (3) is diglynarized, the Grignard agent used is the halogen X ¹ and / or X ² in the general formula (3) MgX (where X is chlorine, bromine, or iodine) And any other alkyl Grignard reagent such as isopropylmagnesium bromide, tert-butylmagnesium bromide, and the like, preferably Mg metal. The form of the Mg metal is not particularly limited, and examples thereof include a cut shape, a ribbon shape, and a granular shape.

Here, diglynarization means that two halogens X ¹ and X ² in the general formula (3) are each substituted with a magnesium halide.

  The diglynarization reaction is preferably carried out in a solvent. The solvent to be used is not specifically limited, For example, the solvent used for the dilithiation reaction can be mentioned.

  For example, in the case of Mg metal, the diglynar agent is preferably used in the range of 1.5 to 5 equivalents, preferably 1.8 to 3 equivalents, relative to the dihalobiphenyl derivative represented by the general formula (3). The temperature of the diglynarization reaction is preferably -20 to 110 ° C, and the reaction time is 1 to 360 minutes, preferably 3 to 60 minutes.

  As described above, the dihalobiphenyl derivative represented by the general formula (3) is dilithiated and / or diglynarized, and then the reaction product is reacted with a silane compound, a germanium compound, or a tin compound to obtain the general formula (2 ) And other spirobi (heterofluorene) derivatives can be produced.

  The silane compound, germanium compound, or tin compound used here reacts with a dilithiated and / or diglynarized compound such as the above general formula (2) to produce a spirobi (heterofluorene) derivative such as the general formula (2). There is no particular limitation as long as it provides the above. A silane compound is preferable.

  Examples of the silane compound include tetrahalogenated silane, tetraalkoxysilane, and dihalogenated dialkoxysilane, and tetrahalogenated silane is preferable. Specific examples of the tetrahalogenated silane include tetrachlorosilane, tetrabromosilane, tetraiodosilane, and tetrafluorosilane, with tetrachlorosilane being preferred. Specific examples of tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. Specific examples of the dihalogenated dialkoxysilane include dichlorodimethoxysilane, dichlorodiethoxysilane, dibromodimethoxysilane and the like.

  Examples of the germanium compound include tetrahalogenated germanium, tetraalkoxygermanium, or dihalogenated dialkoxygermanium, and tetrahalogenated germanium is preferable. Specific examples of the tetrahalogenated germanium include tetrachlorogermanium, tetrabromogermanium, tetraiodogermanium, and tetrafluorogermanium, with tetrachlorogermanium being preferred. Specific examples of tetraalkoxygermanium include tetramethoxygermanium, tetraethoxygermanium, and tetrabutoxygermanium. Specific examples of the dihalogenated dialkoxygermanium include dichlorodimethoxygermanium, dichlorodiethoxygermanium, dibromodimethoxygermanium and the like.

  Examples of the tin compound include tetrahalogenated tin, tetraalkoxytin, and dihalogenated dialkoxytin, and preferred is tetrahalogenated tin. Specific examples of the tin halide include tetrachlorotin, tetrabromotin, tetraiodotin, and tetrafluorotin, and tetrachlorotin is preferred. Specific examples of tetraalkoxytin include tetramethoxytin, tetraethoxytin, and tetrabutoxytin. Specific examples of the dihalogenated dialkoxytin include dichlorodimethoxytin, dichlorodiethoxytin, dibromodimethoxytin and the like.

  The reaction between the dilithiated product and / or diglynarized product and the silane compound, germanium compound, or tin compound is preferably carried out in a solvent. The solvent to be used is not specifically limited, For example, the solvent used for the dilithiation reaction can be mentioned. The amount of the silane compound, germanium compound, or tin compound used is 0.3 to 1.2 equivalents, preferably 0.4 to 0.8 equivalents, relative to the dihalobiphenyl derivative of the general formula (3). . The reaction temperature with the silane compound, germanium compound, or tin compound is −75 to 80 ° C., preferably −40 to 50 ° C., and the reaction time is 1 to 48 hours, preferably 1 to 24 hours.

  The production of the spirobi (heterofluorene) derivative such as the general formula (2) of the present invention is preferably carried out under an inert atmosphere such as nitrogen or argon.

The spirobi (heterofluorene) derivative represented by the general formula (2) and the like thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.
(Dihalobiphenyl derivative production method)
The dihalobiphenyl derivative represented by the general formula (3), which is a precursor of the spirobi (heterofluorene) derivative represented by the general formula (2) or the like, can be derived from the dihalobenzene derivative represented by the following general formula (4).

（ここで、置換基Ｘ^１、Ｒ^１、Ｒ^２、Ｒ^５、及びＲ^６は一般式（３）で示される置換基と同意義を示す。）
即ち、一般式（３）で示されるジハロビフェニル誘導体は、一般式（４）で示されるジハロベンゼン誘導体をリチオ化剤又はグリニャール化剤を用いてホモカップリングすることで製造することができる。

(Here, the substituents X ¹ , R ¹ , R ² , R ⁵ , and R ⁶ have the same meaning as the substituent represented by the general formula (3).)
That is, the dihalobiphenyl derivative represented by the general formula (3) can be produced by homocoupling the dihalobenzene derivative represented by the general formula (4) using a lithiating agent or a Grignard agent.

The lithiating agent used for the homocoupling reaction of the dihalobenzene derivative is not particularly limited as long as it can lithiate halogen X ¹ in the general formula (4). For example, an organic lithium reagent, an organic lithium amide reagent, Mention may be made of lithium metal. Examples of the organic lithium reagent include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, and phenyllithium; examples of the organic lithiumamide reagent include lithium diisopropylamide and lithium hexamethyldisilazide. Etc. Such a lithiating agent is preferably n-butyllithium.

  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, 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 used in an amount of 0.3 to 1.2 equivalents, preferably 0.4 to 0.7 equivalents, relative to the dihalobenzene derivative represented by the general formula (4). The temperature of the lithiation reaction is −110 to 40 ° C., preferably −100 to 30 ° C., and the reaction time is 0.5 to 30 hours, preferably 1 to 20 hours.

On the other hand, the Grignard agent used for the homocoupling reaction of the dihalobenzene derivative represented by the general formula (4) is not particularly limited as long as the halogen X ¹ in the general formula (4) can be Grignard, for example, Mg metal, or alkyl Grignard reagents such as ethylmagnesium bromide, isopropylmagnesium bromide, tert-butylmagnesium bromide, and the like can be mentioned, but Mg metal is preferred. The form of the Mg 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 Mg metal, the Grignard agent is used in the range of 1.8 to 20 equivalents relative to the dihalobenzene derivative represented by the general formula (4). The Grignard reaction is preferably carried out in a solvent. The solvent to be used is not specifically limited, For example, the solvent used by the lithiation reaction can be mentioned. The temperature of the Grignard reaction is -20 to 120 ° C, and the reaction time is in the range of 1 to 30 hours.

  The production of the dihalobiphenyl derivative represented by the general formula (3) is preferably carried out under an inert atmosphere such as nitrogen or argon.

  The dihalobiphenyl derivative represented by the general formula (3) thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

  The homocoupling reaction using n-butyllithium as the lithiating agent can also be carried out by the method described in, for example, “Journal of Chemical Society, Parkin Transaction 1”, 2001, pages 159-165. .

  Furthermore, another method for producing the dihalobiphenyl derivative represented by the general formula (3) will be described.

  The dihalobiphenyl derivative represented by the general formula (3) is obtained by crossing a dihalobenzene derivative represented by the general formula (4) and a 2-haloaryl metal reagent represented by the following general formula (5) in the presence of a palladium and / or nickel catalyst. It can be manufactured by coupling.

（ここで、ＭはＭｇ、Ｂ、Ｚｎ、Ｓｎ又はＳｉのハロゲン化物、ハイドロオキサイド、アルコキサイド又はアルキル化物を示す。置換基Ｘ^２、Ｒ^３、Ｒ^４、Ｒ^７、及びＲ^８は一般式（３）で示される置換基と同意義を示す。）
一般式（５）の置換基ＭはＭｇ、Ｂ、Ｚｎ、Ｓｎ又はＳｉのハロゲン化物、ハイドロオキサイド、アルコキサイド又はアルキル化物であり、上記のパラジウム及び／又はニッケル触媒と反応し、パラジウム及び／又はニッケルと置換できる基である限り特に限定はなく、例えば、ＭｇＣｌ、ＭｇＢｒ、Ｂ（ＯＨ）_２、Ｂ（ＯＭｅ）_２、テトラメチルジオキサボロラニル基、ＺｎＣｌ、ＺｎＢｒ、ＺｎＩ、Ｓｎ（Ｂｕ−ｎ）_３又はＳｉ（Ｂｕ−ｎ）_３を挙げることができ、好ましくはＢ（ＯＨ）_２又はＺｎＣｌである。

(Here, M represents a halide, hydroxide, alkoxide or alkylated product of Mg, B, Zn, Sn or Si. The substituents X ² , R ³ , R ⁴ , R ⁷ and R ⁸ are represented by the general formula ( The same meaning as the substituent shown in 3) is shown.)
The substituent M in the general formula (5) is a halide, hydroxide, alkoxide or alkylated product of Mg, B, Zn, Sn or Si, which reacts with the palladium and / or nickel catalyst described above to produce palladium and / or nickel. As long as it is a group that can be substituted, there is no particular limitation. For example, MgCl, MgBr, B (OH) ₂ , B (OMe) ₂ , tetramethyldioxaborolanyl group, ZnCl, ZnBr, ZnI, Sn (Bu-n ) ₃ or Si (Bu-n) ₃ , preferably B (OH) ₂ or ZnCl.

  The 2-haloaryl metal reagent represented by the general formula (5) is, for example, halogen / metal exchange using an aryl dihalogen-substituted product as a raw material by a Grignard reagent such as isopropylmagnesium bromide or an organic lithium reagent such as n-butyllithium. After the reaction, it can be suitably prepared by reacting with zinc chloride, trimethoxyborane or the like.

  The catalyst used for the cross-coupling reaction of the dihalobenzene derivative represented by the general formula (4) and the 2-haloaryl metal reagent represented by the general formula (5) is not particularly limited as long as it is a palladium and / or nickel catalyst. Specific examples of the catalyst include tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium / triphenylphosphine mixture, dichlorobis (triphenylphosphine) palladium, bis (tri-tert-butylphosphine) palladium, palladium acetate / (Tri-tert-butylphosphine) mixture, diacetatobis (triphenylphosphine) palladium, dichloro (1,2-bis (diphenylphosphino) ethane) palladium, palladium acetate / triphenylphosphine mixed , Palladium acetate / 2- (dicyclohexylphosphino) -1,1′-biphenyl mixture, dichloro (ethylenediamine) palladium, dichloro (N, N, N ′, N′-tetramethylethylenediamine) palladium, dichloro (N, N , N ′, N′-tetramethylethylenediamine) palladium / triphenylphosphine mixture and the like can include zero-valent or divalent palladium compounds; specific examples of nickel catalysts include dichlorobis (triphenylphosphine) nickel, dichloro (1 , 2-bis (diphenylphosphino) ethane) nickel, dichloro (ethylenediamine) nickel, dichloro (N, N, N ′, N′-tetramethylethylenediamine) nickel, dichloro (N, N, N ′, N′-tetra) Methylethylenediamine) Le / triphenylphosphine mixtures, and bis (1,5-cyclooctadiene) nickel / triphenylphosphine zerovalent mixtures or divalent nickel compounds. Among these, a preferable catalyst is a zero-valent palladium compound, and a particularly preferable catalyst is tetrakis (triphenylphosphine) palladium.

  The amount of the catalyst used in the coupling reaction is in the range of 0.1 to 20 mol% with respect to the dihalobenzene derivative of the general formula (4). The amount of the 2-haloaryl metal reagent of the general formula (5) used is 0.6 to 1.5 equivalents, preferably 0.8 to 1.4 equivalents, more preferably 0, based on the dihalobenzene derivative of the general formula (4). It can be used in the range of .9 to 1.2 equivalents.

  The reaction is preferably carried out in a solvent. Specific examples include THF, diethyl ether, methyl tert-butyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol, diisopropylamine, toluene, xylene, hexane, cyclohexane, ethanol, water, and the like. One kind or a mixture of two or more kinds may be used. For example, it can also be used in a 2 to 3 component system such as toluene / water or toluene / ethanol / water.

  A base can also be present in the reaction system. The type of base in this case is not particularly limited. For example, sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, potassium fluoride and other inorganic bases, sodium methoxide, sodium tert- Preferred examples include alkoxides such as butoxide and potassium tert-butoxide, and amines such as triethylamine, trimethylamine, tributylamine and pyridine. These bases can be used in an amount of 1.5 to 10.0 equivalents, preferably 2.0 to 8.0 equivalents, relative to the dihalobenzene derivative of the general formula (4). Furthermore, a phase transfer catalyst can be used in combination with these bases. Although the kind of phase transfer catalyst is not specifically limited, For example, a trioctyl methyl ammonium chloride, tetrabutyl ammonium chloride, a cetyl pyridinium chloride etc. can be mentioned as a suitable thing. The amount of these phase transfer catalysts used is in the range of 0.1 to 1.5 equivalents, preferably 0.2 to 0.8 equivalents, relative to the dihalobenzene derivative of the general formula (4).

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

  A copper compound can also be present in the reaction system. The type of copper compound in this case is not particularly limited. For example, monovalent copper such as copper chloride (I), copper bromide (I), copper iodide (I), copper acetate (I); copper chloride (II ), Copper (II) bromide, copper (II) iodide, copper (II) acetate, copper acetylacetonate (II) and the like. Monovalent copper is preferable, and copper (I) iodide is particularly preferable. These copper compounds can be used in an amount of 0.3-10.0 equivalents, preferably 0.6-6.0 equivalents, relative to the palladium and / or nickel catalyst.

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

Regarding the atmosphere of the reaction system and the purification of the obtained dihalobiphenyl derivative represented by the general formula (3), the method for producing the dihalobiphenyl derivative represented by the general formula (3) described above and Similar methods can be used.
(Dihalobenzene derivative production method)
A method for producing the dihalobenzene derivative represented by the general formula (4) will be described.

  The dihalobenzene derivative represented by the general formula (4) is, for example, a cross-coupling of a tetrahalobenzene derivative represented by the following general formula (6) and a reactant represented by the following general formula (7) in the presence of a palladium and / or nickel catalyst. It can also be produced by ring reaction.

（ここで、置換基Ｘ^３はヨウ素原子又は臭素原子を示し、置換基Ｘ^４はヨウ素原子、臭素原子又は水素原子を示し、置換基Ｘ^１、Ｒ^５、及びＲ^６は一般式（４）で示される置換基と同意義を示す。）
なお、置換基Ｘ^３及びＸ^４は、好ましくはヨウ素原子である。

(Wherein the substituent X ³ represents an iodine atom or a bromine atom, the substituent X ⁴ represents an iodine atom, a bromine atom or a hydrogen atom, and the substituents X ¹ , R ⁵ and R ⁶ are represented by the general formula (4) And the same meaning as the substituent represented by.
The substituents X ³ and X ⁴ are preferably iodine atoms.

AN (7)
(Here, A is a hydrogen atom, a fluorine atom, an alkyl group having 5 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 4 to 30 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, Or an alkenyl group having 2 to 30 carbon atoms, N represents a hydrogen atom, an alkali metal of Li, Na or K, a halide of Mg, B, Zn, Sn or Si, a hydroxide, an alkoxide or an alkylated product.)
In addition, by selecting A in the general formula (7), a desired substituent is introduced into the substituents X ³ and X ⁴ of the tetrahalobenzene represented by the general formula (6). A dihalobenzene derivative represented by the formula (4) can be obtained.

  The substituent A of the general formula (7) is preferably an alkyl group having 5 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 4 to 30 carbon atoms, or an alkynyl having 2 to 20 carbon atoms. Group, an alkenyl group having 2 to 30 carbon atoms, particularly preferably an aryl group having 4 to 30 carbon atoms and an alkynyl group having 2 to 20 carbon atoms.

The substituent N in the general formula (7) is a hydrogen atom, an alkali metal of Li, Na, or K, a halide, a hydroxide, an alkoxide, or an alkylated product of Mg, B, Zn, Sn, or Si. There is no particular limitation as long as it is a group capable of reacting with a nickel catalyst and replacing palladium and / or nickel, or a group that becomes a hydrogen halide in the course of the reaction. For example, MgCl, MgBr, B (OH) ₂ , B (OMe ) ₂ , tetramethyldioxaborolanyl group, ZnCl, ZnBr, ZnI, Sn (Bu-n) ₃ or Si (Bu-n) ₃ , preferably B (OH) ₂ or ZnCl. .

  The reactant represented by the general formula (7) is, for example, a halogen / metal exchange reaction of an aryl halogen-substituted product as a raw material with a Grignard reagent such as isopropyl magnesium bromide or an organic lithium reagent such as n-butyl lithium. Thereafter, it can be suitably prepared by reacting with zinc chloride, trimethoxyborane or the like.

  One type or two types of reactants represented by the general formula (7) may be used.

  The catalyst used for the cross-coupling reaction of the tetrahalobenzene derivative represented by the general formula (6) and the reactant represented by the general formula (7) is not particularly limited as long as it is a palladium and / or nickel catalyst. The palladium and / or nickel catalyst used when obtaining the dihalobiphenyl derivative shown by General formula (3) from the dihalobenzene derivative shown by (4) and the 2-haloaryl metal reagent shown by General formula (5) is mentioned. be able to. Among these, a preferable catalyst is a zero-valent palladium compound, and a particularly preferable catalyst is tetrakis (triphenylphosphine) palladium.

  The amount of the catalyst used in the coupling reaction is in the range of 0.1 to 20 mol% with respect to the tetrahalobenzene derivative of the general formula (6). The amount of the reactant of the general formula (7) used is 1.4 to 3.5 equivalents relative to the tetrahalobenzene derivative of the general formula (6) when one kind of the reactant of the general formula (7) is used. , Preferably 1.6 to 3.0 equivalents, more preferably 1.8 to 2.8 equivalents, and when two types of reactants of the general formula (7) are used, the general formula The tetrahalobenzene derivative (6) may be used in an amount of 0.6 to 1.8 equivalents, preferably 0.7 to 1.5 equivalents, more preferably 0.8 to 1.4 equivalents. it can.

  In the coupling reaction, when two types of reactants of the general formula (7) are used, the two types of reactants can be present at the start of the reaction, or the first and second reactants can be present. It is also possible to add the reaction agent after a sufficient time.

  The reaction is preferably carried out in a solvent. Specific examples include THF, diethyl ether, methyl-tert-butyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol, N, N-dimethylformamide, N-methylpyrrolidone, triethylamine, diisopropylamine, pyrrolidine, piperidine, toluene, xylene, hexane. , Cyclohexane, ethanol, water and the like, and these solvents may be used alone or as a mixture of two or more thereof. For example, it can also be used in a 2 to 3 component system such as toluene / water or toluene / ethanol / water.

  A base can also be present in the reaction system. The type of base in this case is not particularly limited. For example, sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, potassium fluoride and other inorganic bases, sodium methoxide, sodium tert- Preferred examples include alkoxides such as butoxide and potassium tert-butoxide, and amines such as triethylamine, trimethylamine, tributylamine, diisopropylamine and pyridine. These bases can be used in an amount of 1.5 to 10.0 equivalents, preferably 2.0 to 8.0 equivalents, relative to the tetrahalobenzene derivative of the general formula (6). Furthermore, a phase transfer catalyst can be used in combination with these bases. Although the kind of phase transfer catalyst is not specifically limited, For example, a trioctyl methyl ammonium chloride, tetrabutyl ammonium chloride, a cetyl pyridinium chloride etc. can be mentioned as a suitable thing. The amount of these phase transfer catalysts used is in the range of 0.1 to 1.5 equivalents, preferably 0.2 to 0.8 equivalents, relative to the tetrahalobenzene derivative of the general formula (6).

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

  A copper compound can also be present in the reaction system. The type of copper compound in this case is not particularly limited. For example, monovalent copper such as copper chloride (I), copper bromide (I), copper iodide (I), copper acetate (I); copper chloride (II ), Copper (II) bromide, copper (II) iodide, copper (II) acetate, copper acetylacetonate (II) and the like. Monovalent copper is preferable, and copper (I) iodide is particularly preferable. These copper compounds can be used in an amount of 0.3-10.0 equivalents, preferably 0.6-6.0 equivalents, relative to the palladium and / or nickel catalyst.

  The reaction temperature is 10 to 120 ° C., preferably 30 to 100 ° C., and the reaction time is suitably in the range of 1 to 72 hours.

  The position at which a bond is formed by the coupling reaction of the tetrahalobenzene derivative represented by the general formula (6) and the reactant of the general formula (7) can be controlled by the type of halogen.

  That is, since the reactivity of iodine is the highest and the reactivity decreases in the order of bromine and chlorine, the reaction position can be arbitrarily determined by utilizing the reactivity of these halogen types.

Therefore, the synthesis to the dihalobenzene derivative represented by the general formula (4) can be achieved by setting X ³ in the general formula (6) as iodine and X ¹ as bromine and / or chlorine.

  The production of the dihalobenzene derivative represented by the general formula (4) is preferably carried out under an inert atmosphere such as nitrogen or argon.

Among the dihalobenzene derivatives represented by the general formula (4), those in which the substituents R ¹ and R ² are combined to form a ring include, for example, “Journal of Organic Chemistry”, 1983, 48, 2364. It can also be synthesized by the method described on page 2366.

  The dihalobenzene derivative represented by the general formula (4) thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

  Provided are a spirobi (heterofluorene) derivative having a rigid structure, which has excellent oxidation resistance and can form a semiconductor active phase by a coating method, and uses thereof. Furthermore, the present invention provides a method for producing a spirobi (heterofluorene) derivative having a high yield and excellent economic efficiency. In the production method of the present invention, a spirobi (heterofluorene) derivative into which a substituent is introduced 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) was measured by JEOL JMS-700 manufactured by JEOL directly by introducing the sample and by electron impact (EI) method (70 electron volts) or FAB method (6 kiloelectron volts).

  For confirmation of the progress of the reaction, etc., gas chromatography and gas chromatography-mass spectrum (GCMS) analysis were used.

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
X-ray diffraction measurement was performed under the following conditions.

Equipment RAD-C manufactured by Rigaku Corporation
X-ray CuKα ray (using graphite monochromator), 50 kV, 200 mA
Conditions θ-2θ scan, 3 ≦ 2θ ≦ 70 °, scan speed = 4.8 ° / min,
Continuous scan Measurement every 0.04 ° A commercially available dehydrated solvent was used as the solvent for reaction.

Synthesis Example 1 (Synthesis of 3,3′-dibromo-2,2′-binaphthyl)
The raw material 2,3-dibromonaphthalene was synthesized using the method described in Journal of Organic Chemistry, 1983, Vol. 48, pages 2364-2366.

  Under a nitrogen atmosphere, 2,3-dibromonaphthalene (8.31 g, 29.1 mmol) and THF (200 ml) were added to a 500 ml Schlenk reaction vessel. This was cooled to −78 ° C., and 9.6 ml (15.3 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.59 M) was added dropwise. The cooling bath was removed and the mixture was stirred at room temperature for 1 hour. After the treatment with 3N hydrochloric acid, the residue was purified by silica gel column chromatography (solvent: hexane-toluene) to obtain 3.30 g of 3,3′-dibromo-2,2-binaphthyl white solid (yield 55 %).

¹ H NMR (CDCl ₃ , 21 ° C.): δ = 8.20 (s, 2H), 7.97-7.75 (m, 6H), 7.59-7.48 (m, 4H).
MS m / z: 412 (M ⁺ , 26%), 332 (M ⁺ -Br, 5), 252 (M ⁺ -2Br, 100), 126 ((M ⁺ -2Br) / 2, 54).
Example 1 (Synthesis of tetrabenzo-9,9'-spirobi (9-silafluorene))
Under a nitrogen atmosphere, 350 mg (0.849 mmol) of 3,3′-dibromo-2,2′-binaphthyl synthesized in Synthesis Example 1 and 25 ml of diethyl ether were added to a 100 ml Schlenk reaction vessel. After cooling to 0 ° C., 1.16 ml (1.84 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.59 M) was added dropwise. After stirring at 0 ° C. for 15 minutes, 72.4 mg (0.426 mmol) of tetrachlorosilane (manufactured by Wako Pure Chemical Industries) was added. After heating up to room temperature overnight, it stirred at 40 degreeC for 2 hours further. 3N hydrochloric acid aqueous solution and toluene were added, and after phase separation, 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 further dried at 60 ° C. under reduced pressure to remove volatile components. The obtained residue was recrystallized from toluene to obtain the target compound as yellow crystals (138 mg, 61% yield).

FABMS m / z: 533 (M ⁺ +1).
The structural formula of tetrabenzo-9,9′-spirobi (9-silafluorene) obtained is shown below.

実施例２ （耐酸化性評価）
窒素雰囲気下、２０ｍｌシュレンク容器にｏ−ジクロロベンゼン３．５ｇ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１で得られたテトラベンゾ−９，９’−スピロビ（９−シラフルオレン）の固体６．２ｍｇを添加し、１２０℃に加熱し溶解させると黄色溶液となった。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１２０℃で撹拌した。しかし、ガスクロマトグラフィー及びガスクロマトグラフィー−マススペクトル（ＧＣＭＳ）分析で酸化に由来する新たなピークの出現はなかった。従って、実施例１で得られたテトラベンゾ−９，９’−スピロビ（９−シラフルオレン）は耐酸化性を有していることが確認された。

Example 2 (Oxidation resistance evaluation)
Under a nitrogen atmosphere, 3.5 g of o-dichlorobenzene was added to a 20 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle consisting of freezing (liquid nitrogen), reduced pressure, nitrogen substitution, and thawing three times. Thereto was added 6.2 mg of the tetrabenzo-9,9′-spirobi (9-silafluorene) solid obtained in Example 1, and the mixture was heated to 120 ° C. to dissolve it to give a yellow 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 120 ° C. However, there was no new peak due to oxidation in gas chromatography and gas chromatography-mass spectrum (GCMS) analysis. Therefore, it was confirmed that the tetrabenzo-9,9′-spirobi (9-silafluorene) obtained in Example 1 has oxidation resistance.

Synthesis Example 2 (Synthesis of 1,2-dibromo-4,5-diiodobenzene)
1,2-Dibromo-4,5-diiodobenzene was synthesized according to the method described in “Sinlet”, 2003, pages 29-34.

  Periodic acid 36.9 g (162 mmol) and sulfuric acid 150 ml were added to a 1 l three-necked flask equipped with a mechanical stirrer. After the periodic acid was dissolved, 80.7 g (486 mmol) of potassium iodide was added little by little. The temperature of the contents was cooled to 0 ° C., and 75.0 g of 1,2-dibromobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) (318 mmol) was added. The resulting mixture was stirred at 0 ° C. for 30 minutes. The reaction mixture was poured into ice and then filtered to remove the solid. The solid was recrystallized twice from THF / methanol to obtain white crystals of 1,2-dibromo-4,5-diiodobenzene (76.2 g, yield 49%).

¹ H NMR (CDCl ₃ , 21 ° C.): δ = 8.03 (s, 2H).
Synthesis Example 3 (Synthesis of 1,2-dibromo-4,5-diphenylbenzene)
Under a nitrogen atmosphere, 3.074 g (6.30 mmol) of 1,2-dibromo-4,5-diiodobenzene synthesized in Synthesis Example 2 in a 200 ml Schlenk reaction vessel, tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 600 mg (0.519 mmol) and 1.920 g (15.7 mmol) of phenylboronic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added. Further, 50 ml of toluene, 13 ml of ethanol, and an aqueous solution consisting of 4.007 g (37.8 mmol) of sodium carbonate and 16 ml of water were added. Heat to 82 ° C. and stir 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 26 ml of toluene, 1.0 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 the resulting residue was purified by silica gel column chromatography (solvent, hexane), then 1,2-dibromo-4,5-diphenylbenzene white A solid was obtained (1.953 g, 80% yield).

¹ H NMR (CDCl ₃ , 21 ° C.): δ = 7.67 (s, 2H), 7.24-7.13 (m, 6H), 7.12-6.90 (m, 4H).
MS m / z: 388 (M ⁺ , 100%), 308 (M ⁺ -Br, 23), 228 (M ⁺ -2Br, 53).
Synthesis Example 4 (Synthesis of 4,5,4 ′, 5′-tetraphenyl-2,2′-dibromo-1,1′-biphenyl)
Under a nitrogen atmosphere, 1.08 g (2.78 mmol) of 1,2-dibromo-4,5-diphenylbenzene synthesized in Synthesis Example 3 and 20 ml of THF were added to a 100 ml Schlenk reaction vessel. The solution was cooled to −78 ° C., and 0.87 ml (1.38 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) was added dropwise. After raising the temperature to room temperature overnight, the produced solid was filtered out and washed with water. The obtained crude solid was recrystallized from toluene to obtain the objective white solid (722 mg, 84% yield).

¹ H NMR (CDCl ₃ , 21 ° C.): δ = 7.76 (s, 2H), 7.43 (s, 2H), 7.26-7.11 (m, 20H).
MS m / z: 616 (M ⁺ , 100%), 536 (M ⁺ -Br, 8), 456 (M ⁺ -2Br, 38).
Example 3 (Synthesis of 2,2 ′, 3,3 ′, 6,6 ′, 7,7′-octaphenyl-9,9′-spirobi (9-silafluorene))
Under a nitrogen atmosphere, 108 mg (0.175 mmol) of 4,5,4 ′, 5′-tetraphenyl-2,2′-dibromo-1,1′-biphenyl synthesized in Synthesis Example 4 and diethyl in a 100 ml Schlenk reaction vessel 5 ml of ether was added. After cooling this solution to 0 ° C., 0.24 ml (0.38 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) was added dropwise. After stirring at 0 ° C. for 20 minutes, 15.0 mg (0.088 mmol) of tetrachlorosilane (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 40 ° C. for 4 hours. 3N hydrochloric acid aqueous solution and toluene were added, and after phase separation, 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 further dried at 60 ° C. under reduced pressure to remove volatile components. The obtained residue was recrystallized from toluene / hexane (= 5: 1, volume ratio) to obtain white crystals of the target product (48 mg, yield 58%).

¹ H NMR (CDCl ₃ , 21 ° C.): δ = 8.01 (s, 4H), 7.64 (s, 4H), 7.26 (s, 20H), 7.14 (s, 20H).
FABMS m / z: 941 (M ⁺ +1).
The structural formula of the obtained target product is shown below.

実施例４ （耐酸化性評価）
窒素雰囲気下、２０ｍｌシュレンク容器にｏ−ジクロロベンゼン２．９ｇ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３で得られた２，２’，３，３’，６，６’，７，７’−オクタフェニル−９，９’−スピロビ（９−シラフルオレン）の固体５．２ｍｇを添加し、１２０℃に加熱し溶解させると無色溶液となった。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１２０℃で撹拌した。しかし、ガスクロマトグラフィー及びガスクロマトグラフィー−マススペクトル（ＧＣＭＳ）分析で酸化に由来する新たなピークの出現はなかった。従って、実施例３で得られた２，２’，３，３’，６，６’，７，７’−オクタフェニル−９，９’−スピロビ（９−シラフルオレン）は耐酸化性を有していることが確認された。

Example 4 (Oxidation resistance evaluation)
Under a nitrogen atmosphere, 2.9 g of o-dichlorobenzene was added to a 20 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle consisting of freezing (liquid nitrogen), reduced pressure, nitrogen substitution, and thawing three times. Thereto, 5.2 mg of 2,2 ′, 3,3 ′, 6,6 ′, 7,7′-octaphenyl-9,9′-spirobi (9-silafluorene) solid obtained in Example 3 was added. When added and heated to 120 ° C. to dissolve, a colorless solution was formed. 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 120 ° C. However, there was no new peak due to oxidation in gas chromatography and gas chromatography-mass spectrum (GCMS) analysis. Therefore, 2,2 ′, 3,3 ′, 6,6 ′, 7,7′-octaphenyl-9,9′-spirobi (9-silafluorene) obtained in Example 3 has oxidation resistance. It was confirmed that

Comparative Example 1
Under a nitrogen atmosphere, 2.7 g of o-dichlorobenzene was added to a 20 ml Schlenk container, and dissolved oxygen was removed by repeating the cycle of freezing (liquid nitrogen) -depressurization-nitrogen replacement-thawing three times. Thereto, 2.1 mg of pentacene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and when heated to 120 ° 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 pink. The mixture was further stirred at 120 ° 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 at 120 ° C. for 1 hour with stirring, the color of the solution changed to yellow. Gas chromatographic analysis showed increased production of 6,13-pentacenequinone.

Example 5 (Creation of an organic thin film)
Under a nitrogen atmosphere, 9.2 mg of 2,2 ′, 3,3 ′, 6,6 ′, 7,7′-octaphenyl-9,9′-spirobi (9-silafluorene) obtained in Example 3 was added. Mix with 15.5 g of toluene, stir at 110 ° C. for 1 hour, 2,2 ′, 3,3 ′, 6,6 ′, 7,7′-octaphenyl-9,9′-spirobi (9-silafluorene) ) Was prepared.

A quartz substrate having a concave surface was heated to 75 ° C. in an air atmosphere, and the above solution was applied onto the substrate using a dropper and dried under normal pressure to produce a thin film having a thickness of 440 nm. As a result of analyzing the components of this thin film by gas chromatography, it was found that, besides 2,2 ′, 3,3 ′, 6,6 ′, 7,7′-octaphenyl-9,9′-spirobi (9-silafluorene) There were no peaks and no oxidation. Accordingly, a thin film of 2,2 ′, 3,3 ′, 6,6 ′, 7,7′-octaphenyl-9,9′-spirobi (9-silafluorene) can be produced without being oxidized in the air. all right.

Claims (10)

A spirobi (heterofluorene) derivative represented by the following general formula (1).

(Here, Ψ represents a silicon atom, a germanium atom, or a tin atom, and the substituents R ^{1 to} R ⁴ are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group having 5 to 20 carbon atoms, 20 represents a halogenated alkyl group, an aryl group having 4 to 30 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, provided that the substituent group (R ¹ and R ² ) and The substituents in at least one of the substituent groups (R ³ and R ⁴ ) are bonded to each other to form a ring, and the substituents R ^{5 to} R ⁸ are the same or different and represent a hydrogen atom or a fluorine atom.) In the general formula (1), in the substituent group (R ¹ and R ² ) and the substituent group (R ³ and R ⁴ ), the substituents in each group are bonded to each other to form a ring. The spirobi (heterofluorene) derivative according to claim 1. An oxidation-resistant organic semiconductor material containing a spirobi (heterofluorene) derivative represented by the following general formula (2).

(Here, Ψ represents a silicon atom, a germanium atom, or a tin atom, and the substituents R ^{1 to} R ⁸ are the same or different, and are a hydrogen atom, a fluorine atom, an alkyl group having 5 to 20 carbon atoms, 20 represents a halogenated alkyl group, an aryl group having 4 to 30 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, wherein the substituent group (R ¹ and R ² ) and (The substituents in the substituent group (R ³ and R ⁴ ) can be bonded to each other to form a ring.) In the general formula (2), the substituents R ^{1 to} R ⁴ are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group having 5 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 4 to 4 carbon atoms. 30 aryl groups, alkynyl groups having 2 to 20 carbon atoms, or alkenyl groups having 2 to 30 carbon atoms, and the substituents R ^{5 to} R ⁸ are the same or different and are hydrogen atoms or fluorine atoms, The oxidation-resistant organic semiconductor material according to claim 3. In the general formula (2), in the substituent group (R ¹ and R ² ) and the substituent group (R ³ and R ⁴ ), the substituents in each group are bonded to each other to form a ring. The oxidation-resistant organic semiconductor material according to claim 4. The organic thin film using the oxidation-resistant organic-semiconductor material in any one of Claims 3-5. A dihalobiphenyl derivative represented by the following general formula (3) is dilithiated and / or diglynarized, and then reacted with a silane compound, germanium compound, or tin compound. A method for producing a spirobi (heterofluorene) derivative.

(Here, Ψ represents a silicon atom, a germanium atom, or a tin atom, and the substituents R ^{1 to} R ⁸ are the same or different, and are a hydrogen atom, a fluorine atom, an alkyl group having 5 to 20 carbon atoms, 20 represents a halogenated alkyl group, an aryl group having 4 to 30 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, wherein the substituent group (R ¹ and R ² ) and (The substituents in the substituent group (R ³ and R ⁴ ) can be bonded to each other to form a ring.)

(Here, the substituents X ¹ and X ² represent a bromine atom, an iodine atom or a chlorine atom, and the substituents R ^{1 to} R ⁸ have the same meaning as the substituent represented by the general formula (2).) The production method according to claim 7, wherein the production is performed in a dialkyl ether solvent. The method according to claim 7 or 8, wherein the silane compound is tetrahalogenated silane, tetraalkoxysilane, or dihalogenated dialkoxysilane. The method according to any one of claims 7 to 9, wherein the tetrahalogenated silane is tetrachlorosilane or tetrabromosilane.