JP5076599B2 - Method for producing terphenylene derivative - Google Patents

Description

  The present invention relates to a method for producing a terphenylene derivative that can be developed into electronic materials such as organic semiconductors. Furthermore, this invention relates to the manufacturing method from the tetrahalo terphenyl derivative which is a precursor compound of this terphenylene derivative.

  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 organic semiconductor device performance is affected by the carrier mobility of the organic material constituting the organic semiconductor active phase.

  For example, it has been reported that a crystalline material such as pentacene has a carrier mobility as high as that of amorphous silicon and exhibits excellent semiconductor device characteristics (see, for example, Non-Patent Document 1). There has also been reported an attempt to manufacture a device by a coating method by dissolving polyacene such as pentacene (see, for example, Patent Document 1). However, an organic thin film transistor using pentacene as a semiconductor is not practical because of its low stability in the atmosphere. In addition, self-assembled materials such as poly- (3,3 ′ ″-didodecyl-quarterthiophene) are soluble in solvents, and device fabrication by coating has been reported, but carrier mobility is higher than that of crystalline compounds. Since it is one digit lower (for example, see Non-Patent Document 2), there is a problem that the characteristics of the obtained organic semiconductor device are low.

  On the other hand, a terphenylene derivative is a rigid rod-like molecule and is known to have a structure similar to pentacene, but has a feature that it is stable in the atmosphere. (For example, refer to Patent Document 2). The present invention proposes a method for producing a terphenylene derivative at a higher yield than the method of Patent Document 2.

“Journal of Applied Physics” (USA), 2002, 92, 5259-5263. "Journal of American Chemical Society" (USA), 2004, 126, 3378-3379 WO2003 / 016599 pamphlet WO2006 / 109569 pamphlet

  In view of the above-described problems of the prior art, an object of the present invention is to provide a method for efficiently producing a terphenylene derivative capable of forming a semiconductor active phase having excellent atmospheric stability.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a novel method for producing a terphenylene derivative of the present invention and have completed the present invention.

  The production method of the terphenylene derivative represented by the following general formula (1) of the present invention will be described below.

(Here, the substituents R ^{1 to} R ¹⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 20 carbon atoms .
l and n are each an integer of 0 to 2, and m is 0 . )
The terphenylene derivative represented by the general formula (1) of the present invention is a thiol derivative selected from n-butyllithium, sec-butyllithium, and tert-butyllithium as a tetrahaloterphenyl derivative represented by the following general formula (2). It can manufacture by making it react with a copper compound after throwing into an agent and tetralithiating.

(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 ^{14 in} the general formula (2) and the symbols l, m, and n represent the general formula (1). And has the same meaning as the substituents and symbols shown.
In addition, the notation of the general formula (2) is a general term for the para-positional isomer and the meta-positional isomer in which the general formula (2) is represented by the following general formulas (3) and (4).

(Here, the substituents R ^{1 to} R ¹⁴ and X ^{1 to} X ⁴ in the general formula (3) and the general formula (4), and the symbols l, m, and n are the substituents and symbols represented by the general formula (2)). It shows the same meaning as
Here, tetralithiation means that each of the ^four halogens X ^{1 to} X ⁴ in the general formula (2) is replaced with lithium.

  The substituent of the general formula (1) of the present invention will be described.

In the substituents ^R 1 ^{to R 14,} an alkyl group having 1 to 20 carbon atoms is not particularly limited, for example, methyl group, propyl group, n- butyl group, an isobutyl group, t- butyl group, n- hexyl group, an octyl group Alkyl groups consisting only of carbon and hydrogen such as dodecyl group and octadecyl; and halogenated alkyl groups such as trifluoromethyl group, trifluoroethyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, etc. it can.

The aryl group having 4 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- (n-perfluorooctyl) phenyl group, 2-thienyl group, 5- (n-hexyl) -2 -Thienyl group, 2,2'-bithienyl-5-group, biphenyl group, perfluorobiphenyl group, 1-naphthyl group, 2-naphthyl group, 1-perfluoronaphthyl group, anthracenyl group, 2-fluorenyl group, 9, 9-dimethyl-2-fluorenyl group, 1-biphenyleno group, 2-biphenyleno group, terphenyl group, 2-pyridyl group, tetrafluoropyridyl group, bipyridy Group, (diphenylamino) phenyl group, (diphenylamino) biphenyl 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, {4- (n-octyl) phenyl} ethynyl group, naphthylethynyl group, anthracenylethynyl group, biphenylethynyl group, terphenylethynyl group, benzylethynyl group, biphenylenoethynyl group, Perfluorophenylethynyl group, {p- (trifluoromethyl) phenyl} ethynyl group, (n-perfluorooctyl) ethynyl group, (n-perfluorododecyl) ethynyl group, {4- (n-perfluorooctyl) phenyl } An ethynyl group etc. can be mentioned.

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, phenylethenyl, {4- (n-octyl) phenyl} ethenyl, naphthylethenyl, anthracenylethenyl, perfluorophenylethenyl, {p- (trifluoromethyl) phenyl} Ethenyl group, (n-perfluorooctyl) ethenyl group, (n-perfluorododecyl) ethenyl group, biphenylethenyl group, terphenylethenyl group, benzylethenyl group, biphenylenoethenyl group, phenyl (methyl) ethenyl Group, (trimethylsilyl) ethenyl group, (triethylsilyl) ) Ethenyl group, and (triisopropylsilyl) ethenyl group. When the trans isomer and cis isomer are present, the alkenyl group having 2 to 20 carbon atoms may be either a trans isomer or a cis isomer, or may be a mixture of any ratio thereof.

Among the bonded substituents formed when any two or more of the substituents R ^{1 to} R ⁶ are bonded to each other, and when any two or more of the substituents R ^{8 to} R ¹³ are bonded to each other, The following are mentioned as an unsaturated ring group which is a preferable example of a substituent.

  Examples of the unsaturated ring include a benzene ring which may have a substituent, a tetraphenylene ring which may have a substituent, or a thiophene ring which may have a substituent. Examples of the benzene ring which may have a substituent include a benzene ring, a dimethylbenzene ring, a di (n-hexyl) benzene ring, a di (n-octyl) benzene ring, a di (n-dodecyl) benzene ring, and a naphthalene ring. Methylnaphthalene ring, dimethylnaphthalene ring, phenylnaphthalene ring, di (perfluoro-n-octyl) benzene ring, di (perfluoro-n-dodecyl) benzene ring, and the like. Examples of the tetraphenylene ring which may have a substituent include a tetraphenylene ring and a phenyltetraphenylene ring. Examples of the thiophene ring that may have a substituent include a thiophene ring, a methylthiophene ring, an (n-octyl) thiophene ring, and a phenylthiophene ring.

  The unsaturated ring is preferably a benzene ring which may have a substituent or a thiophene ring which may have a substituent, and particularly preferably a benzene ring, a di (n-octyl) benzene ring, (n -Octyl) thiophene ring.

The substituents R ^{1 to} R ¹⁴ are preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 4 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, particularly preferably. A hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 4 to 30 carbon atoms.

In the general formula (1), when two or more of the substituents R ^{1 to} R ⁶ are bonded to each other, a preferable bond is a bond between the substituents R ³ and R ⁴ . In the case where any two or more of the substituents R ^{8 to} R ¹³ are bonded to each other, a preferable bond is a bond between the substituents R ¹⁰ and R ¹¹ . Furthermore, in the case where any two or more of the substituents R ^{1 to} R ⁶ are bonded to each other and in the case where any two or more of the substituents R ^{8 to} R ¹³ are bonded to each other, these The bond may be formed at the same time in both cases, or may be formed only in either case.

  In the values of l, m and n in the general formula (1) of the present invention, a preferred combination is when m is 0, when l and n are both 2, when l is 2, and both m and n are 0. There are some cases.

The ring structure of the terphenylene derivative represented by the general formula (1) of the present invention is not particularly limited, and any structure in which both ends of the ring structure are bilaterally symmetric or bilaterally asymmetric is possible. Here, both ends of the ring structure are symmetrical. When l and n have the same value and the substituents arranged at the corresponding positions of the left and right ring structures match, that is, R ¹ = R ¹³ , R ² = R ¹² , R ³ = R ¹¹ , R ⁴ = R ¹⁰ , R ⁵ = R ⁹ , R ⁶ = R ⁸ . On the other hand, the left-right asymmetry includes, for example, when l and n are different values, and when l and n are the same value but the substituents arranged at the corresponding positions of the left and right ring structures do not match. it can.

  The substituent of the general formula (2) of the present invention will be described.

The substituents X ^{1 to} X ⁴ are a bromine atom, an iodine atom or a chlorine atom, preferably a bromine atom.

The substituents R ^{1 to} R ¹⁴ , and the symbols l, m, and n have the same meanings as the substituent and the symbol represented by the general formula (1).

  The notation of the general formula (2) is a general term for the para-positional isomer and the meta-positional isomer in which the general formula (2) is represented by the general formula (3) and the general formula (4).

  The tetrahaloterphenyl derivative represented by the general formula (2) is not particularly limited, and examples thereof include the following compounds:

The following compounds are particularly preferable.

  The tetrahaloterphenyl derivative represented by the general formula (2) used as a raw material for the production method of the terphenylene derivative represented by the general formula (1) of the present invention is, for example, a tetrahaloarene and a 2-haloaryl reagent, a palladium catalyst And / or by reacting in the presence of a nickel catalyst (WO 2006/109569 pamphlet).

  The production method of the terphenylene derivative represented by the general formula (1) of the present invention will be described.

When tetralithiating 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-fluoro Aryl lithium such as phenyl lithium; lithium amide such as lithium diisopropylamide and lithium hexamethyldisilazide; lithium metal such as lithium powder can be mentioned, preferably alkyllithium, particularly preferably sec-butyllithium. It is a tert- butyl lithium.

  The amount of the lithiating agent used is preferably 6 to 10 equivalents, particularly preferably 7 to 9 equivalents, relative to the tetrahaloterphenyl derivative of the general formula (2).

  The tetralithiation 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, methyl tert-butyl ether, ethylene glycol dimethyl ether, dioxane, toluene, hexane, cyclohexane, and the like, and particularly preferably THF. These solvents may be used alone or as a mixture of two or more.

  The tetralithiation reaction in the method for producing the terphenylene derivative represented by the general formula (1) of the present invention is achieved by introducing the tetrahaloterphenyl derivative represented by the general formula (2) into a lithiating agent and tetralithiating it. Can be achieved efficiently. That is, alkyllithium is preferably used as the lithiating agent. When a tetrahaloterphenyl derivative represented by the general formula (2) is lithiated with alkyllithium, an alkyl halide is simultaneously generated by a halogen-metal exchange reaction. The alkyl halide further reacts with a lithiating agent or a lithiated product of the generated tetrahaloterphenyl derivative, and β-hydrogen elimination occurs due to extraction of protons to generate lithium halide and alkane. Therefore, when the lithiated product of the tetrahaloterphenyl derivative undergoes β-hydrogen elimination, the tetralithio form of the tetrahaloterphenyl derivative cannot be produced, resulting in a decrease in yield. Therefore, it is considered that the yield of the tetralithio form of the tetrahaloterphenyl derivative is improved by causing the β-hydrogen elimination of the alkyl halide generated in the alkyl lithium used as the reactant. Therefore, the present inventors consider that it is important to maintain as long as possible the conditions under which alkyllithium can exist in excess, and by introducing the tetrahaloterphenyl derivative into the lithiating agent, the yield of tetralithiation is improved, Found that the yield of the desired terphenylene derivative was improved.

  The method for introducing the tetrahaloterphenyl derivative into the lithiating agent is not particularly limited, and it is preferable to introduce the tetrahaloterphenyl derivative into the mixture of the lithiating agent and the solvent mentioned above. In this case, the tetrahaloterphenyl derivative can be used even if it is a solution comprising the solvent. The temperature at which the tetrahaloterphenyl derivative is introduced is preferably -90 to 40 ° C, particularly preferably -80 to 20 ° C. The time for introducing the tetrahaloterphenyl derivative is preferably 1 to 60 minutes, particularly preferably 3 to 40 minutes, depending on the temperature at the time of addition.

  After introducing the tetrahaloterphenyl derivative, it is preferable to set an aging time in order to sufficiently advance tetralithiation. The aging time is preferably 1 to 120 minutes, particularly preferably 5 to 60 minutes. The temperature during the aging time is preferably −90 to 40 ° C., particularly preferably −80 to 20 ° C. The progress of the tetralithiation 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 tetralithium salt produced by the tetralithiation reaction is then reacted with a copper compound. The reaction with the copper compound is a method in which the reaction mixture containing the tetralithium salt generated by the tetralithiation reaction is directly reacted with the copper compound; after the generated tetralithium salt is isolated once, it is reacted with the copper compound. Any of the methods may be used.

  The copper compound used in the reaction between the tetralithium salt and the copper compound is not particularly limited. For example, copper (II) chloride, copper (II) bromide, copper (II) iodide, copper (II) acetate, acetylacetonate Examples thereof include divalent copper such as copper (II); monovalent copper such as copper (I) chloride, copper (I) bromide, copper (I) iodide, and copper (I) acetate. Divalent copper is preferable, and copper (II) chloride is particularly preferable.

  The reaction with the copper compound is preferably carried out in a solvent. The solvent to be used is not particularly limited, and examples thereof include THF, diethyl ether, methyl-tert-butyl ether, ethylene glycol dimethyl ether, diglyme, dioxane, toluene, hexane, cyclohexane, and the like, and particularly preferably THF. The amount of the copper compound to be used is preferably 4 to 20 equivalents, particularly preferably 6 to 15 equivalents, with respect to the tetrahaloterphenyl derivative of the general formula (2). The reaction temperature with the copper compound is preferably −90 to 40 ° C., particularly preferably −80 to 20 ° C., and the reaction time is preferably 1 to 30 hours, particularly preferably 1 to 18 hours.

  The copper compound can be used as it is, or a solution dissolved in the above-mentioned solvent can be used.

  The terphenylene derivative represented by the general formula (1) of the present invention is preferably produced under an inert atmosphere such as nitrogen or argon.

  In the method for producing a terphenylene derivative represented by the general formula (1) of the present invention, the tetrahaloterphenyl derivative represented by the general formula (2) is tetralithiated, reacted with zinc chloride, and then reacted with a copper compound. It can also be made.

  The terphenylene 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.

  The terphenylene derivative represented by the general formula (1) that can be produced by the production method of the present invention is not particularly limited, and examples thereof include the following compounds:

  The following compounds are particularly preferable.

  The tetrahaloterphenyl derivative represented by the general formula (2) used as a raw material in the method for producing the terphenylene derivative represented by the general formula (1) of the present invention has a para-type represented by the general formula (3) as its structure. And a meta type represented by the general formula (4). However, as the raw material for the terphenylene derivative represented by the general formula (1), any of these two types of para- and meta-type isomers can be used, and an arbitrary ratio of these two types of isomers. Even a mixture of these can be used as a raw material.

  Since the terphenylene derivative represented by the general formula (1) that can be produced by the production method of the present invention has a molecular structure with high plane rigidity, it can be expected to give excellent semiconductor characteristics. In addition, the terphenylene derivative is dissolved in a halogen-free solvent such as toluene and is not easily oxidized by air even in a solution state. Therefore, a semiconductor thin film can be easily produced by a coating method. Therefore, the terphenylene derivative represented by the general formula (1) that can be produced by the production method 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. It can be used for organic EL display materials, organic semiconductor laser materials, organic thin film solar cell materials, organic memory materials, and the like.

  Provided is a method for efficiently producing a terphenylene derivative capable of forming a semiconductor active phase having excellent atmospheric stability.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited only to these Examples. Unless otherwise noted, commercially available reagents and the like were used.

For identification of the product, ¹ H NMR spectrum and mass spectrum were used. The ¹ H NMR spectrum used JEOL GSX-270WB (270 MHz) manufactured by JEOL, and the mass spectrum (MS) used JEOL JMS-700 manufactured by JEOL. The sample was directly introduced, and the electron impact (EI) method was used. (70 electron volts).

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

Gas chromatography analyzer Shimadzu GC14B
Column J & W Scientific, DB-1, 30m
Gas chromatography-mass spectrum analyzer Perkin Elmer Auto System XL (MS part; Turbomass Gold)
Column J & W Scientific, DB-1,30
A commercially available dehydrated solvent was used as the solvent for the reaction.

Synthesis Example 1 (Synthesis of 1,4-dibromo-2,5-diiodobenzene)
1,4-Dibromo-2,5-diiodobenzene was synthesized as follows with reference to the method described in Journal of American Chemical Society, 1997, Vol. 119, pages 4578-4593.

Periodic acid 16.7 g (73.0 mmol) and sulfuric acid 525 ml were added to a 1 l three-necked flask equipped with a mechanical stirrer. After the periodic acid was dissolved, 36.4 g (219 mmol) of potassium iodide was added little by little. The temperature of the contents was cooled to −30 ° C., and 34.5 g (146 mmol) of 1,4-dibromobenzene was added over 5 minutes. The resulting mixture was stirred at −25 ° C. for 36 hours. The reaction mixture was poured into ice (2 Kg) and filtered to remove the solid. The solid was dissolved in chloroform, washed with 5% aqueous sodium hydroxide solution and water, and the organic phase was dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was recrystallized from chloroform to obtain white crystals of 1,4-dibromo-2,5-diiodobenzene (36.0 g, yield 50%).
¹ H NMR spectrum was consistent with literature values.
¹ H NMR (CDCl ₃ , 21 ° C.): δ = 8.02 (s, 2H).

Synthesis Example 2 (Synthesis of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -terphenyl) [Synthesis of tetrahaloterphenyl derivative]
Under a nitrogen atmosphere, 4.39 g (9.00 mmol) of 1,4-dibromo-2,5-diiodobenzene synthesized in Synthesis Example 1 in a 100 ml Schlenk reaction vessel, tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 974 mg (0.84 mmol) and 2.16 g (20.7 mmol) of 2-bromophenylboronic acid (manufactured by Sigma-Aldrich) were added. Further, 72 ml of toluene, 18 ml of ethanol, and an aqueous solution consisting of 5.72 g (54.0 mmol) of sodium carbonate and 22 ml of water were added. It was immersed in an oil bath at 85 ° C. and stirred for 15 hours. After cooling to room temperature, dichloromethane and saturated brine were added for phase separation. The organic phase was concentrated under reduced pressure and the residue was recrystallized from toluene. 2,2 ′, 5 ′, 2 ″ -Tetrabromo-1,1 ′, 4 ′, 1 ″ -terphenyl white needles were obtained (4.18 g, 85% yield).
Melting point: 230-231 ° C.
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.70 (d, J = 8.0 Hz, 2H), 7.55 (d, J = 1.5 Hz, 2H), 7.45-7.23 (M, 6H).
^{The 1} H NMR spectrum is shown in FIG.
MS m / z: 546 (M ⁺ , 92%), 466 (M ⁺ -Br, 45), 386 (M ⁺ -2Br, 53), 226 (M ⁺ -4Br, 100).

  The structural formula of the obtained 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -terphenyl is shown below.

Example 1 (Synthesis of terphenylene)
Under a nitrogen atmosphere, 23 ml of THF was added to a 100 ml Schlenk reaction vessel, cooled to −73 ° C., and 5.0 ml (4.9 mmol) of a cyclohexane solution of sec-butyllithium (manufactured by Kanto Chemical Co., Ltd., 0.98M) was added. At −73 ° C., 272 mg (0.498 mmol) of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -terphenyl synthesized in Synthesis Example 2 was added over 3 minutes. did. After aging at −73 ° C. to −68 ° C. for 30 minutes, 828 mg (6.2 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added at a stretch at −75 ° C., and the temperature was raised to room temperature overnight. . After adding saturated brine and toluene, the phases were separated, and the organic phase was further washed with saturated brine. Concentrated under reduced pressure, hexane was added to the resulting residue, and the mixture was allowed to stand after stirring. The supernatant was removed, and the residue was dried under reduced pressure. The residue was recrystallized from toluene to obtain red plate crystals of terphenylene (43 mg, yield 38%).
¹ H NMR spectrum (heavy benzene, 30 ° C.): δ = 6.46 (AA ′, J = 4.8 Hz, 2.9 Hz, 4H), 6.20 (BB ′, J = 4.6 Hz, 2.9 Hz) , 4H), 5.93 (s, 2H).
^{The 1} H NMR spectrum is shown in FIG.
MS m / z: 226 (M ^<+> , 100%), 113 (M ^<+ > / 2, 29).

  The structural formula of the obtained terphenylene is shown below.

Reference Example 1 (Synthesis of terphenylene)
Under a nitrogen atmosphere, 280 mg (0.512 mmol) of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -terphenyl synthesized in Synthesis Example 2 and 23 ml of THF were added to a 100 ml Schlenk reaction vessel. Added. This solution was cooled to −73 ° C., and 5.0 ml (4.9 mmol) of a cyclohexane solution of sec-butyllithium (manufactured by Kanto Chemical Co., Ltd., 0.98M) was added dropwise. After aging at −73 ° C. to −68 ° C. for 30 minutes, 828 mg (6.2 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added at a stretch at −75 ° C., and the temperature was raised to room temperature overnight. . After adding saturated brine and toluene, the phases were separated, and the organic phase was further washed with saturated brine. Concentrated under reduced pressure, hexane was added to the resulting residue, and the mixture was allowed to stand after stirring. The supernatant was removed, and the residue was dried under reduced pressure. The residue was recrystallized from toluene to obtain red plate crystals of terphenylene (16 mg, 14% yield).

Synthesis Example 3 (2,2 ′, 4 ′, 2 ″ -tetrabromo-1,1 ′, 5 ′, 1 ″ -terphenyl and 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 Synthesis of ', 1 "-terphenyl) [Synthesis of tetrahaloterphenyl derivatives]
1.70 g (4.31 mmol) of 1,2,4,5-tetrabromobenzene (manufactured by Tokyo Chemical Industry), 253 mg of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry) in a 100 ml Schlenk reaction vessel under a nitrogen atmosphere 0.218 mmol), and 1.99 g (9.90 mmol) of 2-bromophenylboronic acid (Sigma-Aldrich) were added. Further, 34 ml of toluene, 9 ml of ethanol, and an aqueous solution consisting of 2.75 g (25.9 mmol) of sodium carbonate and 10 ml of water were added. It was immersed in an oil bath at 85 ° C. and stirred for 8 hours. After cooling to room temperature, saturated brine was added and the phases were separated. To the obtained organic phase, 1 ml of tertiary butyl hydroperoxide (70% by weight content) was added at room temperature and stirred for 2 hours. Saturated brine was added, the phases were separated, and the organic phase was concentrated under reduced pressure. The residue was purified by silica gel column chromatography.

  First, a component mainly composed of 2,2 ′, 4 ′, 2 ″ -tetrabromo-1,1 ′, 5 ′, 1 ″ -terphenyl was eluted with hexane / toluene = 1/1, and the eluted product was fractionated as fraction 1. Next, a component mainly composed of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -terphenyl was eluted only with toluene, and the eluted product was used as fraction 2. . Each fraction was concentrated under reduced pressure. As a result, the entire fraction 2 (0.32 g) became solid. On the other hand, since fraction 1 (1.97 g) was partially solid, it was divided into an oily part and a solid part. This oily portion was further purified by silica gel column chromatography (solvent, hexane). As a result, a colorless and transparent oily substance was obtained. This colorless and transparent oil solidified over time.

^{From the 1} H NMR spectrum, this colorless and transparent oil was 2,2 ′, 4 ′, 2 ″ -tetrabromo-1,1 ′, 5 ′, 1 ″ -terphenyl (1.37 g, yield 58). %).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.99 (d, J = 1.9 Hz, 1H), 7.68 (dd, J = 7.8 Hz, 1.7 Hz, 2H), 7.42 −7.19 (m, 6H), 7.15 (s, 1H).
^{The 1} H NMR spectrum is shown in FIG.
MS m / z: 546 (M ⁺ , 75%), 466 (M ⁺ -Br, 41), 386 (M ⁺ -2Br, 51), 226 (M ⁺ -4Br, 100).

  The structural formula of the obtained 2,2 ′, 4 ′, 2 ″ -tetrabromo-1,1 ′, 5 ′, 1 ″ -terphenyl is shown below.

  On the other hand, the solid part separated from the previous fraction 1 and the fraction 2 were combined and recrystallized from toluene. White needle crystals were obtained.

^{From the 1} H NMR spectrum, this white needle crystal was consistent with 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -terphenyl synthesized in Synthesis Example 2 (0. 47 g, 20% yield).

Example 2 (Synthesis of terphenylene)
Under a nitrogen atmosphere, 17 ml of THF was added to a 100 ml Schlenk reaction vessel. The mixture was cooled to −73 ° C., and 2.9 ml (2.8 mmol) of a cyclohexane solution of sec-butyllithium (manufactured by Kanto Chemical Co., 0.98M) was added. Under -73 ° C., 188 mg (0.344 mmol) of 2,2 ′, 4 ′, 2 ″ -tetrabromo-1,1 ′, 5 ′, 1 ″ -terphenyl synthesized in Synthesis Example 3 was added over 3 minutes. did. After aging at −73 ° C. to −68 ° C. for 30 minutes, 462 mg (3.44 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was charged at −75 ° C., and the temperature was raised to room temperature overnight. . After adding saturated brine and toluene, the phases were separated, and the organic phase was further washed with saturated brine. Concentrated under reduced pressure, hexane was added to the resulting residue, and the mixture was allowed to stand after stirring. The supernatant was removed, and the residue was dried under reduced pressure. The residue was recrystallized from toluene to obtain red plate crystals of terphenylene (24 mg, yield 31%). ^{The 1} H NMR spectrum (heavy benzene, 30 ° C.) was consistent with that obtained in Example 1.

Synthesis Example 4 (Synthesis of 2-bromo-3-iodonaphthalene)
2-Bromo-3-iodonaphthalene was synthesized as follows with reference to the method described in Synthetic Communications, 2003, Vol. 33, 2751-2756. The raw material 2-bromo-bis (hexachlorocyclopentadiene) naphthalene used as it was purchased from Sigma-Aldrich.

  Under a nitrogen atmosphere, 200 ml of methanesulfonic acid and 1.31 g (5.74 mmol) of orthoperiodic acid were added to a 500 ml three-necked flask reaction vessel. After stirring for 30 minutes, 4.36 g (17.2 mmol) of iodine was added. After stirring this mixture for 2 hours, 30.1 g (40.0 mmol) of 2-bromo-bis (hexachlorocyclopentadiene) naphthalene was added little by little. The mixture was stirred at 30 ° C. for 3 days. The reaction mixture was poured into ice water and the resulting solid was filtered. The solid was further washed with water and dried under reduced pressure to obtain a white powder of 2-bromo-3-iodo-bis (hexachlorocyclopentadiene) naphthalene (34.8 g, yield 99%).

To the end of the glass sublimation tube, 8.05 g (9.16 mmol) of 2-bromo-3-iodo-bis (hexachlorocyclopentadiene) naphthalene obtained above was added. The ends were heated to 210 ° C and depressurized to 1.5 Pascals. The generated 2-bromo-3-iodonaphthalene adhered to the glass tube on the decompression side, and hexachlorocyclopentadiene accumulated on the bottom on the decompression side. After 1 hour, the sublimation operation was interrupted, the adhered matter on the glass tube was taken out, and the same operation was repeated again. After sublimation operation for 1 hour, 2-bromo-3-iodonaphthalene was obtained (2.29 g, yield 75%).
¹ H NMR spectrum was consistent with literature values.
¹ H NMR (CDCl ₃ , 21 ° C.): δ = 8.41 (s, 1H), 8.14 (s, 1H), 7.75-7.65 (m, 2H), 7.54-7. 45 (m, 2H).

Synthesis Example 5 (Synthesis of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -dibenzoterphenyl) [Synthesis of tetrahaloterphenyl derivative]
Under a nitrogen atmosphere, 2.03 g (6.10 mmol) of 2-bromo-3-iodonaphthalene synthesized in Synthesis Example 4 and 12 ml of THF were added to a 100 ml Schlenk reaction vessel. The solution was cooled to −65 ° C., and 9.9 ml (6.4 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, 6.4 ml (6.4 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 white slurry was concentrated under reduced pressure. To the obtained white solid, 1.41-g (2.89 mmol) of 1,4-dibromo-2,5-diiodobenzene synthesized in Synthesis Example 1 and 285 mg of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry) ( 0.247 mmol), and 31 ml of THF were added. After carrying out the reaction at 60 ° C. for 4 hours, the reaction was stopped by cooling the vessel with water and adding 4 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 became neutral, and further washed with chloroform and THF. The obtained crystals were dried under reduced pressure, and white crystals of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -dibenzoterphenyl were obtained (1.20 g, yield 64). %).
Melting point by DSC measurement: 331 ° C.
¹ H NMR (CDCl ₃ , 60 ° C.): δ = 8.22 (s, 2H), 7.90-7.75 (m, 4H), 7.85 (s, 2H), 7.67 (s, 2H), 7.60-7.48 (m, 4H).
^{The 1} H NMR spectrum is shown in FIG.
MS m / z: 646 (M ⁺ , 64%), 566 (M ⁺ -Br, 8), 486 (M ⁺ -2Br, 34), 406 (M ⁺ -3Br, 6), 326 (M ⁺ -4Br) , 92), 163 ((M ⁺ -4Br) / 2, 100).

  The structural formula of the obtained 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -dibenzoterphenyl is shown below.

Example 3 (Synthesis of dibenzoterphenylene)
Under a nitrogen atmosphere, 28 ml of THF was added to a 100 ml Schlenk reaction vessel. After cooling to −73 ° C., 4.4 ml (4.3 mmol) of a cyclohexane solution of sec-butyllithium (manufactured by Kanto Chemical Co., 0.98M) was added. Under −73 ° C., 401 mg (0.621 mmol) of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -dibenzoterphenyl synthesized in Synthesis Example 5 was taken over 3 minutes. I put it in. After aging at −73 ° C. to −68 ° C. for 30 minutes, 740 mg (5.50 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added all at once at −75 ° C. The reaction temperature was raised to room temperature overnight. After adding saturated brine, the resulting solid was filtered. The obtained solid was washed with 3N hydrochloric acid, water and THF, and then dried under reduced pressure to obtain a yellow-orange solid of dibenzoterphenylene. Further, this solid was recrystallized from o-dichlorobenzene to obtain a plate-like dibenzoterphenylene solid having a golden metallic luster (97 mg, yield 48%).
Analysis by DSC measurement (using a sealed container): Exothermic heat due to carbonization was observed at 500 ° C.
MS m / z: 326 (M ^<+> , 100%), 163 (M ^<+ > / 2, 25).

  The structural formula of the obtained dibenzoterphenylene is shown below.

Reference Example 2 (Synthesis of dibenzoterphenylene)
In a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, 389 mg (0.602 mmol) of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -dibenzoterphenyl synthesized in Synthesis Example 5 and 28 ml of THF was added. The suspension was cooled to −73 ° C., and 4.4 ml (4.3 mmol) of a cyclohexane solution of sec-butyllithium (0.98 M manufactured by Kanto Chemical Co., Inc.) was added dropwise. After aging at −73 ° C. to −68 ° C. for 30 minutes, 726 mg (5.40 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added all at once at −75 ° C. The reaction temperature was raised to room temperature overnight. After adding saturated brine, the resulting solid was filtered. The obtained solid was washed with 3N hydrochloric acid, water and THF, and then dried under reduced pressure to obtain a yellow-orange solid of dibenzoterphenylene. Further, this solid was recrystallized from o-dichlorobenzene to obtain a plate-like dibenzoterphenylene solid having a golden metallic luster (55 mg, yield 28%).

Synthesis Example 6 (Synthesis of 4,5,4 ″, 5 ″ -tetrafluoro-2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -terphenyl) [tetrahaloter Synthesis of phenyl derivatives]
Under a nitrogen atmosphere, 2.53 g (9.30 mmol) of 1,2-dibromo-4,5-difluorobenzene (manufactured by Wako Pure Chemical Industries) and 15 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −40 ° C., and 15 ml (9.7 mmol) of a solution of isopropyl magnesium bromide (manufactured by Kanto Chemical Co., Ltd., 0.65 M) in THF was added dropwise. After aging for 30 minutes, 9.8 ml (9.8 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 white slurry was concentrated under reduced pressure. To the obtained white solid, 2.15 g (4.41 mmol) of 1,4-dibromo-2,5-diiodobenzene synthesized in Synthesis Example 1 and 408 mg of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.353 mmol), and 30 ml of THF were added. After carrying out the reaction for 6 hours at 60 ° C., the vessel was cooled with water and the reaction was stopped by adding 3N hydrochloric acid (8 ml). After adding toluene and sodium chloride, the phases were separated, and the organic phase was washed with brine. The organic phase was concentrated under reduced pressure and the solvent was distilled off. The obtained residue was dissolved in 10 ml of toluene, 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.5 ml) was added, and the mixture was stirred at room temperature for 2 hours. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The organic phase was dissolved in toluene: hexane = 1: 1 and passed through a column packed with silica gel. The eluate was concentrated under reduced pressure, and the resulting solid was recrystallized using a mixed solvent of hexane: toluene = 3: 1 to obtain the desired white solid (1.48 g, yield 54%).
¹ H NMR (CDCl ₃ , 21 ° C.): δ = 7.58-7.45 (m, 2H), 7.53 (s, 2H), 7.23-7.09 (m, 2H).
MS m / z: 618 (M ⁺ , 73%), 538 (M ⁺ -Br, 32), 458 (M ⁺ -2Br, 45), 378 (M ⁺ -3Br, 4), 298 (M ⁺ -4Br) , 100).

  The structure of 4,5,4 ″, 5 ″ -tetrafluoro-2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -terphenyl obtained is shown below.

Example 4 (Synthesis of 2,3,7,8-tetrafluoroterphenylene)
Under a nitrogen atmosphere, 28 ml of THF was added to a 100 ml Schlenk reaction vessel. The mixture was cooled to −73 ° C., and 5.9 ml (5.8 mmol) of a cyclohexane solution of sec-butyllithium (0.98M manufactured by Kanto Chemical Co., Inc.) was added. The 4,5,4 ″, 5 ″ -tetrafluoro-2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -ter synthesized in Synthesis Example 6 at −73 ° C. 510 mg (0.825 mmol) of phenyl was added over 4 minutes. After aging at −73 ° C. to −68 ° C. for 20 minutes, 985 mg (7.33 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added at a stretch at −75 ° C. The temperature was gradually raised, and the reaction temperature was raised to -20 ° C over 7 hours. After adding saturated brine and toluene, the phases were separated, and the organic phase was further washed with saturated brine. The mixture was concentrated under reduced pressure, hexane was added to the resulting residue, and the mixture was stirred and allowed to stand. The supernatant was removed, and the residue was dried under reduced pressure. The residue was recrystallized from toluene to obtain red crystals of 2,3,7,8-tetrafluoroterphenylene (81 mg, yield 33%).
¹ H NMR (CDCl ₃ , 21 ° C.): δ = 6.33 (t, J = 7.3 Hz, 4H), 6.14 (s, 2H).
MS m / z: 298 (M ^<+> , 100%), 149 (M ^<+ > / 2, 38).

  The structure of the obtained 2,3,7,8-tetrafluoroterphenylene is shown below.

Synthesis Example 7 (Synthesis of 1,2-dibromo-4,5-diiodobenzene)
1,2-Dibromo-4,5-diiodobenzene was synthesized as follows according to “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).

Synthesis Example 8 (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 7 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 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 2 hours. The toluene solution was washed twice with water, the organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent, hexane), 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).

Synthesis Example 9 (Synthesis of 2-phenyl-5-bromo-4-biphenylboronic acid)
Under a nitrogen atmosphere, 755 mg (1.95 mmol) of 1,2-dibromo-4,5-diphenylbenzene synthesized in Synthesis Example 8 and 12 ml of THF were added to a 100 ml Schlenk reaction vessel. The solution was cooled to −100 ° C., and 1.3 ml (2.1 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) was added dropwise. After aging for 30 minutes, 472 mg (2.51 mmol) of triisopropyl borate (manufactured by Tokyo Chemical Industry) was added dropwise at that temperature. After gradually warming to room temperature, 3N hydrochloric acid was added and the phases were separated. The organic phase was concentrated under reduced pressure to obtain 770 mg of a white solid.

Synthesis Example 10 (Synthesis of 4,5-diphenyl-2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -benzoterphenyl) [Synthesis of tetrahaloterphenyl derivative]
Under a nitrogen atmosphere, 333 mg (1.00 mmol) of 2-bromo-3-iodonaphthalene synthesized in Synthesis Example 4 and 20 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −65 ° C., and 1.3 ml (1.04 mmol) of a THF solution of isopropylmagnesium bromide (Tokyo Chemical Industry, 0.80 M) was added dropwise. After aging for 30 minutes, 1.1 ml (1.1 mmol) of a diethyl ether solution of zinc chloride (manufactured by Sigma-Aldrich, 1.0 M) was added dropwise at that temperature. After gradually warming to room temperature, the produced white slurry was concentrated under reduced pressure. To the obtained white solid, 488 mg (1.00 mmol) of 1,4-dibromo-2,5-diiodobenzene synthesized in Synthesis Example 1 and 83 mg of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.). 072 mmol), and 3 ml of THF were added. After carrying out the reaction for 6 hours at 60 ° C., the vessel was cooled with water and the reaction was stopped by adding 4 ml of 3N hydrochloric acid. After adding toluene and sodium chloride, the phases were separated, and the organic phase was washed with brine. The organic phase was concentrated under reduced pressure and the solvent was distilled off. After further vacuum drying under heating, 222 mg of 2-phenyl-5-bromo-4-biphenylboronic acid synthesized in Synthesis Example 9 and 41 mg of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained residue. 035 mmol), 5.2 ml of toluene, and 1.2 ml of ethanol were added. Further, a solution consisting of 349 mg (3.29 mmol) of sodium carbonate and 1.7 ml of water was added, and this mixture was reacted at 85 ° C. for 6 hours. After cooling to room temperature, toluene and brine were added for phase separation, and the organic phase was washed with brine. The organic phase was concentrated under reduced pressure, the solvent was distilled off, and further dried under vacuum. The obtained crude solid was washed with hexane to obtain the desired product (292 mg, yield 62.1%).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.22 (s, 0.45H), 8.20 (s, 0.55H), 7.87-7.80 (m, 2H), 7. 85 (s, 1H), 7.77 (s, 1H), 7.69 (s, 0.55H), 7.68 (s, 0.45H), 7.66 (s, 1H), 7.59 -7.53 (m, 2H), 7.42 (s, 0.55H), 7.38 (s, 0.45H), 7.28-7.13 (m, 10H).
^{The 1} H NMR spectrum is shown in FIG.
MS m / z: 748 (M ⁺ , 100%), 668 (M ⁺ -Br, 10%), 588 (M ⁺ -2Br, 24%), 508 (M ⁺ -3Br, 14%), 428 (M ⁺ -4Br, 29%).

  The structural formula of the resulting 4,5-diphenyl-2,2 ', 5', 2 "-tetrabromo-1,1 ', 4', 1" -benzoterphenyl is shown below.

Reference Example 3 (Synthesis of 2,3-diphenylbenzoterphenylene)
Under a nitrogen atmosphere, 6 ml of THF was added to a 100 ml Schlenk reaction vessel. After cooling to −73 ° C., 0.95 ml (0.93 mmol) of a cyclohexane solution of sec-butyllithium (0.98M manufactured by Kanto Chemical Co., Inc.) was added. Under −73 ° C., 98 mg (0.131 mmol) of 4,5-diphenyl-2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -benzoterphenyl synthesized in Synthesis Example 10 ) Was added over 2 minutes. After aging at −73 ° C. to −68 ° C. for 20 minutes, 188 mg (1.40 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added all at once at −75 ° C. The temperature was gradually raised, and the reaction temperature was raised to 0 ° C. over 14 hours. After adding 3N hydrochloric acid and toluene, the phases were separated, and the organic phase was washed with saturated brine.
The organic phase was concentrated under reduced pressure, hexane was added to the resulting residue, and the mixture was stirred and allowed to stand. The supernatant was removed, and the residue was dried under reduced pressure. The residue was recrystallized from toluene to give 2,3-diphenylbenzoterphenylene orange crystals (19 mg, 34% yield).
¹ H NMR (heavy benzene, 22 ° C.): δ = 7.26-7.19 (m, 4H), 7.12-6.92 (m, 10H), 6.50 (s, 2H), 6. 49 (s, 2H), 6.21 (s, 2H).
^{The 1} H NMR spectrum is shown in FIG.
MS m / z: 428 (M ⁺ , 100%), 213 ((M ⁺ / 2) -1, 34%).

  The structure of the obtained 2,3-diphenylbenzoterphenylene is shown below.

Synthesis Example 11 (Synthesis of 2,3-dibromoanthracene)
2,3-Dibromoanthracene was synthesized as follows according to “Synthesis”, 1988, pp. 628-630.

Under a nitrogen atmosphere, 0.5 g (1.49 mmol) of 6,7-dibromo-1,4-dihydroanthracene was dissolved in 100 ml of benzene in a 300 ml Schlenk reaction vessel. Dichlorodicyanobenzoquinone 0.60 g (2.51 mmol) was added, and the mixture was stirred for 4 hours under reflux conditions. The produced insoluble hydroquinone was filtered off while hot and removed from the solution. When the obtained solution was cooled to room temperature, a yellow solid of 2,3-dibromoanthracene precipitated. After filtration, drying and concentration under reduced pressure, 180 mg of a yellow solid was obtained (180 mg, 48% yield).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.33 (s, 2H), 8.31 (s, 2H), 7.98 (dd, J = 6.6 Hz, 3.2 Hz, 2H), 7.50 (dd, J = 6.6 Hz, 3.2 Hz, 2H).
^{The 1} H NMR spectrum is shown in FIG.

Synthesis Example 12 (Synthesis of 3-bromo-2-anthracenylboronic acid)
Under a nitrogen atmosphere, 299 mg (0.890 mmol) of 2,3-dibromoanthracene obtained in Synthesis Example 11 and 31 ml of THF were added to a 100 ml Schlenk reaction vessel. This solution was cooled to −76 ° C., and 1.7 ml (2.7 mmol) of a hexane solution of n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.59 M) was added dropwise. After aging for 20 minutes, 595 mg (3.16 mmol) of tri (isopropoxy) boron (manufactured by Tokyo Chemical Industry) was added dropwise at that temperature. After gradually warming to room temperature, 3N hydrochloric acid was added and the phases were separated. The organic phase was concentrated under reduced pressure and washed with hexane. The obtained residue was vacuum-dried to obtain 250 mg of a yellow solid.

  The structural formula of the obtained 3-bromo-2-anthracenylboronic acid is shown below.

Synthesis Example 13 (Synthesis of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -naphthoterphenyl) [Synthesis of tetrahaloterphenyl derivative]
In a 200 ml Schlenk reaction vessel under a nitrogen atmosphere, 1.21 g (6.02 mmol) of 2-bromophenylboronic acid (manufactured by Sigma-Aldrich), 1,4-dibromo-2,5-diiodobenzene 1 synthesized in Synthesis Example 1 .95 g (4.00 mmol), 231 mg (0.200 mmol) of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry), 31 ml of toluene, and 7 ml of ethanol were added. Further, an aqueous solution consisting of 2.54 g (24.0 mmol) of sodium carbonate and 9 ml of water was added, and the mixture was reacted at 75 ° C. for 20 hours. After cooling to room temperature, toluene and brine were added, phase separation was performed, and the organic phase was washed with brine. The organic phase was concentrated under reduced pressure, the solvent was distilled off, and further dried under vacuum. The obtained residue was dissolved in toluene, 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.36 ml) was added, and the mixture was stirred at room temperature for 2 hours. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The residue was filtered by column chromatography packed with silica gel (solvent: hexane) to obtain 1.62 g of a solid. In a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, 787 mg of this solid, 526 mg of 3-bromo-2-anthracenylboronic acid synthesized in Synthesis Example 12, 101 mg of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.087 mmol), 12.2 ml of toluene, and 2.5 ml of ethanol were added. Further, an aqueous solution consisting of 967 mg (9.12 mmol) of sodium carbonate and 3.7 ml of water was added, and the mixture was reacted at 80 ° C. for 15 hours. After cooling to room temperature, toluene and brine were added. The precipitated solid was separated by filtration and re-precipitated twice from chloroform / hexane to obtain a yellow solid (546 mg).
¹ H NMR (CDCl ₃ , 60 ° C.): δ = 8.40-8.34 (m, 3H), 8.05-7.91 (m, 3H), 7.74-7.66 (m, 2H) ), 7.59 (s, 1H), 7.54-7.46 (m, 2H), 7.43-7.27 (m, 3H).
^{The 1} H NMR spectrum is shown in FIG.

MS m / z: 646 (M ⁺ , 100%), 566 (M ⁺ -Br, 2), 486 (M ⁺ -2Br, 27), 406 (M ⁺ -3Br, 5), 326 (M ⁺ -4Br) , 50).

  The structural formula of the obtained 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -naphtherphenyl is shown below.

Example 5 (Synthesis of naphthoterphenylene)
Under a nitrogen atmosphere, 22 ml of THF was added to a 100 ml Schlenk reaction vessel. After cooling to −73 ° C., 3.2 ml (3.2 mmol) of a cyclohexane / hexane solution of sec-butyllithium (manufactured by Kanto Chemical Co., 1.0M) was added. Under −73 ° C., 310 mg (0.480 mmol) of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -naphthophenyl synthesized in Synthesis Example 13 was taken over 3 minutes. I put it in. After aging at −73 ° C. to −68 ° C. for 30 minutes, copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) 603 mg (4.48 mmol) was added at −75 ° C. The temperature was slowly raised to room temperature over 16 hours, and 3N hydrochloric acid and toluene were added. The precipitated solid was separated by filtration, and the solid was further washed with toluene and water. The obtained solid was recrystallized and purified from o-dichlorobenzene to obtain the target orange solid (62 mg, 39% yield).
MS m / z: 326 (M ^<+> , 100%), 163 (M ^<+ > / 2, 21).

  The structural formula of the obtained naphthoterphenylene is shown below.

Synthesis Example 14 (Synthesis of 1,2-di (n-hexyl) benzene)
1,2-di (n-hexyl) benzene can be obtained from 1,2-dichlorobenzene and n-hexylmagnesium bromide by referring to the method of “Organic Synthesis”, 1978, 58, 127-133. Was synthesized.

  Under a nitrogen atmosphere, 2.7 ml (24.1 mmol) of 1,2-dichlorobenzene, 66 mg (0.12 mmol) of nickel chloride {bis (diphenylphosphino) propane}, and 18 ml of diethyl ether were added to a 200 ml Schlenk reaction vessel. The mixture was cooled to 0 ° C., and 30 ml (60 mmol) of a diethyl ether solution of n-hexylmagnesium bromide (manufactured by Sigma-Aldrich, 2.0M) was added dropwise. After 6 hours of reaction at 35 ° C., 3N hydrochloric acid was added to stop the reaction. Extracted with diethyl ether and the organic phase was washed with water and saturated aqueous sodium bicarbonate. It dried with calcium chloride and concentrated the solvent under reduced pressure. The residue was distilled under reduced pressure (0.15 mmHg, 100 ° C.) to obtain a liquid of 1,2-di (n-hexyl) benzene (5.43 g, yield 91%).

Synthesis Example 15 (Synthesis of 1,2-di (n-hexyl) -4-bromo-5-iodobenzene)
Under a nitrogen atmosphere, in a 100 ml Schlenk reaction vessel, 2.95 g (12.0 mmol) of 1,2-di (n-hexyl) benzene, 684 mg (3.00 mmol) of periodic acid dihydrate, 1.62 g of iodine (6 .36 mmol), 6.9 ml acetic acid, 1.4 ml water, and 0.21 ml sulfuric acid were added. After stirring at 65 ° C. for 6 hours and cooling to room temperature, an aqueous sodium hydrogen sulfite solution was added to stop the reaction. Extraction was performed with dichloromethane, and the organic phase was washed with water and then dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (hexane) to obtain 3.73 g of liquid. To 3.47 g of this liquid, 20 ml of dichloromethane was added and cooled to 0 ° C. After adding 67 mg of iron powder (manufactured by Sigma-Aldrich) and 10 mg (0.04 mmol) of iodine, 0.48 ml (9.37 mmol) of bromine was added dropwise. After stirring at 0 ° C. for 2 hours, an aqueous sodium hydrogen sulfite solution was added to stop the reaction. The organic phase was washed with water and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the resulting residue was filtered using silica gel, and the filtrate was concentrated and then recrystallized and purified with hexane at -78 ° C. to obtain 1,2-di (n-hexyl) -4-bromo-5- Iodobenzene was obtained (3.14 g, 75% yield).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 7.59 (s, 1H), 7.37 (s, 1H), 2.58-2.40 (m, 4H), 1.57-1. 45 (m, 4H), 1.42-1.23 (m, 12H), 0.90 (t, J = 6.6 Hz, 6H).
^{The 1} H NMR spectrum is shown in FIG.
MS m / z: 451 (M ⁺ , 98%), 450 (M ⁺ −1, 100), 309 (M ⁺ −2C ₅ H ₁₁ , 71), 183 (M ⁺ −2C ₅ H ₁₁ −I + 1, 17 _{^{), 103 (M + -2C 5}} H 11 -I-Br + 1,8).

Synthesis Example 16 (Synthesis of 4,5-di (n-hexyl) -2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -naphthoterphenyl) [tetrahaloterphenyl Synthesis of derivatives]
Under a nitrogen atmosphere, 1804 mg (4.00 mmol) of 1,2-di (n-hexyl) -4-bromo-5-iodobenzene obtained in Synthesis Example 15 and 30 ml of THF were added to a 200 ml Schlenk reaction vessel. This solution was cooled to −81 ° C., and 10.5 ml (8.40 mmol) of a THF solution of isopropylmagnesium bromide (Tokyo Chemical Industry, 0.80 M) was added dropwise. After aging for 30 minutes, 1.18 ml (10.6 mmol) of tri (methoxy) boron (manufactured by Wako Pure Chemical Industries) was added dropwise at that temperature. After gradually warming to room temperature, 3N hydrochloric acid was added and the phases were separated. The organic phase was concentrated under reduced pressure to obtain 1637 mg of a viscous material. To the resulting viscous material, 1854 mg (3.80 mmol) of 1,4-dibromo-2,5-diiodobenzene synthesized in Synthesis Example 1 and 220 mg of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.). 190 mmol), 45 ml of toluene, and 12 ml of ethanol were added. Further, an aqueous solution consisting of 1611 mg (15.2 mmol) of sodium carbonate and 15 ml of water was added, and the mixture was reacted at 80 ° C. for 13 hours. After cooling to room temperature, toluene and brine were added, phase separation was performed, and the organic phase was washed with brine. The organic phase was concentrated under reduced pressure, the solvent was distilled off, and further dried under vacuum. The obtained residue was dissolved in toluene, 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.34 ml) was added, and the mixture was stirred at room temperature for 2 hours. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The residue was purified by column chromatography packed with silica gel (solvent; hexane: chloroform = 10: 1) to obtain 2227 mg of liquid. In a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, 826 mg of this liquid, 425 mg of 3-bromo-2-anthracenylboronic acid synthesized in Synthesis Example 12, 90 mg of tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.078 mmol), 15 ml of toluene, and 2.6 ml of ethanol were added. Further, an aqueous solution composed of 513 mg (4.84 mmol) of sodium carbonate and 4.8 ml of water was added, and the mixture was reacted at 80 ° C. for 16 hours. After cooling to room temperature, toluene and brine were added for phase separation, and the organic phase was washed with brine. The organic phase was concentrated under reduced pressure, the solvent was distilled off, and further dried under vacuum. The obtained residue was dissolved in toluene, 70% tert-butyl hydroperoxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.14 ml) was added, and the mixture was stirred at room temperature for 2 hours. This solution was washed with water, and the organic phase was concentrated under reduced pressure. The residue was filtered through column chromatography packed with silica gel (solvent; hexane: chloroform = 5: 2), and the filtrate was concentrated under reduced pressure. The obtained residue was washed with hexane and vacuum-dried to obtain the objective yellow solid (705 mg).
¹ H NMR (CDCl ₃ , 22 ° C.): δ = 8.44 (s, 0.7H), 8.41 (s, 0.7H), 8.38 (s, 1H), 8.33 (s, 0.3H), 8.32 (s, 0.3H), 8.08-7.96 (m, 2H), 8.00 (s, 0.7H), 7.93 (s, 0.3H) 7.68 (s, 0.3H), 7.67 (s, 0.3H), 7.60 (s, 0.7H), 7.54-7.47 (m, 2H), 7.46. (S, 0.7H), 7.28-7.20 (m, 1.4H), 7.12 (s, 0.3H), 7.08 (s, 0.3H), 2.60 (m , 4H), 1.62 (m, 4H), 1.38 (m, 12H), 0.92 (m, 6H).
^{The 1} H NMR spectrum is shown in FIG.
MS m / z: 814 (M ⁺ , 100%), 734 (M ⁺ -Br, 13), 673 (M ⁺ + 1-2C ₅ H ₁₁ , 14), 432 (M ⁺ -2C ₅ H ₁₁ -3Br, _{^{7), 352 (M + -2C}} 5 H 11 -4Br, 11).

  The structural formula of the obtained 4,5-di (n-hexyl) -2,2 ', 5', 2 "-tetrabromo-1,1 ', 4', 1" -naphthoterphenyl is shown below.

Example 6 (Synthesis of 2,3-di (n-hexyl) naphthophenylene)
Under a nitrogen atmosphere, 8 ml of THF was added to a 100 ml Schlenk reaction vessel. After cooling to −73 ° C., 1.4 ml (1.4 mmol) of a cyclohexane / hexane solution of sec-butyllithium (manufactured by Kanto Chemical Co., 1.0M) was added. 4,5-di (n-hexyl) -2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -naphthoterphenyl synthesized in Synthesis Example 16 at −73 ° C. 143 mg (0.176 mmol) was added over 3 minutes. After aging at −73 ° C. to −68 ° C. for 30 minutes, 222 mg (1.65 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added at −75 ° C. The temperature was slowly raised to room temperature over 16 hours, and 3N hydrochloric acid and toluene were added. The phases were separated, and the organic phase was further washed with saturated aqueous sodium hydrogen carbonate and water, and concentrated under reduced pressure. The obtained residue was washed with hexane and further recrystallized and purified from toluene to obtain the target orange solid (37 mg, 43% yield).
¹ H NMR (deuterium toluene, 100 ° C.): δ = 7.61-7.55 (m, 2H), 7.58 (s, 2H), 7.22-7.14 (m, 2H), 6. 56 (s, 2H), 6.36 (s, 2H), 6.29 (s, 2H), 2.42 (t, J = 7.6 Hz, 4H), 1.50 (m, 4H), 1 .33 (m, 12H), 0.89 (t, J = 7.1 Hz, 6H).
^{The 1} H NMR spectrum is shown in FIG.
_{^{MS m / z: 494 (M}} +, 100%), 353 (M + -2C 5 H 11 +1,41), 247 (M + / 2,6).

  The structural formula of the obtained 2,3-di (n-hexyl) naphthophenylene is shown below.

Reference Example 4 (Synthesis of 2,3-di (n-hexyl) naphthophenylene)
4,5-Di (n-hexyl) -2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ − synthesized in Synthesis Example 16 in a 100 ml Schlenk reaction vessel under a nitrogen atmosphere Naphthaterphenyl 134 mg (0.165 mmol) and THF 8 ml were added. After cooling this solution to -74 ° C, 1.3 ml (1.3 mmol) of a cyclohexane / hexane solution of sec-butyllithium (manufactured by Kanto Chemical Co., 1.0M) was added dropwise. After stirring at -74 ° C to -68 ° C for 30 minutes, 218 mg (1.62 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The temperature was slowly raised to room temperature over 16 hours, and 3N hydrochloric acid and toluene were added. The phases were separated, and the organic phase was further washed with saturated aqueous sodium hydrogen carbonate and water, and concentrated under reduced pressure. The obtained residue was washed with hexane and further recrystallized and purified from toluene to obtain the target orange solid (15 mg, 18% yield).

Example 7 (Synthesis of 2,3-di (n-hexyl) naphthophenylene)
Under a nitrogen atmosphere, 8 ml of THF was added to a 100 ml Schlenk reaction vessel. After cooling to −73 ° C., 0.81 ml (1.18 mmol) of a pentane solution of tert-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.46 M) was added. 4,5-di (n-hexyl) -2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -naphthoterphenyl synthesized in Synthesis Example 16 at −73 ° C. 121 mg (0.146 mmol) was added over 3 minutes. After aging at −73 ° C. to −68 ° C. for 30 minutes, 177 mg (1.31 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added at −75 ° C. The temperature was slowly raised to room temperature over 16 hours, and 3N hydrochloric acid and toluene were added. The phases were separated, and the organic phase was further washed with saturated aqueous sodium hydrogen carbonate and water, and concentrated under reduced pressure. The obtained residue was washed with hexane and further recrystallized and purified from toluene to obtain the target orange solid (25 mg, yield 35%).

Synthesis Example 17 (Synthesis of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -dinaphthoterphenyl) [Synthesis of tetrahaloterphenyl derivative]
Under a nitrogen atmosphere, 299 mg (0.614 mmol) of 1,4-dibromo-2,5-diiodobenzene synthesized in Synthesis Example 1 and 3-bromo-2-anthracenyl synthesized in Synthesis Example 12 in a 200 ml Schlenk reaction vessel Boronic acid 425 mg, tetrakis (triphenylphosphine) palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 50 mg (0.043 mmol), toluene 9 ml, and ethanol 1.5 ml were added. Further, an aqueous solution composed of 390 mg (3.68 mmol) of sodium carbonate and 2.7 ml of water was added, and the mixture was reacted at 80 ° C. for 18 hours. After cooling to room temperature, toluene and brine were added. The precipitated solid was separated by filtration, washed with water until the filtrate became neutral, and further washed with chloroform and THF. The obtained solid was dried under reduced pressure to obtain a target yellow solid (330 mg, yield 72%).
MS m / z: 746 (M ⁺ , 71%), 666 (M ⁺ -Br, 7), 586 (M ⁺ -2Br, 36), 506 (M ⁺ -3Br, 5), 426 (M ⁺ -4Br) , 100), 373 (M ⁺ / 2, 63).

  The structural formula of the obtained 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -dinaphthoterphenyl is shown below.

Example 8 (Synthesis of dinaphthoterphenylene)
Under a nitrogen atmosphere, 10 ml of THF was added to a 100 ml Schlenk reaction vessel. The mixture was cooled to −73 ° C., and 2.0 ml (2.0 mmol) of a cyclohexane / hexane solution of sec-butyllithium (manufactured by Kanto Chemical Co., 1.0M) was added. Under −73 ° C., 189 mg (0.253 mmol) of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -dinaphthoterphenyl synthesized in Synthesis Example 17 was applied over 3 minutes. And put it in. After aging at −73 ° C. to −68 ° C. for 30 minutes, 306 mg (2.28 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added at −75 ° C. The temperature was slowly raised to room temperature over 16 hours, and 3N hydrochloric acid and toluene were added. The phases were separated, and the organic phase was further washed with saturated aqueous sodium hydrogen carbonate and water, and concentrated under reduced pressure. The obtained residue was washed with hexane and further recrystallized and purified from toluene to obtain the target orange solid (50 mg, 46% yield).
MS m / z: 426 (M ^<+> , 100%), 213 (M ^<+ > / 2, 21).

  The structural formula of the obtained dinaphthoterphenylene is shown below.

¹ H NMR spectrum (CDCl ₃ , 22 ° C.) of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -terphenyl of Synthesis Example 2 ¹ H NMR spectrum of terphenylene of Example 1 (heavy benzene, 30 ° C.) ¹ H NMR spectrum (CDCl ₃ , 22 ° C.) of 2,2 ′, 4 ′, 2 ″ -tetrabromo-1,1 ′, 5 ′, 1 ″ -terphenyl of Synthesis Example 3 ¹ H NMR spectrum (CDCl ₃ , 60 ° C.) of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -dibenzoterphenyl of Synthesis Example 5 ¹ H NMR spectrum (CDCl ₃ , 22 ° C.) of 4,5-diphenyl-2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -benzoterphenyl of Synthesis Example 10 ¹ H NMR spectrum of 2,3-diphenylbenzoterphenylene of Reference Example 3 (heavy benzene, 22 ° C.) ¹ H NMR spectrum of 2,3-dibromoanthracene of Synthesis Example 11 (CDCl ₃ , 22 ° C.) ¹ H NMR spectrum (CDCl ₃ , 60 ° C.) of 2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -naphthoterphenyl of Synthesis Example 13 ¹ H NMR spectrum (CDCl ₃ , 22 ° C.) of 1,2-di (n-hexyl) -4-bromo-5-iodobenzene of Synthesis Example 15 ¹ H NMR spectrum (CDCl ₃ ) of 4,5-di (n-hexyl) -2,2 ′, 5 ′, 2 ″ -tetrabromo-1,1 ′, 4 ′, 1 ″ -naphthoterphenyl of Synthesis Example 16 , 22 ° C) ¹ H NMR spectrum of 2,3-di (n-hexyl) naphthoterphenylene of Example 6 (heavy toluene, 100 ° C.)

Claims (4)

A method for producing a terphenylene derivative represented by the following general formula (1), wherein the tetrahaloterphenyl derivative represented by the following general formula (2) is selected from n-butyllithium, sec-butyllithium, and tert-butyllithium. A method for producing a terphenylene derivative, characterized in that it is introduced into a lithiating agent, tetralithiated, and then reacted with a copper compound.

(Here, the substituents R ^{1 to} R ¹⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 20 carbon atoms .
l and n are each an integer of 0 to 2, and m is 0 . )

(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 ^{14 in} the general formula (2) and the symbols l, m, and n represent the general formula (1). And has the same meaning as the substituents and symbols shown.
In addition, the notation of the general formula (2) is a general term for the para-positional isomer and the meta-positional isomer in which the general formula (2) is represented by the following general formulas (3) and (4).

(Here, the substituents R ^{1 to} R ¹⁴ and X ^{1 to} X ⁴ in the general formula (3) and the general formula (4), and the symbols l, m, and n are the substituents and symbols represented by the general formula (2)). It shows the same meaning as The method for producing a terphenylene derivative according to claim 1, wherein the lithiating agent is used in an amount of 6 to 10 equivalents relative to the tetrahaloterphenyl derivative represented by the general formula (2) . The method for producing a terphenylene derivative according to claim 1 or 2, wherein l and n are both 2 . The method for producing a terphenylene derivative according to claim 1 or 2 , wherein l is 2 and n is 0 .

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