JP4978003B2 - Dibenzosilole derivatives, precursor compounds thereof, and production methods thereof - Google Patents

Description

  The present invention relates to a dibenzosilole derivative that can be developed into an electronic material such as an organic semiconductor, its use, a precursor compound thereof, 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. Application can also be carried out using printing techniques without using high temperature and high vacuum conditions. The coating method is an economically preferable process because the manufacturing cost for device fabrication can be greatly reduced by printing. However, conventionally, there is a problem that a material having higher performance as an organic semiconductor has a difficulty in forming a semiconductor active phase by a coating method.

  For example, self-assembled materials such as poly- (3-hexylthiophene) are soluble in solvents, and device fabrication by coating has been reported, but the electron mobility is one order of magnitude lower than that of crystalline compounds (non- There is a problem that the characteristics of the obtained organic semiconductor device are low. On the other hand, it has been reported that crystalline materials such as pentacene have high carrier mobility similar to amorphous silicon and exhibit excellent semiconductor device characteristics (see Non-Patent Document 2). There has also been reported an attempt to produce a device by a coating method by dissolving polyacene such as pentacene (see Patent Document 1). However, since pentacene has low solubility due to its strong cohesiveness, conditions such as high-temperature heating are required to apply the coating method, and the solution of pentacene is extremely easily oxidized by air. The application of the law was a process and economic challenge.

These organic semiconductor materials are known to exhibit p-type semiconductor characteristics. In order to construct an energy-saving circuit, both p-type and n-type semiconductors are required. It is known that when hydrogen in a p-type organic semiconductor material is replaced with fluorine, a material exhibiting n-type semiconductor characteristics is obtained. For example, perfluoropentacene exhibits n-type semiconductor characteristics (see Non-Patent Document 3). However, there is a problem that a special fluorinating agent is required and the yield of fluorination is low. On the other hand, it has been disclosed that substituted siloles have an energy level of low LUMO (lowest orbital) and can be used as an electron transport material for organic EL (see Patent Document 2). Further, Non-Patent Document 4 discloses 2,5-bis (bipyridyl) -3,4-diphenylsilole. However, due to the low planar rigidity of the molecule, the electron mobility is as low as 2 × 10 ⁻⁴ cm ² / Vs, which is used as an electron transport material for organic EL elements. However, as an n-type semiconductor for organic transistors, It is not used (Non-Patent Document 4).

“Science”, (USA), 1998, 280, 1741-1744. “Journal of Applied Physics” (USA), 2002, 92, 5259-5263. “Journal of American Chemical Society” (USA), 2004, 126, 8138-8140 "Applied Physics Letters", (USA), 2002, 80, 189-191 WO2003 / 016599 Pamphlet JP-A-9-194487

  Accordingly, in view of the above-described problems of the prior art, the present invention has a dibenzosilole derivative having excellent oxidation resistance and capable of forming a semiconductor active phase by a coating method, and an oxidation resistant organic semiconductor using the same. The object is to provide materials and organic thin films.

  As a result of intensive studies to solve the above problems, the present inventors have found a novel dibenzosilole derivative. In addition, the inventors have found an oxidation-resistant organic semiconductor material comprising the dibenzosilole derivative and a thin film thereof. Furthermore, the inventors have found a precursor compound suitable for producing the dibenzosilol derivative and a production method thereof, and have completed the present invention.

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

（ここで、置換基Ｒ ^１ 、Ｒ ^４ 、Ｒ ^５ 及びＲ ^１０ は水素原子であり、置換基Ｒ ^２ 、Ｒ ^３ 、Ｒ ^７ 及びＲ ^８ は炭素数６〜３０のアリール基であるフェニル基、ｐ−トリル基、ｐ−（ｎ−オクチル）フェニル基、ｍ−（ｎ−オクチル）フェニル基、ｐ−メトキシフェニル基、ｐ−フェノキシフェニル基、１−ナフチル基、２−ナフチル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、１−ビフェニレノ基、２−ビフェニレノ基、ビフェニル基、（ジフェニルアミノ）フェニル基、（ジフェニルアミノ）ビフェニル基からなる群から選ばれる少なくとも一種以上の置換基であり、Ｒ ^１１ 及びＲ ^１２ は、炭素数１〜２０のアルキル基であるメチル基、エチル基、プロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ネオペンチル基、オクチル基、ドデシル基なる群から選ばれる少なくとも一種以上の置換基であり、ｎは０である。）
本発明の一般式（１）の置換基について、さらに述べる。

(Here, the substituents R ¹ , R ⁴ , R ⁵ and R ¹⁰ are hydrogen atoms, and the substituents R ² , R ³ , R ⁷ and R ⁸ are phenyl groups having 6 to 30 carbon atoms, p-tolyl group, p- (n-octyl) phenyl group, m- (n-octyl) phenyl group, p-methoxyphenyl group, p-phenoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 2-fluorenyl At least one substituent selected from the group consisting of a group, 9,9-dimethyl-2-fluorenyl group, 1-biphenyleno group, 2-biphenyleno group, biphenyl group, (diphenylamino) phenyl group, and (diphenylamino) biphenyl group a ^{group, R 11} and ^{R 12,} a methyl group, an ethyl group which is an alkyl group having 1 to 20 carbon atoms, a propyl group, n- butyl group, an isobutyl group, t- butyl group, Ne Pentyl group, octyl group, at least one or more substituents selected from dodecyl group consisting, n is 0.)
The substituent of the general formula (1) of the present invention will be further described.

The aryl group having 6 to 30 carbon atoms in the substituents R ^{1 to} R ¹⁴ 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, Preferred examples include 9,9-dimethyl-2-fluorenyl group, 1-biphenyleno group, 2-biphenyleno group, biphenyl group, perfluorobiphenyl group, (diphenylamino) phenyl group, (diphenylamino) biphenyl group, and the like. Are a phenyl group, a p- (trifluoromethyl) phenyl group, and a pentafluorophenyl group.

The heterocyclic group having 2 to 20 carbon atoms in the substituents R ^{1 to} R ¹⁴ is not particularly limited, and includes 2-thienyl group, 5- (n-hexyl) -2-thienyl group, and 2,2′-bithienyl-5. -Group, 2-pyridyl group, 3-pyridyl group, tetrafluoropyridyl group, 2,2'-bipyridyl-6-group, quinolyl group, 2-furyl group, 1-methyl-2-pyrrolyl group, 1-pyrrolyl group 1-indolyl group, 9-carbazolyl group, perfluoro-9-carbazolyl group, 2-oxadiazolyl group, 1-diazolyl group, 1-triazolyl group, triazinyl group, pyrazolyl group, isoxazolyl group, thiazolyl group, thiadiazolyl group, etc. Preferably, 5- (n-hexyl) -2-thienyl group, 2,2′-bithienyl-5 group, 2-pyridyl group, 3-pyridyl group, 2,2′-bi Pyridyl-6-group.

The diarylamino group having 8 to 30 carbon atoms in the substituents R ^{1 to} R ¹⁴ is not particularly limited, and examples thereof include a diphenylamino group, a phenyl (3-methylphenyl) amino group, a di (3-methylphenyl) amino group, and a di {4- (n-octyl) phenyl} amino group, di (3-trifluoromethylphenyl) amino group, (1-naphthyl) phenylamino group, di (1-naphthyl) amino group, phenyl (2-fluorenyl) amino Group, phenyl (9,9-dimethyl-2-fluorenyl) amino group, bis (2-fluorenyl) amino group, di (2-thienyl) amino group, phenyl (2-thienyl) amino group, bis {2- (1 -Phenyl) pyrrolyl} amino group, {2- (1-phenyl) pyrrolyl} phenylamino group, and the like.

The alkynyl group having 2 to 20 carbon atoms in the substituents R ^{1 to} R ¹⁴ is not particularly limited. For example, ethynyl group, methyl ethynyl group, isopropyl ethynyl group, tert-butyl ethynyl group, (n-octyl) ethynyl group, tri Fluoromethylethynyl group, phenylethynyl group, naphthylethynyl group, anthracenylethynyl group, biphenylenoethynyl group, biphenylethynyl group, terphenylethynyl group, benzylethynyl group, perfluorophenylethynyl group, {p- (trifluoromethyl ) Phenyl} ethynyl group, (n-perfluorooctyl) ethynyl group, (trimethylsilyl) ethynyl group, (triethylsilyl) ethynyl group, (triisopropylsilyl) ethynyl group, and the like. Preferably, it is an alkynyl group having 4 to 20 carbon atoms not containing a silyl group, for example, (n-octyl) ethynyl group, phenylethynyl group, naphthylethynyl group, biphenylethynyl group, terphenylethynyl group, benzylethynyl group, par A fluorophenylethynyl group;

The alkenyl group having 2 to 30 carbon atoms in the substituents R ^{1 to} R ¹⁴ is not particularly limited. For example, ethenyl group, methyl ethenyl group, isopropyl ethenyl group, tert-butyl ethenyl group, (n-octyl) ethenyl group, (tri Fluoromethyl) ethenyl group, phenylethenyl group, diphenylethenyl group, triphenylethenyl group, naphthylethenyl group, anthracenylethenyl group, biphenylenoethenyl group, biphenylethenyl group, terphenylethenyl group, benzylethenyl group Examples thereof include a tenenyl group, a phenyl (methyl) ethenyl group, a perfluorophenylethenyl group, a {p- (trifluoromethyl) phenyl} ethenyl group, and an (n-perfluorooctyl) ethenyl group. 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 alkyl group having 1 to 20 carbon atoms in the substituents R ^{1 to} R ¹⁴ is not particularly limited. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a t-butyl group, a neopentyl group, and an octyl group. Group, a dodecyl group, etc. can be mentioned; A C1-C20 halogenated alkyl group is not specifically limited, A trifluoromethyl group, a trifluoroethyl group, a perfluorooctyl group etc. can be mentioned.

Of the substituents R ^{1 to} R ¹⁴ , any two or more substituents may be bonded to each other to form a saturated hydrocarbon ring or an unsaturated ring. The saturated hydrocarbon ring or the unsaturated ring is not particularly limited, for example, a cyclohexene ring that may have a substituent, a thiophene ring that may have a substituent, a benzene ring that may have a substituent, A naphthalene ring which may have a substituent, a silole ring which may have a substituent, and the like can be given. More specific examples of the silole ring that may have a substituent include, for example, a silafluorene ring.

Preferred examples of the substituents R ^{1 to} R ¹⁴ include a hydrogen atom, a fluorine atom, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a diarylamino group having 8 to 30 carbon atoms, and 2 to 2 carbon atoms. 20 alkynyl groups and alkyl groups having 1 to 20 carbon atoms, and more preferred examples are hydrogen atoms, aryl groups having 6 to 30 carbon atoms, heterocyclic groups having 2 to 20 carbon atoms, and alkyl groups having 1 to 20 carbon atoms. It is.

As a preferable substitution mode of the dibenzosilole derivative represented by the general formula (1) of the present invention, the substituents R ² , R ³ , R ⁷ and R ⁸ are a fluorine atom, an aryl group having 6 to 30 carbon atoms, and 2 to 2 carbon atoms. 20 heterocyclic groups, C8-30 diarylamino groups, C2-20 alkynyl groups, C2-30 alkenyl groups, C1-20 alkyl groups, and C1-20 halogens Or at least one substituent selected from the group consisting of an alkyl group, or the substituents R ² and R ³ and / or R ⁷ and R ⁸ are bonded to each other to form an unsaturated ring, and the substituent R ¹ , R ⁴ , R ⁵ , R ⁶ , R ⁹ and R ¹⁰ may be a dibenzosilole derivative which is hydrogen or a fluorine atom, preferably hydrogen.

  In the dibenzosilole derivative represented by the general formula (1) of the present invention, preferably n = 0.

  There is no limitation in particular in the dibenzosilol derivative shown by General formula (1) of this invention, For example, the following compounds can be mentioned.

（ジベンゾシロール誘導体製造方法）
次に、本発明の一般式（１）で表されるジベンゾシロール誘導体の製造方法について述べる。

(Dibenzosilol derivative production method)
Next, the manufacturing method of the dibenzosilol derivative represented by General formula (1) of this invention is described.

  The dibenzosilole derivative represented by the general formula (1) of the present invention is produced by lithiation and / or Grignard conversion of a tetrahaloterphenyl derivative represented by the following general formula (2) and then reacting with a dihalosilicon compound. Can do.

（ここで、置換基Ｘ^１〜Ｘ^４は臭素原子、ヨウ素原子又は塩素原子を示す。置換基Ｒ^１〜Ｒ^１０及び記号ｎは一般式（１）で示される置換基及び記号と同意義を示す。）
一般式（２）におけるＸ^１〜Ｘ^４は好ましくは臭素原子又はヨウ素原子である。

(Here, the substituents X ^{1 to} X ⁴ represent a bromine atom, an iodine atom or a chlorine atom. The substituents R ^{1 to} R ¹⁰ and the symbol n have the same meaning as the substituent and the symbol represented by the general formula (1). Show.)
X ^{1 to} X ⁴ in the general formula (2) are preferably a bromine atom or an iodine atom.

When lithiating the tetrahaloterphenyl derivative represented by the general formula (2), the lithiating agent to be used is particularly as long as the halogen X ^{1 to} X ⁴ in the general formula (2) can be substituted with lithium. Without limitation, for example, alkyllithium such as n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, hexyllithium; phenyllithium, p-tert-butylphenyllithium, p-methoxyphenyllithium, p- Aryl lithium such as fluorophenyl lithium; lithium amide such as lithium diisopropylamide and lithium hexamethyldisilazide; lithium metal such as lithium powder. Alkyl lithium is preferable, and n-butyl lithium, sec-butyl lithium, and tert-butyl lithium are particularly preferable.

The amount of the lithiating agent used is such that the tetrahaloterphenyl derivative represented by the general formula (2) is converted to a lithium represented by the general formula (2) in order to convert the halogen of X ^{1 to} X ⁴ into lithium and lithiate. It can be used in the range of 1.5 to 20 equivalents, preferably 1.8 to 15 equivalents, more preferably 2 to 10 equivalents, relative to the haloterphenyl derivative. By using 2 equivalents or more of the lithiating agent, the conversion rate to lithiation is improved, and when it is 20 equivalents or less, lithiation can be performed economically and without increasing the amount of by-products.

  The lithiation reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include tetrahydrofuran (hereinafter abbreviated as THF), diethyl ether, ethylene glycol dimethyl ether, dioxane, toluene, pentane, hexane, cyclohexane, and the like, and particularly preferably THF and diethyl ether. These solvents may be used alone or as a mixture of two or more.

  The lithiation reaction temperature is -100 to 50 ° C, preferably -90 to 20 ° C. The reaction time is 1 to 120 minutes, preferably 1 to 60 minutes. The progress of the lithiation reaction can be monitored by taking out a part of the reaction solution, stopping the reaction with water, and then analyzing by gas chromatography.

  The lithium salt produced by the lithiation reaction is then reacted with a dihalosilicon compound. The reaction with the dihalosilicon compound is a method of reacting the reaction mixture containing the lithium salt generated by the lithiation reaction by directly using the dihalosilicon compound, and once reacting with the dihalosilicon compound after isolating the generated lithium salt. Any of the methods may be used.

  The dihalosilicon compound used for the reaction between the lithium salt and the dihalosilicon compound is not particularly limited, and examples thereof include dichlorodimethylsilane, dibromodimethylsilane, and dichlorodiethylsilane. Dichlorodi (isobutyl) silane, dichloro (n-dioctyl) silane, dichloromethyl (phenyl) silane, dichlorodiphenylsilane, dibromodiphenylsilane, dichlorodi {4- (n-octyl) phenyl} silane, dichlorodi (p-fluorophenyl) silane , Dichlorodi {p- (trifluoromethyl) phenyl} silane, dichlorodi {bi (pentafluorophenyl)} silane, dichlorodi (biphenyl) silane, dichlorodi {bi (pentafluorophenyl)} silane, dichloro (1-naphthyl) phenylsilane Dichlorodi (1-naphthyl) silane, dichlorodi (2-naphthyl) silane, dichlorodi (pyridyl) silane, dichlorodi (bipyridyl) silane, 1,1-dichlorosilole, 9,9-dichlorosilafluorene, etc.

  The reaction between the resulting lithium salt and the dihalosilicon compound is preferably carried out in a solvent. The solvent to be used is not specifically limited, For example, the solvent used for the lithiation reaction can be mentioned. The amount of the dihalosilicon compound to be used is 0.9 to 10 equivalents, preferably 1.0 to 5 equivalents, relative to the tetrahaloterphenyl derivative of the general formula (2). The reaction temperature with the dihalosilicon compound is −100 to 50 ° C., preferably −90 to 30 ° C., and the reaction time is 1 to 30 hours, preferably 1 to 18 hours.

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

  The dibenzosilol 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 tetrahaloterphenyl derivative represented by the general formula (2) is Grignarded, examples of the Grignard agent to be used include Mg metal or alkyl Grignard reagents such as ethylmagnesium bromide and isopropylmagnesium bromide. However, Mg metal is preferable. 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 tetrahaloterphenyl 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 a solvent using a lithiation reaction. The temperature of the Grignard reaction is -20 to 80 ° C, and the reaction time is in the range of 1 to 120 minutes.

  The magnesium salt produced by the Grignard reaction is then reacted with a dihalosilicon compound. The reaction method with the dihalosilicon compound and the dihalosilicon compound to be used can be carried out in the same manner as in the case of reacting the lithium salt produced by the lithiation reaction with the dihalosilicon compound. The reaction atmosphere and the reaction product can be purified in the same manner.

  In the dibenzosilole derivative represented by the general formula (1) of the present invention, when producing a dibenzosilole derivative where n = 0, the tetrahaloterphenyl derivative represented by the general formula (2) is n = 0. A tetrahaloterphenyl derivative may be used. The tetrahaloterphenyl derivative in which n = 0 is represented as a dihalobiphenyl derivative represented by the following general formula (3).

（ここで、置換基Ｒ^１〜Ｒ^５、Ｒ^７、Ｒ^８、Ｒ^１０、Ｘ^１、及びＸ^２は一般式（２）で示される置換基と同意義を示す。）
さらに、好ましい一般式（３）で示されるジハロビフェニル誘導体として、置換基Ｒ^２、Ｒ^３、Ｒ^７及びＲ^８が炭素数６〜３０のアリール基、炭素数２〜２０の複素環基、炭素数８〜３０のジアリールアミノ基、炭素数２〜２０のアルキニル基、及び炭素数２〜３０のアルケニル基からなる群から選ばれる少なくとも１以上の置換基であるジハロビフェニル誘導体を挙げることができる。

(Here, the substituents R ^{1 to} R ⁵ , R ⁷ , R ⁸ , R ¹⁰ , X ¹ , and X ² have the same meaning as the substituent represented by the general formula (2).)
Furthermore, as a preferable dihalobiphenyl derivative represented by the general formula (3), the substituents R ² , R ³ , R ⁷ and R ⁸ are aryl groups having 6 to 30 carbon atoms, heterocyclic groups having 2 to 20 carbon atoms, Examples include dihalobiphenyl derivatives that are at least one substituent selected from the group consisting of a diarylamino group having 8 to 30 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an alkenyl group having 2 to 30 carbon atoms. it can.

  There is no limitation in particular as a dihalobiphenyl derivative shown by General formula (3), For example, the following compounds can be mentioned.

なお、係る一般式（３）で示されるジハロビフェニル誘導体を用いて、本発明の一般式（１）で示されるジベンゾシロール誘導体においてｎ＝０であるジベンゾシロール誘導体を製造する場合も、上記のジベンゾシロール誘導体製造方法で製造できる。

In addition, when manufacturing the dibenzosilol derivative in which n = 0 in the dibenzosilole derivative represented by the general formula (1) of the present invention using the dihalobiphenyl derivative represented by the general formula (3), It can be produced by a dibenzosilol derivative production method.

  However, when the dihalobiphenyl derivative represented by the formula (3) is dilithiated and then reacted with a dihalosilicon compound, the amount of the dilithiating agent used is preferably the same as the dihalobiphenyl derivative of the general formula (3). On the other hand, it is 1.5 to 2.8 equivalents. The amount of the dihalosilicon compound used is preferably 0.8 to 2 equivalents relative to the dihalobiphenyl derivative of the general formula (3).

When the dihalobiphenyl derivative represented by the general formula (3) is diglynarized, the amount of the diglynarizing agent used is, for example, Mg metal, preferably the dihalobiphenyl derivative of the general formula (3) It is 1.8-10 equivalent with respect to.

(Tetrahaloterphenyl derivative, dihalobiphenyl derivative production method)
The tetrahaloterphenyl derivative represented by the general formula (2), which is a precursor of the dibenzosilol derivative represented by the general formula (1), can be derived from the dihalobenzene derivative represented by the following general formula (4).

（ここで、置換基Ｘ^１及びＲ^１〜Ｒ^４は一般式（３）で示される置換基と同意義を示す。）
一般式（４）で示されるジハロベンゼン誘導体として、好ましくは、置換基Ｒ^２及びＲ^３が炭素数６〜３０のアリール基、炭素数２〜２０の複素環基、炭素数８〜３０のジアリールアミノ基、及びシリル基を含まない炭素数４〜２０のアルキニル基からなる群から選ばれる少なくとも１以上の置換基であるジハロベンゼン誘導体を挙げることができる。

(Here, the substituents X ¹ and R ^{1 to} R ⁴ have the same meaning as the substituent represented by the general formula (3).)
As the dihalobenzene derivative represented by the general formula (4), the substituents R ² and R ³ are preferably an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a diarylamino having 8 to 30 carbon atoms. And a dihalobenzene derivative which is at least one substituent selected from the group consisting of a group and a C 4-20 alkynyl group not containing a silyl group.

  There is no limitation in particular in the dihalobenzene derivative shown by General formula (4), For example, the following compounds can be mentioned.

なお、一般式（２）で示されるテトラハロターフェニル誘導体においてｎ＝１の場合は、好ましくは、一般式（４）で示されるジハロベンゼン誘導体を、例えば、イソプロピルマグネシウムブロマイド等のグリニャール試薬あるいはｎ−ブチルリチウム等の有機リチウム試薬によりハロゲン／金属交換反応を行った後、塩化亜鉛、トリメトキシボラン等と反応させることで２−ハロアリール亜鉛化合物又は２−ハロアリールボロン酸とし、係る化合物と下記一般式（７）で示されるテトラハロベンゼン誘導体をパラジウム触媒を用いてクロスカップリングすることにより製造することができる。

When n = 1 in the tetrahaloterphenyl derivative represented by the general formula (2), the dihalobenzene derivative represented by the general formula (4) is preferably converted to a Grignard reagent such as isopropyl magnesium bromide or n- After a halogen / metal exchange reaction with an organolithium reagent such as butyllithium, a 2-haloarylzinc compound or 2-haloarylboronic acid is obtained by reacting with zinc chloride, trimethoxyborane, etc. The tetrahalobenzene derivative represented by (7) can be produced by cross-coupling using a palladium catalyst.

（ここで、置換基Ｘ^６は臭素原子又はヨウ素原子を示す。置換基Ｘ^２、Ｘ^３、Ｒ^５及びＲ^１０は一般式（２）で示される置換基と同意義を示す。）
即ち、一般式（７）で示されるテトラハロベンゼン誘導体に対し、一般式（４）で示されるジハロベンゼン誘導体から調製された２−ハロアリール亜鉛化合物又は２−ハロアリールボロン酸を２当量用いることで一般式（２）で示されるテトラハロターフェニル誘導体を製造することができる。この反応において一般式（７）で示されるテトラハロベンゼン誘導体の反応する位置は、ハロゲンの種類により制御することができる。即ち、ヨウ素の反応性が最も高く、臭素、塩素の順に反応性が低下することから、これらハロゲンの種類の反応性を利用することでテトラハロベンゼン誘導体の２つのＸ^６の位置で炭素−炭素結合を形成させることができる。

(Here, the substituent X ⁶ represents a bromine atom or an iodine atom. The substituents X ² , X ³ , R ⁵ and R ¹⁰ have the same meaning as the substituent represented by the general formula (2).)
That is, the 2-haloaryl zinc compound or 2-haloaryl boronic acid prepared from the dihalobenzene derivative represented by the general formula (4) is used in an amount equivalent to the tetrahalobenzene derivative represented by the general formula (7). A tetrahaloterphenyl derivative represented by the formula (2) can be produced. In this reaction, the position at which the tetrahalobenzene derivative represented by the general formula (7) reacts can be controlled by the type of halogen. That is, the reactivity of iodine is the highest, and the reactivity decreases in the order of bromine and chlorine. Therefore, by utilizing the reactivity of these halogen types, carbon-carbon is obtained at two X ⁶ positions of the tetrahalobenzene derivative. Bonds can be formed.

  Further, the tetrahaloterphenyl derivative with n = 1 represented by the general formula (2) is a 2-haloaryl zinc compound or 1 equivalent of a 2-haloarylboronic acid prepared from a dihalobenzene derivative represented by the general formula (4), It can also be produced using 1 equivalent of a tetrahalobenzene derivative represented by the general formula (7) and 1 equivalent of a 2-haloaryl metal reagent represented by the following general formula (8).

（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^５、Ｒ^７、Ｒ^８及びＲ^１０は一般式（３）で示される置換基と同意義を示す。）
一方、一般式（２）で示されるテトラハロターフェニル誘導体においてｎ＝０の場合は、即ち一般式（３）で示されるジハロビフェニル誘導体の場合は、好ましくは、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, M represents a halide, hydroxide, alkoxide or alkylated product of Mg, B, Zn, Sn or Si . The substituents X ² , R ⁵ , R ⁷ , R ⁸ and R ¹⁰ are represented by the general formula (3 And the same meaning as the substituent represented by
On the other hand, when n = 0 in the tetrahaloterphenyl derivative represented by the general formula (2), that is, in the case of the dihalobiphenyl derivative represented by the general formula (3), it is preferably represented by the general formula (4). The dihalobenzene derivative can be produced by homocoupling 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 N, N-diisopropylamide and lithium hexamethyl. A disilazide etc. can be mentioned. 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, 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 1 to 240 minutes, preferably 3 to 120 minutes.

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 and isopropylmagnesium bromide can be mentioned, and 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 particularly limited, and examples thereof include a solvent using a lithiation reaction. The temperature of the Grignard reaction is -20 to 120 ° C, and the reaction time is in the range of 1 to 120 minutes.

  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.

  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 cross-linking a dihalobenzene derivative represented by the general formula (4) and a 2-haloaryl metal reagent represented by the general formula (8) in the presence of a palladium and / or nickel catalyst. It can be manufactured by ringing.

The substituent M in the general formula (8) 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 (8) is obtained by, for example, halogen / metal exchange using an aryl dihalogen-substituted product as a raw material with 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 (8) 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 / tri-tert-butylphosphine mixture, palladium acetate / 2- (dicyclohexylphosphino) -1,1'-biphenyl mixture, dichloro (ethylenediamine) palladium, dichloro (N, N, N ', N'- There may be mentioned zero-valent or divalent palladium compounds such as tetramethylethylenediamine) palladium, dichloro (N, N, N ′, N′-tetramethylethylenediamine) palladium / triphenylphosphine mixture; 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′-tetramethylethylenediamine) nickel / triphenylphosphine mixture, bis (1,5-cyclooctadiene) nickel / triphenylphosphine mixture, etc. it can. 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 0.5 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 (8) used is 0.6 to 1.5 equivalents, preferably 0.8 to 1.4 equivalents, more preferably 0, relative to 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, dioxane, ethylene glycol dimethyl ether, toluene, xylene, hexane, cyclohexane, ethanol, water, and the like. These solvents may be used alone or as a mixture of two or more. good. 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 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 catalyst used in the cross-coupling reaction.

  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 a cross-coupling of a tetrahalobenzene derivative represented by the following general formula (5) and a reactant represented by the following general formula (6) in the presence of a palladium and / or nickel catalyst. It can be produced by reacting.

（ここで、置換基Ｘ^５はヨウ素原子又は臭素原子を示し、置換基Ｘ^１、Ｒ^１及びＲ^４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^５は、好ましくはヨウ素原子である。

(Here, the substituent X ⁵ represents an iodine atom or a bromine atom, and the substituents X ¹ , R ¹ and R ⁴ have the same meaning as the substituent represented by the general formula (4).)
Incidentally, the substituent X ⁵ is preferably a iodine atom.

AM (6)
(Here, A is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a diarylamino group having 8 to 30 carbon atoms, an alkynyl group having 4 to 20 carbon atoms that does not include a silyl group, An alkenyl group having 2 to 30 carbon atoms, or an alkyl group or halogenated alkyl group having 1 to 20 carbon atoms, wherein M is a hydrogen atom, an alkali metal of Li , Na or K, Mg, B, Zn, Sn or Si ; Halide, hydroxide, alkoxide or alkylated product is shown.)
The substituent A of the general formula (6) is preferably an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a diarylamino group having 8 to 30 carbon atoms, or a carbon number not containing a silyl group. It is a 4-20 alkynyl group, More preferably, it is a C6-C30 aryl group and a C2-C20 heterocyclic group.

The substituent M in the general formula (6) is 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. Alternatively, there is no particular limitation as long as it is a group capable of reacting with a nickel catalyst and substituting with palladium and / or nickel. 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 (6) is, for example, a halogen / metal exchange reaction of an aryl halogen-substituted product as a raw material with a Grignard reagent such as isopropylmagnesium bromide or an organic lithium reagent such as n-butyllithium. 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 (6) may be used.

  The catalyst used for the cross-coupling reaction of the tetrahalobenzene derivative represented by the general formula (5) and the reactant represented by the general formula (6) 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 (8) 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 0.5 to 20 mol% with respect to the tetrahalobenzene derivative of the general formula (5). The amount of the reactant of the general formula (6) used is 1.4 to 3.5 equivalents relative to the tetrahalobenzene derivative of the general formula (5) when one kind of the reactant of the general formula (6) 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 (6) are used, the general formula The tetrahalobenzene derivative (5) is 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 (6) are used, 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, dioxane, ethylene glycol dimethyl ether, toluene, xylene, hexane, cyclohexane, ethanol, water, and the like. These solvents may be used alone or as a mixture of two or more. good. 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. The amount of these bases used can be 1.5 to 10.0 equivalents, preferably 2.0 to 8.0 equivalents, relative to the tetrahalobenzene derivative of the general formula (5). 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 (5).

  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 (5) and the reactant of the general formula (6) 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.

Accordingly, the general formula X ⁵ (5) as a iodine, by a X ¹ is bromine and / or chlorine, to obtain the synthesis of the dihalobenzene derivative represented by the general formula (4).

  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.

In the dihalobenzene derivative represented by the general formula (4), the alkynyl group in which the substituents R ^{1 to} R ⁴ include an alkynyl group having 1 to 3 carbon atoms or a silyl group having 4 to 20 carbon atoms can be obtained by a known method, for example, Sinlet, 2003, pages 29-34 and Sinlet, 2004, pages 165-168.

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.
(Oxidation-resistant organic semiconductor materials)
Next, the oxidation-resistant organic semiconductor material containing the dibenzosilole 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.

  The solvent used for dissolving the dibenzosilole derivative represented by the general formula (1) of the present invention is preferably a halogen-based solvent containing halogen such as chlorine, such as o-dichlorobenzene, 1,2-dichloroethane, 1,1, 2,2-tetrachloroethane, chloroform; ether solvents containing 1 to 2 oxygens such as THF, dioxane; aromatic hydrocarbon solvents such as toluene, xylene; ester solvents such as ethyl acetate, 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.

  By mixing and stirring the above-mentioned solvent and the dibenzosilol derivative represented by the general formula (1), a solution of an oxidation-resistant organic semiconductor containing the dibenzosilol derivative represented by the general formula (1) can be prepared. . The temperature in this case is 20 to 200 ° C., preferably 30 ° C. to 190 ° C. If it is lower than 20 ° C., the concentration becomes too low and it is difficult to obtain a good thin film, which is not preferred. The concentration of the resulting solution can be varied depending on the solvent and temperature, but is 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 dibenzosilol 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 suitably 0.5 minutes to 1 hour. The progress of oxidation can be performed by changing the color of the solution and detecting the oxide by gas chromatography and gas chromatography-mass spectrum (GCMS) analysis.

The solution of the oxidation-resistant organic semiconductor material containing the dibenzosilole derivative represented by the general formula (1) of the present invention is compared because the dibenzosilole derivative itself represented by the general formula (1) used has a suitable cohesiveness. In particular, since it can be dissolved in a solvent at 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 addition, in order to obtain suitable coating property, the viscosity of the solution of the oxidation-resistant organic semiconductor material containing the dibenzosilol derivative represented by the general formula (1) of the present invention is in the range of 0.1 to 20 poise. Is preferred.
(Organic thin film)
Next, an organic thin film using an oxidation-resistant organic semiconductor material containing the dibenzosilole 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 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 of the general formula (1) 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. Further, it can be produced using a printing technique such as screen printing or inkjet 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. 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 dibenzosilol derivative represented by the general formula (1) 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 15 nm-100 micrometers, Most preferably, it is 10 nm-20 micrometers.

  Since the dibenzosilole 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. Further, the dibenzosilole 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. Accordingly, the dibenzosilole derivative represented by the general formula (1) of the present invention is used for an organic semiconductor active phase of a transistor such as an electronic paper, an organic EL display, a liquid crystal display, or an IC tag, and further an electron transport agent for an organic EL display, It can be used for an organic semiconductor laser material, an organic thin film solar cell material, a photonic crystal material, or the like.

  Disclosed are a dibenzosilol derivative having excellent oxidation resistance and capable of forming a semiconductor active phase by a coating method, and uses thereof. Furthermore, in the production method of the present invention, a dibenzosilole 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. Mass spectrum (MS) was measured by electron impact (EI) method (70 electron volts) by directly introducing a sample using JEOL JMS-700 manufactured by JEOL.

  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-1,30
A commercially available dehydrated solvent was used as the solvent for the reaction.

Synthesis Example 1 (Synthesis of 1,2-dibromo-4,5-diiodobenzene)
The raw material 1,2-dibromo-4,5-diiodobenzene was synthesized according to the method described in “Sinlet”, 2003, pp. 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 (318 mmol) of 1,2-dibromobenzene 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).
Example 1 (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 1 in a 200 ml Schlenk reaction vessel, tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 600 mg (0.519 mmol) and phenylboronic acid (manufactured by Wako Pure Chemical Industries, Ltd.) 1.920 mg (15.7 mmol) 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 tert-butyl hydroperoxide (70% aqueous solution) 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), and 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).
The structure of the obtained target product is shown below.

実施例２ （１，２−ジブロモ−４，５−ビス｛４−（トリフルオロメチル）フェニル｝ベンゼンの合成）
窒素雰囲気下、１００ｍｌシュレンク反応容器に４−ヨードベンゾトリフルオライド３．７０ｇ（１３．６ｍｍｏｌ）及びＴＨＦ２８ｍｌを添加した。この溶液を−３０℃に冷却し、イソプロピルマグネシウムブロマイド（関東化学製、０．６５Ｍ）のＴＨＦ溶液２１ｍｌ（１３．６ｍｍｏｌ）を滴下した。３０分間熟成後、その温度で塩化亜鉛（シグマ−アルドリッチ製、１．０Ｍ）のジエチルエーテル溶液１３ｍｌ（１３ｍｍｏｌ）を滴下した。徐々に室温まで昇温した後、生成した淡黄色スラリー液を減圧濃縮した。得られたあずき色粘性物に、合成例１で合成した１，２−ジブロモ−４，５−ジヨードベンゼン２．２２ｇ（４．５５ｍｍｏｌ）、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）１７４ｍｇ（０．１５ｍｍｏｌ）、及びＴＨＦ５６ｍｌを添加した。６５℃で４時間反応を実施した後、容器を水冷し３Ｎ塩酸６ｍｌを添加することで反応を停止させた。トルエン及び食塩を添加し、分相後、有機相を水で２回洗浄した。全体を減圧濃縮し、溶媒を留去した。得られた残渣をトルエン１５ｍｌに溶解後、ｔｅｒｔ−ブチルハイドロパーオキサイド（７０％水溶液）０．２３ｍｌを添加し、室温で２時間撹拌した。このトルエン溶液を水で２回洗浄後、有機相を減圧濃縮し、得られた残渣をシリカゲル（１０ｇ）を充填したカラムで濾過した（溶媒、ヘキサン）。濾液を減圧濃縮し、得られた残渣をガラスチューブオーブンを用いて減圧蒸留を実施し、１９Ｐａで１５０〜２００℃の留分を取り出した（１．２２ｇ）。さらにこの留分をヘプタンから再結晶精製し、１，２−ジブロモ−４，５−ビス｛４−（トリフルオロメチル）フェニル｝ベンゼンの結晶を得た（８４２ｍｇ、収率３５％）。

Example 2 (Synthesis of 1,2-dibromo-4,5-bis {4- (trifluoromethyl) phenyl} benzene)
Under a nitrogen atmosphere, 3.70 g (13.6 mmol) of 4-iodobenzotrifluoride and 28 ml of THF were added to a 100 ml Schlenk reaction vessel. The solution was cooled to −30 ° C., and 21 ml (13.6 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65 M) was added dropwise. After aging for 30 minutes, 13 ml (13 mmol) of a diethyl ether solution of zinc chloride (manufactured by Sigma-Aldrich, 1.0 M) was added dropwise at that temperature. After gradually warming to room temperature, the produced pale yellow slurry was concentrated under reduced pressure. To the obtained maroon viscous material, 2.22-g (4.55 mmol) of 1,2-dibromo-4,5-diiodobenzene synthesized in Synthesis Example 1 and tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 174 mg (0.15 mmol) and 56 ml of THF were added. After carrying out the reaction at 65 ° C. for 4 hours, the reaction was stopped by cooling the vessel with water and adding 6 ml of 3N hydrochloric acid. Toluene and sodium chloride were added, and after phase separation, the organic phase was washed twice with water. The whole was concentrated under reduced pressure, and the solvent was distilled off. The obtained residue was dissolved in 15 ml of toluene, 0.23 ml of tert-butyl hydroperoxide (70% aqueous solution) 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 filtered through a column packed with silica gel (10 g) (solvent, hexane). The filtrate was concentrated under reduced pressure, and the resulting residue was subjected to vacuum distillation using a glass tube oven, and a fraction at 150 to 200 ° C. was taken out at 19 Pa (1.22 g). Further, this fraction was recrystallized and purified from heptane to obtain 1,2-dibromo-4,5-bis {4- (trifluoromethyl) phenyl} benzene crystals (842 mg, yield 35%).

¹ H NMR (CDCl ₃ , 21 ° C.): δ = 7.69 (s, 2H), 7.51 (d, J = 8.3 Hz, 2H), 7.20 (d, J = 8.1 Hz, 2H) ).
^{MS m / z: 524 (M} +, 52%), 444 (M + -Br, 10), 376 (M + - (Br + CF 3) +1,64), 364 (M + -2Br, 100).
The structure of the obtained target product is shown below.

実施例３ （１，２−ジブロモ−４，５−ビス｛２−（ピリジル）｝ベンゼンの合成）
窒素雰囲気下、１００ｍｌシュレンク反応容器に４−ヨードピリジン６４１ｍｇ（３．１３ｍｍｏｌ）及びＴＨＦ６ｍｌを添加した。この溶液を−１７℃に冷却し、イソプロピルマグネシウムブロマイド（東京化成工業製、０．８１Ｍ）のＴＨＦ溶液３．７ｍｌ（３．０ｍｍｏｌ）を滴下した。３０分間熟成後、その温度で塩化亜鉛（シグマ−アルドリッチ製、１．０Ｍ）のジエチルエーテル溶液３．１ｍｌ（３．１ｍｍｏｌ）を滴下した。徐々に室温まで昇温した後、生成したスラリー液を減圧濃縮した。得られた固形物に、合成例１で合成した１，２−ジブロモ−４，５−ジヨードベンゼン５０９ｇ（１．０４ｍｍｏｌ）、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）９０ｍｇ（０．０７８ｍｍｏｌ）、及びＴＨＦ１６ｍｌを添加した。６０℃で２５時間反応を実施した後、容器を水冷し３Ｎ塩酸６ｍｌを添加することで反応を停止させた。トルエンを添加して分相後、水相にもう一度トルエンを添加し洗浄し、得られた水相に苛性ソーダを添加し、アルカリ性とした後、トルエンで２回抽出した。無水硫酸ナトリウムで乾燥し、濾過、減圧濃縮した。得られた残渣をガラスチューブオーブンを用いて減圧蒸留を実施し、２７Ｐａで８０〜１３０℃の留分を取り出した（１１５ｍｇ、収率２８％）。

Example 3 Synthesis of 1,2-dibromo-4,5-bis {2- (pyridyl)} benzene
Under a nitrogen atmosphere, 641 mg (3.13 mmol) of 4-iodopyridine and 6 ml of THF were added to a 100 ml Schlenk reaction vessel. The solution was cooled to −17 ° C., and 3.7 ml (3.0 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.81M) was added dropwise. After aging for 30 minutes, 3.1 ml (3.1 mmol) of a diethyl ether solution of zinc chloride (manufactured by Sigma-Aldrich, 1.0 M) was added dropwise at that temperature. After gradually raising the temperature to room temperature, the produced slurry was concentrated under reduced pressure. To the obtained solid, 509 g (1.04 mmol) of 1,2-dibromo-4,5-diiodobenzene synthesized in Synthesis Example 1 and 90 mg of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.). 078 mmol), and 16 ml of THF were added. After carrying out the reaction at 60 ° C. for 25 hours, the vessel was cooled with water and the reaction was stopped by adding 6 ml of 3N hydrochloric acid. Toluene was added and the phases were separated. Toluene was once again added to the aqueous phase for washing, and caustic soda was added to the obtained aqueous phase to make it alkaline, followed by extraction with toluene twice. The extract was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The obtained residue was subjected to vacuum distillation using a glass tube oven, and a fraction at 80 to 130 ° C. was taken out at 27 Pa (115 mg, yield 28%).

¹ H NMR (CDCl ₃ , 21 ° C.): δ = 8.63-8.58 (m, 2H), 7.96 (s, 2H), 7.47 (dt, J = 7.8 Hz, 1.7 Hz) , 2H), 7.20-7.13 (m, 2H), 6.95 (d, J = 7.8 Hz, 2H).
MS m / z: 389 (M ⁺ -1,100%), 310 (M ⁺ -Br, 8), 229 (M ⁺ -1-2Br, 42).
The structure of the obtained target product is shown below.

実施例４ （４，５，４’，５’−テトラフェニル−２，２’−ジブロモ−１，１’−ビフェニルの合成）
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１，２−ジブロモ−４，５−ジフェニルベンゼン７１７ｍｇ（１．８５ｍｍｏｌ）及びＴＨＦ１４ｍｌを添加した。この溶液を−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０．５８ｍｌ（０．９２ｍｍｏｌ）を滴下した。一晩かけて室温まで昇温した後、生成した固体を濾過して取り出し、水で洗浄した。この得られた粗固体をトルエンから再結晶化し、目的物の白色固体を得た（４８１ｍｇ、収率８４％）。

Example 4 (Synthesis of 4,5,4 ′, 5′-tetraphenyl-2,2′-dibromo-1,1′-biphenyl)
Under a nitrogen atmosphere, 717 mg (1.85 mmol) of 1,2-dibromo-4,5-diphenylbenzene synthesized in Example 1 and 14 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −78 ° C., and 0.58 ml (0.92 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 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 desired white solid (481 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).
The structure of the obtained target product is shown below.

実施例５ （４，５，４’，５’−テトラキス｛４−（トリフルオロメチル）フェニル｝−２，２’−ジブロモ−１，１’−ビフェニルの合成）
窒素雰囲気下、１００ｍｌシュレンク反応容器に実施例２で合成した１，２−ジブロモ−４，５−ビス｛４−（トリフルオロメチル）フェニル｝ベンゼン７６４ｍｇ（１．４６ｍｍｏｌ）及びＴＨＦ１５ｍｌを添加した。この溶液を−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０．４６ｍｌ（０．７３ｍｍｏｌ）を滴下した。一晩かけて室温まで昇温した後、飽和食塩水及びトルエンを添加した。分相し、有機相を水で洗浄し、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、得られた粗固体をヘキサンから再結晶化し、目的物の白色固体を得た（２１４ｍｇ、収率３３％）。

Example 5 (Synthesis of 4,5,4 ′, 5′-tetrakis {4- (trifluoromethyl) phenyl} -2,2′-dibromo-1,1′-biphenyl)
Under a nitrogen atmosphere, 764 mg (1.46 mmol) of 1,2-dibromo-4,5-bis {4- (trifluoromethyl) phenyl} benzene synthesized in Example 2 and 15 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −78 ° C., and 0.46 ml (0.73 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, saturated brine and toluene were added. 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 crude solid was recrystallized from hexane to obtain the desired white solid (214 mg, 33% yield).

¹ H NMR (CDCl ₃ , 21 ° C.): δ = 7.80 (s, 2H), 7.53 (dd, J = 12.2 Hz, 7.8 Hz, 8H), 7.43 (s, 2H), 7.29 (dd, J = 12.2 Hz, 7.8 Hz, 8H).
MS m / z: 888 (M ⁺ , 100%), 808 (M ⁺ -Br, 11), 728 (M ⁺ -2Br, 44).
The structure of the obtained target product is shown below.

参考例１ （４，５，４’，５’−テトラキス｛４−（トリフルオロメチル）フェニル｝−２，２’−ジブロモ−１，１’−ビフェニルの合成）
窒素雰囲気下、１００ｍｌシュレンク反応容器に実施例２で合成した１，２−ジブロモ−４，５−ビス｛４−（トリフルオロメチル）フェニル｝ベンゼン２５４ｍｇ（０．４８ｍｍｏｌ）及びＴＨＦ４ｍｌを添加した。この溶液を−１０℃に冷却し、イソプロピルマグネシウムブロマイド（東京化成工業製、０．８１Ｍ）のＴＨＦ溶液０．６５ｍｌ（０．５３ｍｍｏｌ）を滴下した。１時間熟成後、塩化亜鉛（シグマ−アルドリッチ製、１．０Ｍ）のジエチルエーテル溶液０．５ｍｌ（０．５ｍｍｏｌ）を滴下した。徐々に室温まで昇温した後、生成したスラリー液を減圧濃縮した。得られた固形物に、実施例２で合成した１，２−ジブロモ−４，５−ビス｛４−（トリフルオロメチル）フェニル｝ベンゼン２３０ｍｇ（０．４４ｍｍｏｌ）、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）４１ｍｇ（０．０３５ｍｍｏｌ）、及びＴＨＦ１０ｍｌを添加した。６７℃で４０時間反応を実施した。室温まで冷却後、トルエン及び水を添加し分相した。有機相を濃縮し、得られた残渣をトルエン５ｍｌに溶解後、ｔｅｒｔ−ブチルハイドロパーオキサイド（７０％水溶液）０．１ｍｌを添加し、室温で２時間撹拌した。このトルエン溶液を水で２回洗浄後、有機相を減圧濃縮し、得られた残渣を飽和食塩水及びトルエンを添加した。分相し、有機相を水で洗浄し、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、得られた残渣をシリカゲルを充填したカラムで濾過した（溶媒、ヘキサン）。得られた粗固体をヘキサンから再結晶化し、目的物の白色固体を得た（１７５ｍｇ、収率４５％）。

Reference Example 1 (Synthesis of 4,5,4 ′, 5′-tetrakis {4- (trifluoromethyl) phenyl} -2,2′-dibromo-1,1′-biphenyl)
Under a nitrogen atmosphere, 254 mg (0.48 mmol) of 1,2-dibromo-4,5-bis {4- (trifluoromethyl) phenyl} benzene synthesized in Example 2 and 4 ml of THF were added to a 100 ml Schlenk reaction vessel. The solution was cooled to −10 ° C., and 0.65 ml (0.53 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 1 hour, 0.5 ml (0.5 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, 230 mg (0.44 mmol) of 1,2-dibromo-4,5-bis {4- (trifluoromethyl) phenyl} benzene synthesized in Example 2 and tetrakis (triphenylphosphine) palladium ( Tokyo Chemical Industry Co., Ltd.) 41 mg (0.035 mmol) and THF 10 ml were added. The reaction was carried out at 67 ° C. for 40 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 tert-butyl hydroperoxide (70% aqueous solution) 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 hexane to obtain the objective white solid (175 mg, yield 45%).

Example 6 (Synthesis of 9,9-dimethyl-2,3,6,7-tetraphenyldibenzosilol)
Under a nitrogen atmosphere, 164 mg (0.266 mmol) of 4,5,4 ′, 5′-tetraphenyl-2,2′-dibromo-1,1′-biphenyl synthesized in Example 4 and diethyl ether in a 100 ml Schlenk reaction vessel 4 ml was added. After cooling this solution to 0 ° C., 0.40 ml (0.64 mol) 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 60 minutes, 48.2 mg (0.373) of dichlorodimethylsilane was added. After reacting for 8 hours under reflux of diethyl ether, the mixture was cooled to room temperature, and saturated brine 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 the desired white solid (79 mg, yield 58%).

¹ H NMR (CDCl ₃ , 21 ° C.): δ = 7.90 (s, 2H), 7.71 (s, 2H), 7.25-7.18 (m, 20H).
MS m / z: 515 (M ^{++ 1,} 46%), 514 (M ⁺ , 100%), 499 (M ⁺ -Me, 61), 257 (M ⁺ / 2, 8).
The structure of the obtained target product is shown below.

実施例７ （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６で得られた９，９−ジメチル−２，３，６，７−テトラフェニルジベンゾシロールの白色固体１０．５ｍｇを添加し、１１０℃に加熱溶解させると無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、１０分間、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。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。

Example 7 (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 white solid of 9,9-dimethyl-2,3,6,7-tetraphenyldibenzosilole obtained in Example 6 and dissolved by heating at 110 ° C. to obtain a colorless transparent solution. . Next, the stopper at the top of the Schlenk container was opened, air was introduced by contacting with the outside air for 10 minutes, and the mixture was further stirred at 110 ° C. There were no new peaks due to oxidation in gas chromatography and gas chromatography-mass spectrum (GCMS) analysis.

Comparative Example 1
Under a nitrogen atmosphere, 23.9 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. When 4.2 mg of pentacene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and heated to 110 ° C. and dissolved, a reddish purple solution was obtained. Next, the stopper at the top of the Schlenk container was opened, air was introduced by contacting with the outside air for 10 minutes, and the mixture was further stirred at 110 ° C. The color of the solution changed from red purple to red yellow. From gas chromatography and gas chromatography-mass spectrum (GCMS) analysis, it was found that 6,13-pentacenequinone was produced.

Example 8 (Creation of an organic thin film)
Under a nitrogen atmosphere, 7.2 mg of 9,9-dimethyl-2,3,6,7-tetraphenyldibenzosilole obtained in Example 6 was mixed with toluene (10.2 g) and stirred at 80 ° C. for 1 hour. A colorless and transparent solution of 9,9-dimethyl-2,3,6,7-tetraphenyldibenzosilol was prepared.

A glass 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 a thin film having a thickness of 450 nm. As a result of analyzing the components of this thin film by gas chromatography, there was no peak other than 9,9-dimethyl-2,3,6,7-tetraphenyldibenzosilole, and it was not oxidized. Therefore, it was found that a thin film of 9,9-dimethyl-2,3,6,7-tetraphenyldibenzosilole can be produced without being oxidized even in air.

Claims (6)

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

(Here, the substituents R ¹ , R ⁴ , R ⁵ and R ¹⁰ are hydrogen atoms, and the substituents R ² , R ³ , R ⁷ and R ⁸ are phenyl groups having 6 to 30 carbon atoms, p-tolyl group, p- (n-octyl) phenyl group, m- (n-octyl) phenyl group, p-methoxyphenyl group, p-phenoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 2-fluorenyl At least one substituent selected from the group consisting of a group, 9,9-dimethyl-2-fluorenyl group, 1-biphenylenyl group, 2-biphenylenyl group, biphenylyl group, (diphenylamino) phenyl group, (diphenylamino) biphenylyl group a ^{group, R 11} and ^{R 12,} a methyl group, an ethyl group which is an alkyl group having 1 to 20 carbon atoms, a propyl group, n- butyl group, isobutyl group, t-Bed Group, a neopentyl group, an octyl group, at least one or more substituents selected from the group consisting of dodecyl group, n is 0.) In the dibenzosilole derivative represented by the general formula (1), the substituents R ¹ , R ⁴ , R ⁵ and R ¹⁰ are hydrogen atoms, the substituents R ² , R ³ , R ⁷ and R ⁸ are phenyl groups, R ¹¹ and The dibenzosilol derivative according to claim 1, wherein R ¹² is a methyl group. An oxidation-resistant organic semiconductor material comprising the dibenzosilole derivative according to claim 1 or 2. An organic thin film using the oxidation-resistant organic semiconductor material according to claim 3. The method for producing a dibenzosilole derivative according to claim 1 or 2, wherein a tetrahaloterphenyl derivative represented by the following general formula (2) is lithiated or Grignard and then reacted with a dihalosilicon compound.

(Here, the substituents X ^{1 to} X ⁴ represent a bromine atom, an iodine atom or a chlorine atom. The substituents R ^{1 to} R ¹⁰ and the symbol n have the same meaning as the substituent and the symbol represented by the general formula (1). Show.) In the tetrahaloterphenyl derivative represented by the general formula (2), the substituents R ¹ , R ⁴ , R ⁵ and R ¹⁰ are hydrogen atoms, and the substituents R ² , R ³ , R ⁷ and R ⁸ are phenyl groups. The method for producing a dibenzosilole derivative according to claim 5, wherein X ¹ and X ² are bromine atoms, and n is 0.