JP5218605B2 - 2,3-Dihalobiphenylene derivative, precursor compound thereof and production method thereof - Google Patents

Description

  The present invention relates to a novel 2,3-dihalobiphenylene derivative and a novel tetrahalobiphenyl derivative which is a precursor thereof, and a method for producing them.

  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.

  It has been reported that acenes having a rod-like structure such as pentacene have high carrier mobility similar to amorphous silicon and exhibit excellent semiconductor device characteristics (see Non-Patent Document 1). 2,3-Dibromonaphthalene and 2,3-dibromomoanthracene are used as raw materials for rod-shaped acenes (see Non-Patent Document 2). However, the synthesis of 2,3-dibromonaphthalene requires the use of toxic hexachlorocyclopentadiene, which is unfavorable from the environmental viewpoint (see Non-Patent Document 3). In addition, 2,3-dibromoanthracene required many steps for its synthesis, resulting in a low yield (see Non-Patent Documents 2 and 4). Furthermore, since acene synthesized from such raw materials has low solubility due to its strong cohesiveness, it is not suitable for a method for economically forming a semiconductor active phase by a coating method.

  On the other hand, since a compound having a biphenylene structure has moderate cohesiveness and solubility unlike acenes, it is expected as a raw material for an organic semiconductor active phase constituent material capable of forming a semiconductor active phase by coating.

  As a method for producing a biphenylene derivative, a reaction in which dibromobiphenyl is dilithiated with n-butyllithium and treated with zinc chloride / copper (II) or copper (II) chloride is known (see Non-Patent Document 5). ). However, this method has a problem that when biphenyl having a halogen other than the target reaction site is used as a raw material, selective dilithiation is difficult, and halogen other than the target reaction site is also lithiated. . Also, a method for synthesizing 2,3-diiodobiphenylene has been disclosed by Volhard et al. (See Non-Patent Document 6). However, in addition to the multi-step process, this method uses an expensive cyclopentadienylcobalt dicarbonyl as a catalyst in the synthesis of its precursor 2,3-bis (trimethylsilyl) biphenylene under light irradiation (7.5 mol). %) And bis (trimethylsilyl) acetylene are used in large amounts, which is economically undesirable.

“Journal of Applied Physics” (USA), 2002, 92, 5259-5263. "Organic Letters" (USA), 2000, Volume 2, pages 85-87 “Journal of Organic Chemistry” (USA), 1983, 48, 2364-2366. "Synthesis", 1988, pp. 628-630 “Journal of Chemical Society, Perkin Transaction 1” (UK), 2001, pp. 159-165 “Journal of American Chemical Society” (USA), 1985, 107, 5670-5687.

  The present invention has been made in view of the above-mentioned problems of the prior art, and aims to provide a novel 2,3-dihalobiphenylene derivative, a novel tetrahalobiphenyl derivative serving as a precursor thereof, and a method for producing them. To do. In particular, the present invention aims to provide a 2,3-dihalobiphenylene derivative capable of selectively having a substituent such as fluorine, and further, an organic semiconductor phase constituent material capable of forming a semiconductor active phase by a coating method The purpose is to provide raw materials.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a novel specific 2,3-dihalobiphenylene derivative and a specific method for producing the same, and have completed the present invention. Furthermore, the present inventors have found a novel tetrahalobiphenyl derivative that is a precursor of the specific 2,3-dihalobiphenylene derivative and have found a specific method for producing the derivative, thereby completing the present invention. That is, the present inventors have found a novel specific 2,3-dihalobiphenylene derivative, a novel specific tetrahalobiphenyl derivative that is a precursor compound thereof, and a production method thereof, and completed the present invention. Arrived.

  The present invention is described in detail below.

  The description will be given in the order of 2,3-dihalobiphenylene derivative, tetrahalobiphenyl derivative serving as a precursor thereof, and production methods thereof.

(2,3-dihalobiphenylene derivative)
First, the 2,3-dihalobiphenylene derivative of the present invention will be described.

  The 2,3-dihalobiphenylene derivative of the present invention is represented by the following general formula (1).

（ここで、置換基Ｘ^１及びＸ^２は同一又は異なって、臭素又はヨウ素を示し、Ｒ^１〜Ｒ^６は同一又は異なって、水素原子、炭素数１〜２０のアルキル基若しくはハロゲン化アルキル基、炭素数４〜２０のアリール基、炭素数３〜３０のトリアルキルシリル基、又はフッ素、塩素、臭素、ヨウ素から選ばれるハロゲン原子を示す。なお、Ｒ^１〜Ｒ^４の内、任意の二以上のものは互いに結合することができる。但し、Ｒ^１〜Ｒ^６が水素原子である時、Ｘ^１及びＸ^２は同時にヨウ素ではない。Ｒ^１、Ｒ^４、Ｒ^５、Ｒ^６が水素原子である時、Ｘ^１、Ｘ^２、Ｒ^２、及びＲ^３が同時に臭素ではない。）
本発明の一般式（１）の置換基について、さらに述べる。

(Wherein the substituents X ¹ and X ² are the same or different and each represents bromine or iodine, and R ^{1 to} R ⁶ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group. , An aryl group having 4 to 20 carbon atoms, a trialkylsilyl group having 3 to 30 carbon atoms, or a halogen atom selected from fluorine, chlorine, bromine and iodine, and any two of R ^{1 to} R ⁴ The above can be bonded to each other, provided that when R ^{1 to} R ⁶ are hydrogen atoms, X ¹ and X ² are not iodine at the same time, and R ¹ , R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms. , X ¹ , X ² , R ² , and R ³ are not simultaneously bromine.)
The substituent of the general formula (1) of the present invention will be further described.

The substituents X ¹ and X ² are preferably bromine, particularly preferably both.

In the substituents R ¹ to R ^6, the alkyl group having 1 to 20 carbon atoms is not particularly limited, for example, methyl group, ethyl group, propyl group, n- butyl group, an isobutyl group, a neopentyl group, octyl group, dodecyl group The halogenated alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include a trifluoromethyl group, a trifluoroethyl group, a perfluorohexyl group, and the like; The aryl group is not particularly limited. For example, a phenyl group, a p-tolyl group, a p-fluorophenyl group, a pentafluorophenyl group, a p- (trifluoromethyl) phenyl group, a pyridinyl group, a tetrafluoropyridinyl group, 2- Examples include thienyl group, 2,2′-bithienyl-5-group, biphenyl group, perfluorobiphenyl group, bipyridinyl group and the like. Yes; the trialkylsilyl group having 3 to 30 carbon atoms is not particularly limited, and examples thereof include a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group, a trioctylsilyl group, and a triisobutylsilyl group.

In addition, when arbitrary two or more of substituents R ^{1 to} R ⁴ are bonded to each other, the bond is not particularly limited except for a benzene ring having no substituent. For example, a benzene ring having a substituent , A cyclohexane ring which may have a substituent, a thiophene ring which may have a substituent, and the like.

The halogen atom in the substituents R ^{1 to} R ⁶ is preferably fluorine.

Furthermore, particularly preferably, the substituents R ^{1 to} R ⁶ are a hydrogen atom and / or fluorine.

However, when R ^{1 to} R ⁶ are hydrogen atoms, X ¹ and X ² are not iodine at the same time. Furthermore, when R ¹ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, X ¹ , X ² , R ² and R ³ are not simultaneously bromine.

  There is no limitation in particular in the 2, 3- dihalobiphenylene derivative shown by General formula (1) of this invention, For example, the following compounds can be mentioned.

（テトラハロビフェニル誘導体）
次に、本発明の一般式（１）で示される２，３−ジハロビフェニレン誘導体の前駆化合物であるテトラハロビフェニル誘導体について述べる。

(Tetrahalobiphenyl derivative)
Next, a tetrahalobiphenyl derivative which is a precursor compound of the 2,3-dihalobiphenylene derivative represented by the general formula (1) of the present invention will be described.

  The tetrahalobiphenyl derivative which is a precursor compound of the 2,3-dihalobiphenylene derivative represented by the general formula (1) of the present invention is a compound represented by the following general formula (2).

（ここで、置換基Ｘ^３及びＸ^４は同一又は異なって、臭素、塩素又はヨウ素を示し、Ｘ^５及びＸ^６は同一又は異なって、臭素又はヨウ素を示し、Ｒ^７〜Ｒ^１２は同一又は異なって、水素原子、炭素数１〜２０のアルキル基若しくはハロゲン化アルキル基、炭素数４〜２０のアリール基、炭素数３〜３０のトリアルキルシリル基、又はフッ素、塩素、臭素、ヨウ素から選ばれるハロゲン原子を示す。Ｒ^７〜Ｒ^１０の内、任意の二以上のものは互いに結合することができる。）
本発明の一般式（２）の置換基について、さらに述べる。

(Wherein the substituents X ³ and X ⁴ are the same or different and represent bromine, chlorine or iodine, X ⁵ and X ⁶ are the same or different and represent bromine or iodine, and R ^{7 to} R ¹² are the same or Differently, selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group, an aryl group having 4 to 20 carbon atoms, a trialkylsilyl group having 3 to 30 carbon atoms, or fluorine, chlorine, bromine and iodine (Any two or more of R ^{7 to} R ¹⁰ can be bonded to each other.)
The substituent of the general formula (2) of the present invention will be further described.

The substituents X ³ and X ⁴ are preferably bromine, particularly preferably both.

The substituents X ⁵ and X ⁶ are preferably iodine, particularly preferably both iodine. That is, a more preferable precursor compound of the 2,3-dihalobiphenylene derivative represented by the general formula (1) by adopting a preferred form in which X ⁵ and X ⁶ of the tetrahalobiphenyl derivative represented by the general formula (2) are related. Can be used as

The alkyl group having 1 to 20 carbon atoms in the substituents R ^{7 to} R ¹² is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a neopentyl group, an octyl group, and a dodecyl group. The halogenated alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include a trifluoromethyl group, a trifluoroethyl group, a perfluorohexyl group, and the like; The aryl group is not particularly limited. For example, a phenyl group, a p-tolyl group, a p-fluorophenyl group, a pentafluorophenyl group, a p- (trifluoromethyl) phenyl group, a pyridinyl group, a tetrafluoropyridinyl group, 2- List thienyl group, 2,2'-bithienyl-5-group, biphenyl group, perfluorobiphenyl group, bipyridinyl group, etc. The trialkylsilyl group having 3 to 30 carbon atoms is not particularly limited, and examples thereof include a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group, a trioctylsilyl group, and a triisobutylsilyl group.

In addition, when arbitrary two or more of the substituents R ^{7 to} R ¹² are bonded to each other, the bond is not particularly limited. For example, the substituent may have a benzene ring or a substituent that may have a substituent. A cyclohexane ring that may be substituted, a thiophene ring that may have a substituent, and the like.

The halogen atom in the substituents R ^{7 to} R ¹² is preferably fluorine.

Further, particularly preferably, the substituents R ^{7 to} R ¹⁰ are particularly preferably a hydrogen atom and / or fluorine.

  There is no limitation in particular in the tetrahalobiphenyl derivative which is a precursor compound of the 2, 3- dihalobiphenylene derivative shown by General formula (2) of this invention, For example, the following compounds can be mentioned.

（２，３−ジハロビフェニレン誘導体製造方法）
次に、本発明の一般式（１）で表される２，３−ジハロビフェニレン誘導体の製造方法について述べる。なお、製造方法として異なる２種類の方法について述べる。

(Method for producing 2,3-dihalobiphenylene derivative)
Next, a method for producing the 2,3-dihalobiphenylene derivative represented by the general formula (1) of the present invention will be described. Two different types of manufacturing methods will be described.

(Method for producing 2,3-dihalobiphenylene derivative-part 1)
The 2,3-dihalobiphenylene derivative represented by the general formula (1) of the present invention can be produced from the tetrahalobiphenyl derivative represented by the general formula (2).

That is, the tetrahalobiphenyl derivative represented by the general formula (2) is dilithiated with substituents X ⁵ and X ⁶ using aryllithium, and further reacted with a copper compound to represent the general formula (1). 2,3-dihalobiphenylene derivatives can be produced.

The aryllithium used for dilithiation of the substituents X ⁵ and X ^{6 in} the general formula (2) is not particularly limited as long as the substituents X ⁵ and X ⁶ can be selectively dilithiated. Specific examples include, for example, phenyl lithium, p-fluorophenyl lithium, m-fluorophenyl lithium, o-fluorophenyl lithium, p-chlorophenyl lithium, 3,5-difluorophenyl lithium, p- (trifluoromethyl) phenyl lithium, Examples thereof include 1,1′-biphenyl-4-lithium and 1-naphthyllithium, preferably p-fluorophenyllithium. The aryllithium can be prepared by lithiating an aryl halide having a corresponding aryl group with an alkyllithium such as n-butyllithium.

  The dilithiation reaction of the tetrahalobiphenyl derivative represented by the general formula (2) is preferably carried out in a solvent. The solvent used is not particularly limited, and examples thereof include tetrahydrofuran (hereinafter abbreviated as THF), diethyl ether, dioxane, toluene, hexane, cyclohexane, and the like, and preferably THF. These solvents may be used alone or as a mixture of two or more. In the dilithiation reaction, the amount of aryllithium used is in the range of 1.2 to 3.8 equivalents, preferably 1.8 to 3.2 equivalents, relative to the tetrahalobiphenyl derivative represented by the general formula (2). Range. The temperature of the dilithiation reaction is −110 to 20 ° C., preferably −100 to −50 ° C. The reaction time is in the range of 0.5 to 120 minutes, preferably 1 to 30 minutes.

  The copper compound used when the dihalogenated tetrahalobiphenyl derivative represented by the general formula (2) is reacted with the copper compound is not particularly limited, and any copper compound that reacts with the dilithiated compound may be used. (II), copper bromide (II), copper iodide (II), copper acetate (II), divalent copper such as copper acetylacetonate (II), copper chloride (I), copper bromide (I) And monovalent copper such as copper (I) iodide and copper (I) acetate, preferably divalent copper, and particularly preferably copper (II) chloride.

  The reaction between the dihalogenated tetrahalobiphenyl derivative represented by the general formula (2) and the copper compound is preferably carried out in a solvent. There is no limitation to the solvent to be used, and examples thereof include THF, diethyl ether, dioxane, toluene, hexane, cyclohexane and the like, and preferably THF. These solvents may be used alone or as a mixture of two or more. In the reaction with the copper compound, the amount of the copper compound to be used is in the range of 0.8 to 10.0 equivalents, preferably 1.5 to 4.4, with respect to the tetrahalobiphenyl derivative represented by the general formula (2). The range is 0 equivalent. The temperature of the reaction with the copper compound is −110 to 50 ° C., preferably −100 to 20 ° C. The reaction time is 1 to 24 hours, preferably 2 to 16 hours.

(Method for producing 2,3-dihalobiphenylene derivative-part 2)
As another method, the 2,3-dihalobiphenylene derivative represented by the general formula (1) of the present invention is reacted with a tetrahalobiphenyl derivative represented by the general formula (2) with copper or a copper compound. Can also be manufactured.

  The copper or copper compound used in the reaction is not particularly limited as long as it reacts with iodine or bromine. Specific examples include copper, copper chloride (I), copper bromide (I), copper iodide (I), copper bromide (II), copper (II) iodide, preferably copper. is there. Moreover, even if this copper is an alloy with zinc and / or tin, it can be used without any problem. The shape of the copper and / or copper alloy is preferably powder. This reaction with copper, a copper alloy or a copper compound can be carried out with or without a solvent. When a solvent is used, examples of the solvent include polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile or dimethyl sulfoxide. In the reaction with such copper or copper compound, the amount of copper or copper compound to be used is in the range of 1 to 50 equivalents, preferably 5 to 30 equivalents, relative to the tetrahalobiphenyl derivative represented by the general formula (2). The temperature is 30 to 250 ° C., preferably 50 to 250 ° C., and the reaction time is 1 to 120 minutes, preferably 3 to 80 minutes. The 2,3-dihalobiphenylene derivative represented by the general formula (1) of the present invention thus obtained can be further purified. The method for purification is not particularly limited, and examples thereof include column chromatography, recrystallization, or sublimation.

(Method for producing tetrahalobiphenyl derivative)
Furthermore, the manufacturing method of the tetrahalobiphenyl derivative shown by General formula (2) of this invention is described.

  The tetrahalobiphenyl derivative represented by the general formula (2) of the present invention comprises a tetrahalobenzene represented by the following general formula (3) and a 2-haloaryl metal reagent represented by the following general formula (4) as paradium and / or nickel catalyst. It can manufacture by making it react in presence.

（ここで、Ｘ^７は臭素又はヨウ素を示し、Ｘ^５は臭素又はヨウ素を示し、その他の記号は一般式（２）で示される記号と同意義を示す。）

(Here, X ⁷ represents bromine or iodine, X ⁵ represents bromine or iodine, and other symbols have the same meanings as those represented by the general formula (2).)

（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体を示し、Ｘ^６は臭素又はヨウ素を示し、その他の記号は一般式（２）で示される記号と同意義を示す。）
本発明の一般式（３）で示されるテトラハロベンゼンの置換基Ｘ^７は、好ましくはヨウ素である。

(Here, M represents a halide, hydroxide, alkoxide or alkylated product of Mg, B, Zn, Sn or Si, X ⁶ represents bromine or iodine, and other symbols are represented by the general formula (2). The same meaning as the symbol
The substituent X ⁷ of the tetrahalobenzene represented by the general formula (3) of the present invention is preferably iodine.

The substituent M of the 2-haloaryl metal reagent represented by the general formula (4) of the present invention is a halide, hydroxide, alkoxide or alkylated product of Mg, B, Zn, Sn or Si, and the above palladium and / or 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. For example, MgCl, MgBr, B (OH) ₂ , ZnCl, ZnBr, Si (Bu-n) ₃ or Sn ( Bu-n) ₃ may be mentioned, and B (OH) ₂ or ZnCl is preferable.

The 2-haloaryl metal reagent represented by the general formula (4) can be obtained by a known method. For example, an aryl dihalogen-substituted product is prepared by reacting with a zinc / trimethoxyborane or the like after a halogen / metal exchange reaction with a Grignard reagent such as isopropylmagnesium bromide or an organic lithium reagent such as n-butyllithium. be able to. When reacted with trimethoxyborane, the B (OH) ₂ group can be introduced by further treatment with an acidic aqueous solution.

  The catalyst used for the reaction of the tetrahalobenzene represented by the general formula (3) and the 2-haloaryl metal reagent represented by the general formula (4) is not particularly limited as long as it is a palladium and / or nickel catalyst. Specific examples include tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium / triphenylphosphine mixture, dichlorobis (triphenylphosphine) palladium, bis (tri-tert-butylphosphine) palladium, diacetatobis (triphenylphosphine). ) Palladium, dichloro (1,2-bis (diphenylphosphino) ethane) palladium, palladium acetate / triphenylphosphine mixture, palladium acetate / 2- (dicyclohexylphosphino) -1,1'-biphenyl It can be mentioned things like; as specific examples of the nickel catalyst include dichlorobis (triphenylphosphine) nickel, dichloro (1,2-bis (diphenylphosphino) ethane) nickel. Among these, a preferable catalyst is a zero-valent palladium compound, and a particularly preferable catalyst is tetrakis (triphenylphosphine) palladium. These catalysts may be used alone or as a mixture of two or more.

  In the reaction, the amount of the 2-haloaryl metal reagent of the general formula (4) used is 0.8 to 2.2 equivalents, preferably 1.0 to 1.8, relative to the tetrahalobenzene of the general formula (3). is there. The amount of palladium and / or nickel catalyst used in the reaction is 0.1 mol% to 20 mol%, preferably 0.5 mol% to 10 mol%, based on the tetrahalobenzene of the general formula (3). It is.

  The reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited, and specific examples include THF, diethyl ether, dioxane, toluene, xylene, hexane, cyclohexane, ethanol, water, and the like, and these solvents are one kind or a mixture of two or more kinds. May be used. For example, a three-component system such as toluene / ethanol / water can be used.

  The temperature of reaction is 10-100 degreeC, Preferably it is 30-90 degreeC. The reaction time is 0.5 to 72 hours, preferably 1 to 15 hours.

  In general, when a polyhalogen-substituted benzene such as a tetrahalobenzene represented by the general formula (3) is used as a raw material for the tetrahalobiphenyl derivative represented by the general formula (2), a dehalogenation reaction of the raw material and the product occurs. It is difficult to obtain a precursor compound. However, the present invention suppresses the dehalogenation reaction by selectively using the 2-haloaryl metal reagent and catalyst of the present invention, selectively promotes the cross-coupling reaction, and is represented by the general formula (2) as the target product. The tetrahalobiphenyl derivative can be obtained efficiently. As a result, the 2,3-dihalobiphenylene derivative represented by the general formula (1) can be selectively and efficiently obtained. In addition, according to the present invention, the tetrahalobiphenyl derivative having a substituent such as fluorine and the 2,3-dihalobiphenylene derivative having a substituent such as fluorine can be selectively and efficiently obtained.

  The 2,3-dihalobiphenylene derivative represented by the general formula (1) of the present invention is used as a raw material for organic semiconductor materials for flexible displays such as electronic paper and organic EL, or transistors for IC tags. It can be used as a raw material.

  The present invention relates to a novel 2,3-dihalobiphenylene derivative represented by the general formula (1), a novel method for producing the same, and a novel tetrahalo to be a precursor of the 2,3-dihalobiphenylene derivative Biphenyl derivatives and novel methods for producing the same are provided. Furthermore, the present invention can provide a 2,3-dihalobiphenylene derivative having a substituent such as fluorine and a tetrahalobiphenyl derivative which is a precursor compound thereof.

  The 2,3-dihalobiphenylene derivative of the present invention is useful as a raw material for a compound having a bi (biphenylene) structure because a homocoupling reaction is possible, and an organic semiconductor active phase capable of forming a semiconductor active phase by coating It can be used as a raw material for constituent materials.

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

For the identification of the product, ¹ H-NMR spectrum and mass spectrum were used. ¹ H-NMR spectrum was obtained by using JEOL GSX-270WB (270 MHz) manufactured by JEOL, and mass spectrum (MS) was obtained by using JEOL JMS-700 manufactured by JEOL. Measured using the method (70 electron volts).

  As the solvent in the reaction, a commercially available dehydrated solvent was used as it was.

Example 1 (Synthesis of 4,5-dibromo-2,2'-diiodobiphenyl)
As a tetrahalobenzene represented by the general formula (3), 1,2-dibromo-4,5-diiodobenzene is referred to “Synlet”, 2003, pages 29-34, and 1, Synthesized from 2-dibromobenzene.

  The aryl metal reagent represented by the general formula (4) was obtained by the following method. Under a nitrogen atmosphere, 8.13 g (24.6 mmol) of 1,2-diiodobenzene and 35 ml of THF were added to a 300 ml Schlenk reaction vessel. This solution was cooled to −70 ° C., and 40 ml (26 mmol) of a THF solution of isopropyl magnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65 M) was added dropwise. After raising the temperature to −65 ° C. over 30 minutes, 26 ml (26 mmol) of a diethyl ether solution of zinc chloride (manufactured by Sigma-Aldrich, 1.0 M) was added dropwise at that temperature. After the temperature of the solution was gradually raised to room temperature, the produced white slurry was concentrated under reduced pressure to obtain a white solid.

To the obtained white solid, 10.02-g (20.6 mmol) of 1,2-dibromo-4,5-diiodobenzene, 691 mg (0.597 mmol) of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry), and 56 ml of THF. Was added. After carrying out the reaction for 3 hours under heating and refluxing conditions, the vessel was cooled with water and the reaction was stopped by adding 20 ml of 3N hydrochloric acid. The reaction mixture was concentrated under reduced pressure, and the solvent was distilled off. The precipitated solid was washed with water until the filtrate became neutral, and further washed with hexane. The obtained mixture was dried under reduced pressure, and purified by recrystallization using 22 ml of toluene. The precipitated solid was filtered and washed with 2 ml of toluene and 8 ml of hexane. After drying under reduced pressure, a white solid of 4,5-dibromo-2,2′-diiodobiphenyl was obtained (7.58 g, yield 65%).
Melting point: 177-179 ° C (decomposition)
¹ H-NMR (CDCl ₃ , 21 ° C.): δ = 8.16 (s, 1H), 7.93 (d, J =
7.8 Hz, 1 H), 7.43 (s, 1 H), 7.42 (t, J = 7.6 Hz, 1 H), 7.17 to 7.06 (m, 2 H)
MS m / z: 564 (M ⁺ , 25%), 437 (M ⁺ -I, 80), 310 (M ⁺ -2I, 26), 150 (M ⁺ -(2Br + 2I), 100)
^{The 1} H-NMR spectrum is shown in FIG.

Example 2 (Synthesis of 4,5,4 ′, 5′-tetrabromo-2,2′-diiodobiphenyl)
Under a nitrogen atmosphere, 1.01 g (2.06 mmol) of 1,2-dibromo-4,5-diiodobenzene and 4 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −63 ° C., and 3.3 ml (2.1 mmol) of isopropyl magnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65 M) in THF was added dropwise. After aging at −63 ° C. for 40 minutes, 4.3 ml (2.2 mmol) of a THF solution of zinc chloride (manufactured by Sigma-Aldrich, 0.5M) was added dropwise at that temperature. After the temperature of the solution was gradually raised to room temperature, the produced white slurry was concentrated under reduced pressure. To the obtained white solid, 882 mg (1.80 mmol) of 1,2-dibromo-4,5-diiodobenzene, 92 mg (0.079 mmol) of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry), and 7 ml of THF were added. did. After carrying out the reaction for 5 hours under heating and refluxing conditions, the vessel was cooled with water and the reaction was stopped by adding 20 ml of 3N hydrochloric acid. The whole was concentrated under reduced pressure, and the solvent was distilled off. The precipitated solid was washed with water until the filtrate was neutral.

The obtained solid was dried under reduced pressure and purified by recrystallization using 3 ml of toluene. A white solid of 4,5,4 ′, 5′-tetrabromo-2,2′-diiodobiphenyl was obtained (641 mg, yield 49%).
Melting point: 193-195 ° C.
¹ H-NMR (CDCl ₃ , 21 ° C.): δ = 8.17 (s, 2H), 7.40 (s, 2H)
) MS m / z: 722 (M ⁺ , 40%), 595 (M ⁺ −I, 56), 488 (M ⁺ −
3Br + 6, 84), 308 (M ⁺ − (2Br + 2I), 43), 149 (M ⁺ − (4B
r + 2I) +1,100)
^{The 1} H-NMR spectrum is shown in FIG.

Example 3 (Synthesis of 2,3-dibromobiphenylene)
Under a nitrogen atmosphere, 1.43 g (8.16 mmol) of p-fluorobromobenzene and 50 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −72 ° C., and 4.8 ml (7.6 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.59 M) was added dropwise. After reacting at −72 ° C. for 15 minutes, the solution was cooled to −98 ° C. to prepare a p-fluorophenyllithium solution.

Meanwhile, 2.00 g (3.55 mmol) of 4,5-dibromo-2,2′-diiodobiphenyl synthesized in Example 1 and 65 ml of THF were added to a 300 ml Schlenk reaction vessel under a nitrogen atmosphere. This solution was cooled to −98 ° C., and a solution of p-fluorophenyllithium was introduced thereto using a cannula. After stirring for 2 minutes, 1.45 g (10.8 mmol) of copper (II) chloride was added at −97 ° C. The reaction temperature was raised to room temperature overnight. 3N hydrochloric acid was added, toluene (40 ml) and NaCl were added, and the phases were separated. The organic phase was washed with saturated brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the reaction mixture was purified by silica gel flash chromatography (eluent: hexane) to obtain 627 mg of a solid containing the desired product. Purification by recrystallization was performed using 5.8 ml of heptane to obtain a yellow solid of 2,3-dibromobiphenylene (300 mg). Further, the filtrate was concentrated and recrystallized from hexane to obtain 2,3-dibromobiphenylene yellow solid (57 mg) as a target product. (Total yield 32%).
Melting point: 152-153 ° C
¹ H-NMR (CDCl ₃ , 21 ° C.): δ = 6.86 (s, 2H), 6.83 (dd, J = 5.0 Hz, 2.9 Hz, 2H), 6.70 (dd, J = (4.9Hz, 2.9Hz, 2H)
MS m / z: 310 (M ⁺ , 73%), 229 (M ⁺ -Br, 5), 150 (M ⁺ -2Br, 100)
^{The 1} H-NMR spectrum is shown in FIG.

Comparative Example 1
Under a nitrogen atmosphere, 394 mg (0.699 mmol) of 4,5-dibromo-2,2′-diiodobiphenyl synthesized in Example 1 and 20 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −95 ° C., and 0.95 ml (1.5 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Inc., 1.59 M) was added dropwise thereto. After stirring for 2 minutes, 283 mg (2.10 mmol) of copper (II) chloride was added at −95 ° C. The reaction temperature was raised to room temperature overnight. 3N hydrochloric acid was added, 5 ml of toluene and NaCl were added, and the phases were separated. The organic phase was washed with saturated brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the ¹ H NMR spectrum of the crude product was measured, but the peak of the desired 2,3-dibromobiphenylene was very weak. Instead, the normal aromatic region (δ = 7-8) and n- The peak intensity of the butyl group was increased.

^{The 1} H-NMR spectrum is shown in FIG.

Example 4 (Synthesis of 2,3-dibromobiphenylene)
Under a nitrogen atmosphere, 150 mg (0.266 mmol) of 4,5-dibromo-2,2′-diiodobiphenyl synthesized in Example 1 and 417 mg (6.56 mmol) of copper powder (manufactured by Sigma-Aldrich) were synthesized in a 20 ml Schlenk reaction vessel. Was added. After stirring for 20 minutes, the reaction vessel was immersed in an oil bath at 230 ° C. After reacting at this temperature for 20 minutes, the mixture was cooled to room temperature and extracted with toluene. The toluene solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel flash chromatography (eluent: hexane) to obtain a yellow solid of 2,3-dibromobiphenylene (28 mg, yield 34%).

; ¹ H-NMR spectrum (CDCl ₃ , 21 ° C.) of 4,5-dibromo-2,2′-diiodobiphenyl synthesized in Example 1 ; ¹ H-NMR spectrum (CDCl ₃ , 21 ° C.) of 4,5,4 ′, 5′-tetrabromo-2,2′-diiodobiphenyl synthesized in Example 2 ; ¹ H-NMR spectrum (CDCl ₃ , 21 ° C.) of 2,3-dibromobiphenylene synthesized in Example 3 ; ¹ H-NMR spectrum (CDCl ₃ , 21 ° C.) of the crude product obtained in Comparative Example 1

Claims (5)

A tetrahalobenzene represented by the following general formula (3) and a 2-haloaryl metal reagent represented by the following general formula (4) are reacted in the presence of a palladium and / or nickel catalyst to produce a tetra represented by the following general formula (2). A method for producing a tetrahalobiphenyl derivative, characterized by producing a halobiphenyl derivative.

(Wherein the substituents X ³ and X ⁴ are the same or different and represent bromine, chlorine or iodine, X ⁵ and X ⁶ are the same or different and represent bromine or iodine, and R ^{7 to} R ¹² are the same or Differently, selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group, an aryl group having 4 to 20 carbon atoms, a trialkylsilyl group having 3 to 30 carbon atoms, or fluorine, chlorine, bromine and iodine In addition, any two or more of R ^{7 to} R ¹⁰ are bonded to each other and may have a benzene ring which may have a substituent, a cyclohexane ring which may have a substituent, or A thiophene ring which may have a substituent can be formed.)

(Here, X ⁷ represents bromine or iodine, X ⁵ represents bromine or iodine, and other symbols have the same meanings as those represented by the general formula (2).)

(Here, M represents a halide, hydroxide, alkoxide or alkylated product of Mg, B, Zn, Sn or Si, X ⁶ represents bromine or iodine, and other symbols are represented by the general formula (2). The same meaning as the symbol The X ^{5 of the} tetrahalobenzene represented by the general formula (3) is iodine, and the X ^{6 of the} 2-haloaryl metal reagent represented by the general formula (4) is iodine. A method for producing the described tetrahalobiphenyl derivative. The method for producing a tetrahalobiphenyl derivative according to claim 1 or 2, wherein M of the 2-haloaryl metal reagent represented by the general formula (4) is ZnCl or B (OH) ₂ . The method for producing a tetrahalobiphenyl derivative according to any one of claims 1 to 3, wherein the catalyst is tetrakis (triphenylphosphine) palladium. A tetrahalobiphenyl derivative represented by the following general formula (2), wherein the substituents X ⁵ and X ⁶ are iodine.

(Wherein the substituents X ³ and X ⁴ are the same or different and represent bromine, chlorine or iodine, X ⁵ and X ⁶ are the same or different and represent bromine or iodine, and R ^{7 to} R ¹² are the same or Differently, selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group, an aryl group having 4 to 20 carbon atoms, a trialkylsilyl group having 3 to 30 carbon atoms, or fluorine, chlorine, bromine and iodine In addition, any two or more of R ^{7 to} R ¹⁰ are bonded to each other and may have a benzene ring which may have a substituent, a cyclohexane ring which may have a substituent, or A thiophene ring which may have a substituent can be formed.)

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