WO2014024769A1 - Method for synthesizing anti-anthradichalcogenophene - Google Patents

Abstract

A method for synthesizing anti-anthradichalcogenophene comprises: a step of reacting a compound represented by formula (1) with a halogenating agent to produce a compound represented by formula (2); a step of reacting the compound represented by formula (2) with a dealkylating agent to produce a compound represented by formula (3); a step of reacting the compound represented by formula (3) with an acetylating agent to produce a compound represented by formula (4); a step of reacting the compound represented by formula (4) with a terminal-acethylene compound to produce a compound represented by formula (5); and a step of reacting the compound represented by formula (5) with a base to cause the cyclization of the compound, thereby producing a compound represented by formula (6). In the formulae, R¹ represents an alkyl group; X represents a halogen atom; Ac represents an acetyl group; R² represents a trimethylsilyl group, a phenyl group or an alkyl group; and R³ represents a hydrogen atom, a phenyl group or an alkyl group.

Description

Method for synthesizing anti-ant radical kogenophene

The present invention relates to a method for synthesizing an anti-ant radical cogenophene.

Acene dichalcogenophene compounds such as benzodithiophene, naphthodithiophene and anthradithiophene are promising as organic semiconductor materials. In these ascendichalcogenophenes, there are anti-isomers and syn-isomers. It is known that the isomers of benzodithiophene and naphthodithiophene have different semiconductor characteristics, and the anti isomer exhibits higher carrier mobility than the syn isomer.

Further, as a material for the thin film transistor, anant radical cogenophene is disclosed (for example, Patent Document 1 and Non-Patent Document 1). These are a mixture of a syn isomer and an anti isomer, and it is reported that the carrier mobility of anthradithiophene mixed with a syn isomer and an anti isomer was 0.09 cm ² V ⁻¹ s ⁻¹ .

JP-A-11-195790

In Patent Document 1 and Non-Patent Document 1, a mixture of an anti-form and syn-form of anantradical cogenophene is obtained, and a method for selectively synthesizing an anti-form is not described.

The present invention has been made in view of the above-described matters, and an object of the present invention is to provide a method for producing an anti-ant radical cogenophene capable of selectively synthesizing an anti isomer of an anant radical cogenophene.

The method for synthesizing the anti-ant radical cogenophene according to the first aspect of the present invention includes:
Reacting a compound represented by Formula 1 with a halogenating agent to obtain a compound represented by Formula 2;

Reacting the compound represented by Formula 2 with a dealkylating agent to obtain a compound represented by Formula 3;

Reacting the compound represented by Formula 3 with an acetylating agent to obtain a compound represented by Formula 4,

Reacting the compound represented by Formula 4 with a terminal acetylene compound to obtain a compound represented by Formula 5;

Cyclizing the compound represented by Formula 5 by allowing a base to act to obtain a compound represented by Formula 6;

It is characterized by that.
(In formulas 1 and 2, R ¹ represents an alkyl group, in formulas 2 to 4, X represents a halogen, in formulas 4 and 5, Ac represents an acetyl group, and in formula 5, R ² represents trimethylsilyl group, a phenyl group, or an alkyl group, in the formula 6, R ³ is hydrogen, phenyl or an alkyl group.)

The method for synthesizing the anti-ant radical cogenophene according to the second aspect of the present invention comprises:
Reacting a compound represented by Formula 11 with a sulfur compound or a selenium compound to obtain a compound represented by Formula 12;

Reacting the compound represented by Formula 12 with a dealkylating agent to obtain a compound represented by Formula 13;

Reacting the compound represented by Formula 13 with trifluoromethanesulfonic anhydride to obtain a compound represented by Formula 14;

Reacting the compound represented by Formula 14 with a terminal acetylene compound to obtain a compound represented by Formula 15;

Cyclizing the compound represented by Formula 15 with iodine to obtain a compound represented by Formula 16;

It is characterized by that.
(In Formula 11 and Formula 12, R ¹¹ represents an alkyl group; in Formula 12 to Formula 15, R ¹² represents an alkyl group; in Formula 12 to Formula 16, Y represents sulfur or selenium; Tf represents a trifluoromethanesulfonyl group, and in formulas 15 and 16, R ¹³ represents a trimethylsilyl group, a phenyl group, or an alkyl group.)

Further, after obtaining the compound represented by the formula 16 wherein R ¹³ is a trimethylsilyl group, the compound is reduced to anthra [2,3-b: 6,7-b ′] dithiophene or anthra [2,3- b: 6,7-b ′] diselenophene may be obtained.

Further, after obtaining the compound represented by the formula 16 wherein R ¹³ is a phenyl group, the compound is reduced to 2,8-diphenylanthra [2,3-b: 6,7-b ′] dithiophene or 2, 8-Diphenylanthra [2,3-b: 6,7-b ′] diselenophene may be obtained.

In the method for synthesizing anti-ant radical kogenophene according to the present invention, anti-ant radical kogenophene can be selectively synthesized.

FIG. 1A is a graph showing transistor characteristics of an FET element ADT, FIG. 1A is a graph showing output characteristics, and FIG. 1B is a graph showing transfer characteristics. FIG. 2A is a graph showing transistor characteristics of an FET element ADS, FIG. 2A is an output characteristic, and FIG. 2B is a graph showing transfer characteristics. FIG. 3A is a graph showing transistor characteristics of the FET element DPh-ADF, FIG. 3A is a graph showing output characteristics, and FIG. 3B is a graph showing transfer characteristics. FIG. 4A is a graph showing transistor characteristics of the FET element DPh-ADT, FIG. 4A is a graph showing output characteristics, and FIG. 4B is a graph showing transfer characteristics.

(Embodiment 1)
The method for synthesizing the anti-ant radical cogenophene according to Embodiment 1 is a method for synthesizing anti-anthradifuran. Hereinafter, the synthesis of anti-anthradifuran will be described step by step.

First, the compound represented by Formula 1 is halogenated. In Formula 1, R ¹ represents an alkyl group, and the alkyl group preferably has 6 or less carbon atoms, and more preferably a methyl group.

By reacting with a halogenating agent, a halogen is bonded to the 3rd and 7th carbons adjacent to the carbon to which the alkoxy group of 2,6-dialkoxyanthracene represented by Formula 1 is bonded. 2,6-dialkoxy-3,7-dihalogenoanthracene is obtained. In formula 2, R ¹ has the same meaning as described above, and X represents halogen.

Examples of the halogenating agent include Cl ₂ , Br ₂ , I ₂ , hexa-chloroethane, 1,2-dichlorotetrafluoroethane, toluene-4-sulfonyl chloride, 1,2-dibromo-tetrachloroethane, 1,2- Dibromotetrafluoroethane, toluene-4-sulfonyl bromide, 2,3-dimethyl-2,3-dibromobutane, 1,2-diiodotetrafluoroethane, perfluoropropyl iodide, perfluoroethyl iodide, toluene- Examples include 4-sulfonyl iodide and perfluoromethyl iodide.

In the above reaction, it is preferable to lithiate 2,6-dialkoxyanthracene with a lithium reagent. Hydrogen bonded to the 3- and 7-position carbons of 2,6-dialkoxyanthracene is selectively substituted with lithium, and this reacts with the halogenating agent, whereby the halogenation proceeds. Examples of the lithium reagent include organic lithium reagents such as n-BuLi, s-BuLi, and t-BuLi.

The starting material 2,6-dialkoxyanthracene can be referred to the synthesis method described in “J. Mater. Chem. 2003, 13, 1622-1630” and the like.

Subsequently, dealkylation of the compound represented by Formula 2 is performed. By reacting with a dealkylating agent, the alkoxy group of 2,6-dialkoxy-3,7-dihalogenoanthracene is dealkylated into a hydroxyl group, and 2,6-dihalogeno-3 represented by Formula 3 , 7-dihydroxyanthracene is obtained. In Formula 3, X has the same meaning as Formula 2.

The dealkylating agent is not limited as long as the alkoxy group can be dealkylated. For example, boron halides such as boron tribromide and boron trichloride, sodium thioetherate, potassium thioetherate, etc. Alkali metal thioetherates (alkyl mercapto alkali metal salts, etc.), alkylsilyl halides such as trimethylsilyl iodide, mixed liquids of hydrogen bromide and acetic acid, other protic acids such as sulfuric acid, Lewis acids such as aluminum chloride, etc. It is done.

Subsequently, acetylation of the compound represented by Formula 3 is performed. Examples of the acetylating agent include acetic anhydride, acetyl chloride, acetyl bromide and the like.

By reacting with an acetylating agent, the hydroxyl group of 2,6-dihalogeno-3,7-dihydroxyanthracene is acetylated to an acetoxy group, and 2,6-diacetoxy-3,7-dia Halogenoanthracene is obtained. In Formula 4, Ac represents an acetyl group, and X has the same meaning as Formula 2.

Subsequently, the compound represented by Formula 4 is reacted with the terminal acetylene compound. Examples of the terminal acetylene compound include trimethylsilylacetylene, phenylacetylene, 1-decyne and the like. The acetylene hydrogen of the terminal acetylene compound can be used in the same manner even when it is substituted with a reactive substituent such as trialkyltin, borate ester, zinc halide or the like.

As a result, a 2,6-diacetoxy-3,7-diethynylacetylene derivative represented by the formula 5 is obtained. In Formula 5, R ² represents a trimethylsilyl group, a phenyl group or an alkyl group, and Ac has the same meaning as in Formula 4.

The above reaction is preferably carried out by dissolving dihalogeno-diacetoxyanthracene in a solvent such as DMF and a base such as triethylamine, a palladium catalyst such as Pd (PPh ₃ ) ₂ Cl _{2 and} a copper catalyst such as CuI.

Then, a base is allowed to act on the compound represented by Formula 5. Examples of the base include cesium carbonate.

As a result, an intramolecular cyclization reaction occurs in the compound represented by Formula 5 to form a furan ring, and an anti-anthradifuran having a linear structure represented by Formula 6 is obtained. In formula 6, R ³ represents hydrogen, a phenyl group or an alkyl group.

An anti-anthradifuran corresponding to the terminal acetylene compound used is obtained. For example, when trimethylsilylacetylene is used as the terminal acetylene compound, anthra [2,3-b: 6,7-b ′] difuran is obtained. In addition, when phenylacetylene is used as the terminal acetylene compound, 2,8-diphenylanthra [2,3-b: 6,7-b ′] difuran is obtained. Further, when 1-decyne is used as the terminal acetylene compound, 2,8-dioctylanthra [2,3-b: 6,7-b ′] difuran is obtained.

In each of the above steps, the reaction may be appropriately performed using a solvent, a catalyst or the like.

(Embodiment 2)
The method for synthesizing anti-ant radical cogenophene according to Embodiment 2 is a method for synthesizing anti-anthradithiophene or anti-anthradiselenophene.

First, the compound represented by Formula 11 is reacted with a sulfur compound or selenium compound. In Formula 11, R ¹¹ represents an alkyl group, preferably having 6 or less carbon atoms, and more preferably a methyl group.

As the sulfur compound, an organic sulfur compound having an alkylthio group is used. For example, dialkyl disulfides such as dimethyl disulfide and diethyl disulfide are preferably used. Alternatively, simple sulfur may be used as the sulfur compound, and alkylthiolation may be performed using an alkyl halide such as iodomethane as the alkylating agent.

In addition, simple selenium can be used as the selenium compound, and in this case, an alkyl halide such as iodomethane is preferably used as the alkylating agent. Alternatively, an organic selenium compound having an alkylseleno group may be used.

Thereby, an alkylthio group or an alkylseleno group is selectively bonded to the 3rd and 7th position carbons adjacent to the carbon to which the alkoxy group of 2,6-dialkoxyanthracene is bonded, and the compound is represented by Formula 12. 2,6-dialkoxy-3,7-bis (alkylthio) anthracene or 2,6-dialkoxy-3,7-bis (alkylseleno) anthracene is obtained. In Formula 12, R ¹¹ has the same meaning as Formula 11, R ¹² represents an alkyl group, and Y represents sulfur or selenium.

In addition, it is preferable to lithiate 2,6-dialkoxyanthracene with a lithium reagent. Hydrogen bonded to the 3rd and 7th carbons of 2,6-dialkoxyanthracene is selectively substituted with lithium, and alkylthiolation or alkylselenation proceeds. Examples of the lithium reagent include organic lithium reagents such as n-BuLi, s-BuLi, and t-BuLi.

The starting material 2,6-dialkoxyanthracene is synthesized and used in the same manner as in the first embodiment.

Subsequently, 2,6-dialkoxy-3,7-bis (alkylthio) anthracene is reacted with a dealkylating agent. The alkoxy group is selectively dealkylated to a hydroxyl group, and 2,6-hydroxy-3,7-bis (alkylthio) anthracene or 2,6-dihydroxy-3,7-bis (alkyl) represented by formula 13 Seleno) anthracene is obtained. In Formula 13, R ¹² and Y are synonymous with Formula 12.

As the dealkylating agent, the dealkylating agent exemplified in the first embodiment can be used.

Subsequently, the compound represented by Formula 13 is reacted with trifluoromethanesulfonic anhydride. The hydroxyl group is substituted with a trifluoromethanesulfonyl group, and 2,6-bis (alkylthio) -3,7-bis (trifluoromethanesulfonyl) anthracene represented by the formula 14 is obtained. In Formula 14, R ¹² and Y have the same meanings as in Formula 12, and Tf represents a trifluoromethanesulfonyl group.

Subsequently, the compound represented by Formula 14 is reacted with the terminal acetylene compound. As the terminal acetylene compound, the terminal acetylene compound exemplified in Embodiment 1 may be used.

Thereby, a 2,6-bis (alkylthio) -3,7-diethynylanthracene derivative or a 2,6-bis (alkylseleno) -3,7-diethynylanthracene derivative represented by the formula 15 is obtained. In Formula 15, R ¹² and Y have the same meaning as in Formula 12, and R ¹³ represents a trimethylsilyl group, a phenyl group, or an alkyl group.

Subsequently, iodine is allowed to act on the compound represented by Formula 15 to cause cyclization (iodine cyclization reaction). As a result, an intramolecular cyclization reaction occurs, and anti-anthradithiophene or anti-anthradiselenophene having a linear structure represented by Formula 16 is obtained. In Formula 16, R ¹³ has the same meaning as Formula 15, and Y has the same meaning as Formula 12.

When trimethylsilylacetylene is used as the terminal acetylene compound, 2,6-bis (alkylthio) -3,7-bis (trimethylsilylethynyl) anthracene derivative or 2,6-bis (alkylseleno) -3,7-bis ( A trimethylsilylethynyl) anthracene derivative is obtained. When this is cyclized with iodine, 3,9-diiodo-2,8-bis (trimethylsilyl) anthra [2,3-b: 7,8-b ′] dithiophene or 3,9-diiodo-2,8- Bis (trimethylsilyl) anthra [2,3-b: 7,8-b ′] diselenophene is obtained. When this is reduced, iodine and trimethylsilyl groups are eliminated, and anthra [2,3-b: 7,8-b ′] dithiophene or anthra [2,3-b: 7,8-b ′] diselenophene is obtained. be able to. For the reduction, for example, a known reducing agent such as sodium hydroxide (NaOH), tetra-n-butylammonium fluoride (TBAF), sodium borohydride (NaBH ₄ ), lithium aluminum hydride (LiAlH ₄ ) or the like is used. It is done.

In addition, 3,9-diiodo-2,8-bis (trimethylsilyl) anthra [2,3-b: 7,8-b ′] dithiophene or 3,9-diiodo-2,8-bis (trimethylsilyl) anthra [2 , 3-b: 7,8-b ′] diselenophene is treated with phenylboronic acid (PhB (OH) ₂ ) or the like to give 3,9-diphenylanthra [2,3-b: 7,8-b ′] dithiophene. Alternatively, 3,9-diphenylanthra [2,3-b: 7,8-b ′] diselenophene can be obtained.

Further, when phenylacetylene is used as the terminal acetylene compound, 2,6-bis (alkylthio) -3,7-bis (phenylethynyl) anthracene derivative or 2,6-bis (alkylseleno) -3,7-bis ( Phenylethynyl) anthracene derivative is obtained and cyclized with iodine to give 3,9-diiodo-2,8-diphenylanthra [2,3-b: 7,8-b ′] dithiophene or 3,9- Diiodo-2,8-diphenylanthra [2,3-b: 7,8-b ′] diselenophene is obtained. When this is treated with a reducing agent such as sodium borohydride described above, 2,8-diphenylanthra [2,3-b: 7,8-b ′] dithiophene or 2,8-diphenylanthra [2,3 -B: 7,8-b '] diselenophene can be obtained.

In each of the above steps, the reaction may be appropriately performed using a solvent or a reaction promoting catalyst.

The above-described synthesis method can selectively synthesize the anti-body of the anth radical cogenophene. The anti-body of anant radical kogenophene exhibits good semiconductor properties such as superior carrier mobility compared to the syn-body. Therefore, it is useful as a method for synthesizing an excellent organic semiconductor material.

Hereinafter, synthesis examples of the antiant radical cogenophene will be described in detail based on examples, but the present invention is not limited to the following examples.

(General information)
All compounds and solvents used were reagent grade unless otherwise stated. Tetrahydrofuran (THF), triethylamine, N, N-dimethylformamide (DMF) and dichloromethane were used after purification according to standard distillation procedures. 2,6-Dimethoxyanthracene was synthesized and used with reference to “J. Mater. Chem. 2003, 13, 1622-1630”. Also, unless otherwise noted, all reactions were performed under nitrogen air. The structure of the compound was determined by ¹ H NMR ( ¹ H nuclear magnetic resonance spectrum), ¹³ C NMR ( ¹³ C nuclear magnetic resonance spectrum), and EIMS (mass spectrometry spectrum).

(Synthesis of anthra [2,3-b: 6,7-b ′] difuran)
Anthra [2,3-b: 6,7-b ′] difuran was synthesized stepwise as follows.

First, 2,6-dibromo-3,7-dimethoxyanthracene was synthesized as shown in the following reaction formula.

To a suspension of 2,6-dimethoxyanthracene (12 g, 50 mmol) in THF (2.0 L) was added n-BuLi in hexane (1.67 M) (140 mL, 234 mmol) at 0 ° C.
After stirring at room temperature for 1 hour, 1,2-dibromo-1,1,2,2-tetrachloroethane (100 g, 307 mmol) was added at 0 ° C., and this was stirred at room temperature for 12 hours.
The reaction solution was poured into saturated aqueous ammonium chloride (200 mL) and the organic phase was removed by evaporation.
The formed precipitate was collected by filtration, washed with water, methanol and a small amount of chloroform, and dried under reduced pressure to obtain 2,6-dibromo-3,7-dimethoxyanthracene (20.0 g, quantitative yield) as a pale green solid. It was.

The measurement results of the obtained 2,6-dibromo-3,7-dimethoxyanthracene are shown below.
Mp 282-283 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.18 (s, 2H), 8.12 (s, 2H), 7.21 (s, 2H), 4.04 (s, 6H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 176.0, 132.7, 124.0, 1120.9, 115.0, 105.8, 90.1, 56.9;
EI-MS (70 eV) m / z = 394 (M ⁺ ); HRMS: Calcd for C ₁₆ H ₁₂ Br ₂ O ₂ : 394.92768, [MH ⁺ ]. Found: 394.92789.

Subsequently, 3,7-dibromoanthracene-2,6-diol was synthesized as shown in the following reaction formula.

To a solution of 2,6-dibromo-3,7-dimethoxyanthracene (25 g, 63 mmol) dissolved in dichloromethane (700 mL), a dichloromethane solution of BBr ₃ (ca.4M, 50 mL, 100 mmol) was added dropwise at 0 ° C.
After refluxing for 12 hours, ice was added at 0 ° C. The organic phase was removed by evaporation and the resulting precipitate was collected by filtration and washed with water and methanol.
Drying under reduced pressure gave 3,7-dibromoanthracene-2,6-diol (23.2 g, quantitative yield) as a pale green solid.

The measurement results of 3,7-dibromoanthracene-2,6-diol obtained are shown below.
Mp> 300 ° C;
¹ H NMR (400 MHz, DMSO-d ₆ ) δ 10.61 (s, 2H), 8.27 (s, 2H), 8.20 (s, 2H), 7.31 (s, 2H); ¹³ C NMR (100 MHz, DMSO- d ₆ ) δ 150.2, 131.4, 129.9, 128.2, 122.3, 114.8, 107.8; IR (KBr) ν = 3359 cm ^-1 (OH);
EI-MS (70 eV) m / z = 366 (M ⁺ ); HRMS: Calcd for C ₁₄ H ₉ Br ₂ O ₂ : 366.89638, [MH ⁺ ]. Found: 366.89654.

Subsequently, 2,6-diacetoxy-3,7-dibromoanthracene was synthesized as shown in the following reaction formula.

Acetic anhydride (3.4 mL, 36 mmol) was added to a suspension of 3,7-dibromoanthracene-2,6-diol (5.0 g, 14 mmol) and triethylamine (15 mL, 107 mmol) in dichloromethane (400 mL) at 0 ° C. Added in.
After stirring at room temperature for 7 hours, it was diluted with water (100 mL) and hydrochloric acid (4M, 100 mL).
The organic phase was removed by evaporation, and the resulting precipitate was collected by filtration, washed with water and a small amount of chloroform, and dried under reduced pressure to give 2,6-diacetoxy-3,7-dibromoanthracene as a white solid.

The measurement results of 2,6-diacetoxy-3,7-dibromoanthracene obtained are shown below.
Mp> 300 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (s, 2H), 8.25 (s, 2H), 7.75 (s, 2H), 2.45 (s, 2H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 168.6 145.6, 132.6, 131.0, 130.9, 125.5, 120.6, 116.7, 20.8; IR (KBr) ν = 1763 cm ^-1 (C = O);
EI-MS (70 eV) m / z = 450 (M ⁺ ). HRMS: Calcd for C ₁₈ H ₁₂ Br ₂ O ₄ : 472.89946, [MNa ⁺ ]. Found: 472.89948.

Subsequently, 2,6-diacetoxy-3,7-bis (trimethylsilylethynyl) anthracene was synthesized as shown in the following reaction formula.

To a degassed solution of 2,6-bis (acetoxy) -3,7-dibromoanthracene (1.8 g, 4.0 mmol) in triethylamine (20 mL) and DMF (20 mL) was added trimethylsilylacetylene (1.2 mL, 9.6 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (200 mg, 0.004 mmol, 1.0 mol%), CuI (100 mg, 0.01 mmol, 2.5 mol%) were added.
After stirring at 60 ° C. for 12 hours, the mixed solution was diluted with water (10 mL) and hydrochloric acid (4M, 20 mL).
The formed precipitate was collected by filtration and washed with water. Separation and purification by silica gel column chromatography (Rf = 1.0, chloroform) gave 2,6-diacetoxy-3,7-bis (trimethylsilylethynyl) anthracene (1.6 g, 84%) as a yellow solid. .

The measurement results of the obtained 2,6-diacetoxy-3,7-bis (trimethylsilylethynyl) anthracene are shown below.
Mp 232-233 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.26 (s, 2H), 8.18 (s, 2H), 7.65 (s, 2H), 2.40 (s, 6H), 0.30 (s, 18H); ¹³ C NMR ( 100 MHz, CDCl ₃ ) δ 169.5, 147.9, 134.6, 131.4, 130.4, 126.5, 119.4, 117.8, 100.8, 100.4, 21.2, 0.24; IR (KBr) ν = 1774 cm ^-1 (C = O);
EI-MS (70 eV) m / z = 486 (M ⁺ ). HRMS: Calcd for C ₂₈ H ₃₀ O ₄ Si ₂ : 487.17554, [M ⁺ ]. Found: 487.17480.

Subsequently, anthra [2,3-b: 6,7-b ′] difuran was synthesized as shown in the following reaction formula.

To a suspension of cesium carbonate (6.0 g, 18 mmol) in dimethylacetamide (50 mL) and water (6 mL) was added 2,6-diacetoxy-3,7-bis (trimethylsilylethynyl) anthracene (1.0 g, 2 0.1 mmol) and stirred at 80 ° C. for 4 hours.
The mixed solution was poured into 200 mL of saturated aqueous ammonium chloride solution, and the resulting precipitate was collected by filtration, washed with water, and anthra [2,3-b: 6,7-b ′] difuran (0.33 g, 63%). Was obtained as a yellow solid.
This was purified by a temperature gradient thermal sublimation method (ca. 240 ° C. at <10 ⁻² Pa) in a nitrogen atmosphere, and washed with a solvent (chloroform) to obtain a sample for analysis.

The measurement results of the obtained anthra [2,3-b: 6,7-b ′] difuran are shown below.
Mp> 300 ° C;
¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.83 (s, 2H), 8.35 (s, 2H), 8.17 (s, 2H), 8.03 (d, J = 8.0 Hz, 2H), 7.07 (d, J = 8.0 Hz, 2H); ¹³ C NMR (100 MHz, DMSO-d ₆ ) δ 153.5, 149.1, 129.7, 129.1, 129.0, 125.5, 118.2, 106.3, 105.0;
EI-MS (70 eV) m / z = 258 (M ⁺ ). Anal.Calcd for C ₁₈ H ₁₀ O ₂ : C, 83.71; H, 3.90%. Found C, 83.77; H, 4.11%; HRMS: Calcd for C ₁₈ H ₁₀ O ₂ : 259.07536, [MH ⁺ ]. Found: 259.07547.

(Synthesis of 2,8-diphenylanthra [2,3-b: 6,7-b ′] difuran)
Anthra [2,3-b: 6,7-b ′] difuran was synthesized stepwise as follows.

First, as shown in the following reaction formula, 2,6-diacetoxy-3,7-bis (phenylethynyl) anthracene was synthesized.

To a degassed solution of 2,6-bis (acetoxy) -3,7-dibromoanthracene (1.8 g, 4.0 mmol) in triethylamine (20 mL) and DMF (20 mL) was added phenylacetylene (0.98 g). 9.6 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (200 mg, 0.004 mmol, 1.0 mol%) and CuI (100 mg, 0.01 mmol, 2.5 mol%)).
After stirring at 60 ° C. for 12 hours, the mixture was diluted with water (10 mL) and hydrochloric acid (4M, 20 mL).
The resulting precipitate was collected by filtration and washed with water, methanol, and dichloromethane to give 2,6-diacetoxy-3,7-bis (phenylethynyl) anthracene (1.6 g, 81%) as a yellow solid.

The measurement results of the obtained 2,6-diacetoxy-3,7-bis (phenylethynyl) anthracene are shown below.
Mp> 300 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.34 (s, 2H), 8.26 (s, 2H), 7.73 (s, 2H), 7.56-7.55 (m, 4H), 7.40-7.39 (m, 6H), 2.46 (s, 6H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 186.7, 146.3, 140.4, 139.1, 133.7, 133.3, 130.3, 129.9, 12.7, 122.6, 122.5, 118.8, 144.0, 93.9, 23.3; IR ( KBr) ν = 1752.36 cm ^-1 (C = O);
EI-MS (70 eV) m / z = 494 (M ⁺ ). HRMS: Calcd for C ₃₄ H ₂₂ O ₄ : 494.15126, [M ⁺ ]. Found: 494.15195.

Subsequently, 2,8-diphenylanthra [2,3-b: 6,7-b ′] difuran was synthesized as shown in the following reaction formula.

To a suspension of cesium carbonate (6.0 g, 18 mmol) in dimethylacetamide (200 mL) and water (24 mL) was added 2,6-diacetoxy-3,7-bis (phenylethynyl) anthracene (1.04 g, 2 0.1 mmol) and stirred at 100 ° C. for 24 hours.
Poured into 200 mL of saturated aqueous ammonium chloride, and the resulting precipitate was collected by filtration, washed with water, and 2,8-diphenylanthra [2,3-b: 6,7-b ′] difuran (0.74 g, 86%) as an orange solid.
This solid was purified by a temperature gradient thermal sublimation method (ca. 280 ° C. at <10 ⁻² Pa) in a nitrogen atmosphere, and washed with a solvent (chloroform) to obtain a sample for analysis.

The measurement results of the obtained 2,8-diphenylanthra [2,3-b: 6,7-b ′] difuran are shown below.
Mp> 300 ° C;
EI-MS (70 eV) m / z = 410 (M ⁺ ). Anal. Calcd for; HRMS: Calcd for C ₃₀ H ₁₈ O ₂ : 410.13013, [M ⁺ ]. Found: 410.13120.
The solubility of 2,8-Diphenylanthra [2,3-b: 6,7-b '] difuran was not sufficient to obtain ¹ H and ¹³ C NMR spectra useful for structural characterization.

(Synthesis of anthra [2,3-b: 6,7-b ′] dithiophene)
Anthra [2,3-b: 6,7-b ′] dithiophene was synthesized stepwise as follows.

First, 2,6-dimethoxy-3,7-bis (methylthio) anthracene was synthesized as shown in the following reaction formula.

To a suspension of 2,6-dimethoxyanthracene (16.5 g, 69 mmol) in THF (2.0 L), a hexane solution of n-BuLi (1.62 M, 175 mL, 276 mmol) was added at 0 ° C.
After stirring this at room temperature for 1 hour, dimethyl disulfide (31 mL, 345 mmol) was added to this reaction solution at 0 ° C., followed by stirring at room temperature for 9 hours.
The reaction solution was poured into saturated aqueous ammonium chloride solution (500 mL) and the organic phase was removed by evaporation, and the resulting precipitate was collected by filtration and washed with water. And it was made to melt | dissolve in chloroform.
The solution was dried over MgSO ₄ and concentrated in vacuo.
Then, separation and purification by silica gel column chromatography (Rf = 1.0, chloroform) gave 2,6-dimethoxy-3,7-bis (methylthio) anthracene (22.7 g, quantitative yield) as a pale yellow solid. It was.

The measurement results of the obtained 2,6-dimethoxy-3,7-bis (methylthio) anthracene are shown below.
Mp 253-255 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.08 (s, 2H), 7.50 (s, 2H), 7.12 (s, 2H), 4.03 (s, 6H), 2.58 (s, 6H); ¹³ C NMR ( 100 MHz, CDCl ₃ ) δ 153.8, 130.7, 129.5, 128.3, 122.4, 122.0, 103.3, 55.9, 14.5;
EI-MS (70 eV) m / z = 330 (M ⁺ ). Anal. Calcd for C ₁₈ H ₁₈ O ₂ S ₂ : C, 65.42; H, 5.49%. Found: C, 65.47; H, 5.34%.

Subsequently, 3,7-bis (methylthio) anthracene-2,6-diol was synthesized as shown in the following reaction formula.

To a solution of 2,6-dimethoxy-3,7-bis (methylthio) anthracene (14 g, 42 mmol) dissolved in dichloromethane (2 L), a solution of BBr ₃ in dichloromethane (ca.4M, 40 mL, 160 mmol) at 0 ° C. Added dropwise.
After stirring for 18 hours at room temperature, ice (approximately 100 g) was added at 0 ° C.
The organic phase is removed by evaporation and the precipitate formed is filtered off, washed with water and dried under reduced pressure to give almost pure 3,7-bis (methylthio) anthracene-2,6-diol (12.7 g). , Quantitative yield) as a pale green solid.

The measurement results of the obtained 3,7-bis (methylthio) anthracene-2,6-diol are shown below.
Mp 252-255 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.10 (s, 2H), 8.05 (s, 2H), 7.36 (s, 2H), 6.37 (s, 2H), 2.48 (s, 6H); ¹³ C NMR ( 100 MHz, CDCl ₃ ) δ 151.1, 132.9, 131.6, 129.2, 127.3, 123.7, 107.8, 19.4; IR (KBr) ν = 3396 cm ^-1 (OH);
EI-MS (70 eV) m / z = 302 (M ⁺ ). Anal. Calcd for C ₁₆ H ₁₄ O ₂ S ₂ : C, 63.55; H, 4.67%. Found: C, 63.32; H, 4.42%.

Subsequently, 2,6-bis (trifluoromethanesulfonyloxy) -3,7-bis (methylthio) anthracene was synthesized as shown in the following reaction formula.

To a suspension of 3,7-bis (methylthio) anthracene-2,6-diol (10 g, 33 mmol) and triethylamine (30 mL, 214 mmol) in dichloromethane (500 mL) was added trifluoromethanesulfonic anhydride (15 mL, 89 mmol). Was added at 0 ° C.
After stirring at room temperature for 20 hours, the reaction solution was diluted with water (100 mL) and hydrochloric acid (4M, 100 mL).
The organic phase is removed by evaporation, the precipitate is collected by filtration, washed with water and a small amount of chloroform, and 2,6-bis (trifluoromethanesulfonyloxy) -3,7-bis (methylthio) anthracene (10. 5 g, 56%) was obtained as a yellow solid.

The measurement results of the obtained 2,6-bis (trifluoromethanesulfonyloxy) -3,7-bis (methylthio) anthracene are shown below.
Mp 212-213 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.28 (s, 2H), 7.86 (s, 2H), 7.73 (s, 2H), 2.63 (s, 6H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 145.9, 132.2, 130.6, 130.0, 125.9, 125.6, 120.5, 119.1, 117.3, 15.6; IR (KBr) ν = 1429, 1222 cm ^-1 (-O-SO _2- );
EI-MS (70 eV) m / z = 566 (M ⁺ ). Anal. Calcd for C ₁₈ H ₁₂ F ₆ O ₆ S ₄ : C, 38.16; H, 2.13%. Found C, 38.37; H, 1.83% .

Subsequently, 2,6-bis (methylthio) -3,7-bis (trimethylsilylethynyl) anthracene was synthesized as shown in the following reaction formula.

2,6-bis (trifluoromethanesulfonyloxy) -3,7-bis (methylthio) anthracene (283 mg, 0.5 mmol) was added to triethylamine (5.0 mL) and DMF (5.0 mL), and the degassed solution was added. , Trimethylsilylacetylene (0.17 mL, 1.2 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (13 mg, 0.00025 mmol, 5 mol%) and CuI (5 mg, 0.0005 mmol, 10 mol%) were added.
After stirring at 60 ° C. for 12 hours, the reaction solution was diluted with water (10 mL) and hydrochloric acid (4M, 2.0 mL).
The formed precipitate was collected by filtration and washed with water.
The precipitate collected by filtration was separated and purified by silica gel column chromatography (Rf = 1.0, chloroform), and 2,6-bis (methylthio) -3,7-bis (trimethylsilylethynyl) anthracene (230 mg, quantitative yield) Was obtained as a pale yellow solid.

The measurement results of the obtained 2,6-bis (methylthio) -3,7-bis (trimethylsilylethynyl) anthracene are shown below.
Mp 210-213 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.08 (s, 2H), 8.05 (s, 2H), 7.47 (s, 2H), 2.60 (s, 6H), 0.33 (s, 18H); ¹³ C NMR ( 100 MHz, CDCl ₃ ) δ 137.9, 133.5, 131.5, 130.4, 124.9, 121.4, 120.7, 102.7, 102.1, 15.8, 0.51;
EI-MS (70 eV) m / z = 462 (M ⁺ ). Anal. Calcd for C ₂₆ H ₃₀ F ₃ S ₂ Si ₂ : C, 68.51; H, 6.98%. Found C, 68.72; H, 6.76% .

Subsequently, 3,9-diiodo-2,8-bis (trimethylsilyl) anthra [2,3-b: 7,8-b ′] dithiophene was synthesized as shown in the following reaction formula.

To a solution of 2,6-bis (methylthio) -3,7-bis (trimethylsilylethynyl) anthracene (2.9 g, 6.3 mmol) dissolved in dichloromethane (200 mL), iodine (8.0 g, 31 mmol) was added to 0. Added at ° C.
After stirring at room temperature for 3 hours, the mixture was poured into a well-stirred aqueous bisulfite solution (50 mL).
The formed precipitate was collected by filtration, washed successively with water (100 mL) and ethanol (100 mL), dried under reduced pressure, and 3,9-diiodo-2,8-bis (trimethylsilyl) anthra [2,3-b: 7,8-b ′] dithiophene (4.1 g, 88%) was obtained as a dark red solid.

The measurement results of the obtained 3,9-diiodo-2,8-bis (trimethylsilyl) anthra [2,3-b: 7,8-b ′] dithiophene are shown below.
Mp 250 ° C (Decomp.);
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.84 (s, 2H), 8.52 (s, 2H), 8.51 (s, 2H), 0.56 (s, 18H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 144.6, 142.4, 137.6, 129.8, 129.6, 126.1, 124.1, 119.9, 86.9, 0.8;
EI-MS (70 eV) m / z = 686 (M ⁺ ). Anal. Calcd for C ₂₄ H ₂₄ I ₂ S ₂ Si ₂ : C, 68.51; H, 6.98%. Found: C, 68.72; H, 6.74 %.

Subsequently, anthra [2,3-b: 6,7-b ′] dithiophene was synthesized as shown in the following reaction formula.

Suspension obtained by adding 3,9-diiodo-2,8-bis (trimethylsilyl) anthra [2,3-b: 7,8-b ′] dithiophene (2.0 g, 2.9 mmol) to ethanol (200 mL) Was added sodium borohydride (8.0 g, 31 mmol).
The mixture was refluxed for 24 hours.
After cooling to 0 ° C., hydrochloric acid (4M, 50 mL) was added and stirred for about 10 minutes.
The resulting dark red solid was collected by filtration, washed successively with water (100 mL) and ethanol (100 mL), and anthra [2,3-b: 6,7-b ′] dithiophene (4.1 g, 88%) Was obtained as an orange solid.
The obtained solid was purified by a temperature gradient thermal sublimation method (ca. 290 ° C. at <10 ⁻² Pa) in a nitrogen atmosphere, and washed with a solvent (chloroform) to obtain a sample for analysis.

The measurement results of the obtained anthra [2,3-b: 6,7-b ′] dithiophene are shown below.
Mp> 300 ° C;
¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.84 (s, 2H), 8.69 (s, 2H), 8.63 (s, 2H), 7.75 (d, J = 5.2 Hz, 2H), 7.51 (d, J = 5.2 Hz, 2H);
EI-MS (70 eV) m / z = 290 (M ⁺ ). Anal.Calcd for C ₁₈ H ₁₀ S ₂ : C, 74.45; H, 3.47%. Found: C, 74.18; H, 3.22%; HRMS: Calcd for C ₁₈ H ₁₀ S ₂ : 291.02967, [MH ⁺ ]. Found: 291.02991. The solubility of Anthra [2,3-b: 6,7-b '] dithiophene was not sufficient for measuring ¹³ C NMR spectra.

(Synthesis of 3,9-diphenylanthra [2,3-b: 6,7-b ′] dithiophene)
3,9-Diphenylanthra [2,3-b: 6,7-b ′] dithiophene was synthesized as follows.

First, as shown in the following reaction formula, 3,9-diphenylanthra [2,3-b: 6,7-b ′] dithiophene was synthesized.

To DMF (3.0 mL), 3,9-diiodo-2,8-bis (trimethylsilyl) anthra [2,3-b: 7,8-b ′] dithiophene (69 mg, 0.1 mmol), phenylboronic acid (36 0.6 mg, 0.3 mmol), and Pd (PPh ₃ ) ₄ (12 mg, 0.01 mmol, 10 mol%) was added to the suspension degassed by adding K ₃ PO ₄ .nH ₂ O (200 mg).
This was stirred for 15 hours, and then poured into a saturated aqueous sodium hydrogen sulfite solution (50 mL) over about 10 minutes with stirring.
The formed precipitate was collected by filtration and washed successively with water (100 mL) and ethanol (100 mL). Then, recrystallization was performed using trichloromethane to obtain 3,9-diphenylanthra [2,3-b: 6,7-b ′] dithiophene (30 mg, 68%) as a dark red solid.

The measurement results of the obtained 3,9-diphenylanthra [2,3-b: 6,7-b ′] dithiophene are shown below.
Mp> 300 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.71 (s, 2H), 8.60 (s, 2H), 8.56 (s, 2H), 7.72 (d, J = 8.0 Hz, 4H), 7.59-7.43 (m, 6H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 138.5, 137.8, 137.2, 135.9, 129.4, 129.1, 128.9, 128.8, 127.9, 125.9, 125.7, 121.3, 120.8;
EI-MS (70 eV) m / z = 442 (M ⁺ ); HRMS: Calcd for C ₃₀ H ₁₈ S ₂ : 442.08444, [M ⁺ ]. Found: 442.08450.

(Synthesis of 2,8-diphenylanthra [2,3-b: 6,7-b ′] dithiophene)
2,8-Diphenylanthra [2,3-b: 6,7-b ′] dithiophene was synthesized stepwise as follows.

First, as shown in the following reaction formula, 2,6-bis (methylthio) -3,7-bis (phenylethynyl) anthracene was synthesized.

To a degassed solution was dissolved 2,6-bis (methylthio) -3,7bis (trifluoromethanesulfonyloxy) anthracene (283 mg, 0.5 mmol) in triethylamine (5.0 mL) and DMF (5.0 mL). , Phenylacetylene (1.23 g, 1.2 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (13 mg, 0.00025 mmol, 5 mol%), CuI (5 mg, 0.0005 mmol, 10 mol%)) were added.
After stirring at 60 ° C. for 12 hours, the mixture was diluted with water (10 mL) and hydrochloric acid (4M, 2.0 mL).
The formed precipitate was collected by filtration and washed with water.
The obtained solid was separated and purified by silica gel column chromatography (Rf = 1.0, chloroform), and 2,6-bis (methylthio) -3,7-bis (phenylethynyl) anthracene (234 mg, quantitative yield) was pale. Obtained as a yellow solid.

The measurement results of the obtained 2,6-bis (methylthio) -3,7-bis (phenylethynyl) anthracene are shown below.
Mp 222-223 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.12 (s, 2H), 8.10 (s, 2H), 7.66-7.64 (m, 2H), 7.52 (s, 2H), 7.40-7.38 (m, 6H), 2.63 (s, 6H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 138.1, 132.8, 132.3, 131.6, 130.5, 129.2, 129.0, 124.9, 123.6, 121.6, 120.9, 96.4, 87.8, 15.9;
EI-MS (70 eV) m / z = 470 (M ⁺ ). Anal.Calcd for C ₃₂ H ₂₂ S ₂ : C, 81.66; H, 4.71%. Found C, 81.56; H, 4.69%.

(Synthesis of 3,9-Diiodo-2,8-diphenylanthra [2,3-b: 6,7-b ′] dithiophene)
As shown in the following reaction formula, 3,9-diiodo-2,8-diphenylanthra [2,3-b: 6,7-b ′] dithiophene was synthesized.

To a solution of 2,6-bis (methylthio) -3,7-bis (phenylethynyl) anthracene (2.96 g, 6.3 mmol) dissolved in dichloromethane (200 mL), iodine (8.0 g, 31 mmol) was added to 0. Added at ° C.
After stirring at room temperature for 3 hours, the mixture was poured into a well-stirred aqueous solution of hydrogen sulfite (50 mL).
The resulting precipitate was collected by filtration, washed successively with water (100 mL) and ethanol (100 mL), dried under reduced pressure, and 3,9-diiodo-2,8-diphenylanthra [2,3-b: 6 , 7-b ′] dithiophene (4.71 g, quantitative yield) was obtained as a dark red solid. And it recrystallized using chlorobenzene and obtained the analysis sample.

The measurement results of the obtained 3,9-diiodo-2,8-diphenylanthra [2,3-b: 6,7-b ′] dithiophene are shown below.
Mp> 300 ° C;
EI-MS (70 eV) m / z = 694 (M ⁺ ). Anal.Calcd for C ₃₀ H ₁₆ I ₂ S ₂ : C, 51.89; H, 2.32%. Found: C, 52.11; H, 2.42%.
Poor solubility of 3,9-diiodo-2,8-diphenylanthra [2,3-b: 7,8-b '] dithiophene did not allow its characterization by means of ¹ H and ¹³ C NMR spectra.

Subsequently, 2,8-diphenylanthra [2,3-b: 6,7-b ′] dithiophene was synthesized as shown in the following reaction formula.

To a suspension in which 3,9-diiodo-2,8-diphenylanthra [2,3-b: 6,7-b ′] dithiophene (2.17 g, 2.9 mmol) was added to ethanol (200 mL) was added hydrogen. Sodium borohydride (8.0 g, 31 mmol) was added and refluxed for 24 hours.
After cooling the reaction solution to 0 ° C., hydrochloric acid (4M, 50 mL) was added with stirring (approximately 10 minutes) to precipitate a dark red solid.
This solid was collected by filtration, washed successively with water (100 mL) and ethanol (100 mL), dried under reduced pressure, and 2,8-diphenylanthra [2,3-b: 6,7-b ′] dithiophene (1 .28 g, quantitative yield) was obtained as a dark red solid.
The crude product was purified by a temperature gradient thermal sublimation method (ca. 320 ° C. at <10 ⁻² Pa) under a nitrogen atmosphere, and washed with a solvent (chloroform) to obtain a sample for analysis.

The measurement results of the obtained 2,8-diphenylanthra [2,3-b: 6,7-b ′] dithiophene are shown below.
Mp> 300 ° C;
EI-MS (70 eV) m / z = 442 (M ⁺ ). Anal.Calcd for C ₃₀ H ₁₈ S ₂ : C, 81.41; H, 4.10%. Found: C, 81.49; H, 4.11%.
The solubility of 2,8-DiphenylAnthra [2,3-b: 6,7-b '] dithiophene was too low to obtain ¹ H and ¹³ C NMR spectra for structural characterization.

(Synthesis of anthra [2,3-b: 6,7-b ′] diselenophene)
Anthra [2,3-b: 6,7-b ′] diselenophene was synthesized stepwise as follows.

First, as shown in the following reaction formula, 2,6-dimethoxy-3,7-bis (methylseleno) anthracene was synthesized.

To a suspension of 2,6-dimethoxyanthracene (12 g, 50 mmol) in THF (2.0 L) was added n-BuLi in hexane (1.67 M, 140 mL, 234 mmol) at 0 ° C.
After the mixture was stirred at room temperature for 1 hour, powdered selenium (16.6 g, 210 mmol) was added to the solution at 0 ° C. and stirred at room temperature for 30 minutes to form the corresponding selenic acid. And iodomethane (15 mL, 243 mmol) was added to the solution at 0 ° C. and stirred for 12 hours.
The reaction solution was poured into a saturated aqueous ammonium chloride solution (500 mL), the organic phase was evaporated and washed with water and methanol.
Drying under reduced pressure gave 2,6-dimethoxy-3,7-bis (methylseleno) anthracene (16.0 g, 76%) as a white solid.

The measurement results of the obtained 2,6-dimethoxy-3,7-bis (methylseleno) anthracene are shown below.
Mp 267-268 ° C (Decomp.);
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.08 (s, 2H), 7.62 (s, 2H), 7.11 (s, 2H), 4.02 (s, 6H), 2.42 (s, 6H); ¹³ C NMR ( 100 MHz, CDCl ₃ ) δ 154.6, 130.1, 128.8, 125.9, 125.4, 122.5, 103.1, 55.9, 5.0;
EI-MS (70 eV) m / z = 426 (M ⁺ ). HRMS: Calcd for C ₁₈ H ₁₈ O ₂ Se ₂ : 426.97100, [M ⁺ ]. Found: 426.97018.

Subsequently, 3,7-bis (methylseleno) anthracene-2,6-diol was synthesized as shown in the following reaction formula.

To a solution of 2,6-dimethoxy-3,7-bis (methylseleno) anthracene (14 g, 33 mmol) added to dichloromethane (2 L), a dichloromethane solution of BBr ₃ (about 4 M, 50 mL, 200 mmol) was added dropwise at 0 ° C. .
After stirring at room temperature for 12 hours, ice (about 100 g) was added at 0 ° C.
The organic phase was removed by evaporation and the resulting precipitate was collected by filtration.
This was washed successively with water, a small amount of ethanol, and chloroform, and dried under reduced pressure to give almost pure 3,7-bis (methylseleno) anthracene-2,6-diol (13.0 g, quantitative yield) as a pale green solid. Obtained.

The measurement results of the obtained 3,7-bis (methylseleno) anthracene-2,6-diol are shown below.
Mp 272-273 ° C (Decomp.);
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.21 (s, 2H), 8.13 (s, 2H), 7.36 (s, 2H), 2.32 (s, 6H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 151.2, 135.5, 131.8, 129.1, 123.6, 122.9, 107.1, 9.7; IR (KBr) ν = 3404 cm ^-1 (OH);
EI-MS (70 eV) m / z = 398 (M ⁺ ); HRMS: Calcd for C ₁₆ H ₁₄ O ₂ Se ₂ : 398.93970, [MH ⁺ ]. Found: 398.93930.

Subsequently, 2,6-bis (methylseleno) -3,7-bis (trifluoromethanesulfonyloxy) anthracene was synthesized as shown in the following reaction formula.

To a suspension of 3,7-bis (methylseleno) anthracene-2,6-diol (12 g, 30 mmol) and triethylamine (40.0 mL, 285 mmol) in dichloromethane (700 mL) was added trifluoromethanesulfonic anhydride (15 mL, 89 mmol) was added at 0 ° C.
After stirring at room temperature for 3 hours, the reaction solution was diluted with water (100 mL) and hydrochloric acid (4M, 100 mL).
The resulting mixture was extracted with dichloromethane (400 mL × 3).
The organic phase was washed with brine (400 mL × 3), dried using MgSO ₄ , separated and purified by silica gel column chromatography (Rf = 1.0, chloroform), and 2,6-bis (methylseleno) -3 , 7-bis (trifluoromethanesulfonyloxy) anthracene (7.5 g, 38%) was obtained as a yellow solid.

The measurement results of the resulting 2,6-bis (methylseleno) -3,7-bis (trifluoromethanesulfonyloxy) anthracene are shown below.
Mp 223-224 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.31 (s, 2H), 7.90 (s, 2H), 7.88 (s, 2H), 2.51 (s, 6H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 146.9 130.8, 130.4, 129.8, 126.1, 125,7, 118.7, 7.2; IR (KBr) ν = 1425, 1222 cm ^-1 (-O-SO _2- );
EI-MS (70 eV) m / z = 662 (M ⁺ ); HRMS: Calcd for C ₁₈ H ₁₂ O ₆ F ₆ S ₂ Se ₂ : 661.83044, [M ⁺ ]. Found: 661.82971.

Subsequently, 2,6-bis (methylseleno) -3,7-bis [(trimethylsilyl) ethynyl] anthracene was synthesized as shown in the following reaction formula.

To a degassed solution of 2,6-bis (methylseleno) -3,7-bis (trifluoromethanesulfonyloxy) anthracene (1.50 g, 2.27 mmol) in DMF (40 mL) was added trimethyl [(tributylstannyl). ) Ethynyl] silane (2.2 g, 5.68 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (161 mg, 0.0031 mmol, 5 mol%) was added.
After stirring at 60 ° C. for 2 hours, the reaction solution was diluted with water (10 mL) and hydrochloric acid (4M, 2.0 mL).
The resulting precipitate was collected by filtration, washed with water, separated and purified by silica gel column chromatography (Rf = 1.0, chloroform), and 2,6-bis (methylseleno) -3,7-bis [(trimethylsilyl) Ethynyl] anthracene (1.02 g, 81%) was obtained as a pale yellow solid.

The measurement results of the obtained 2,6-bis (methylseleno) -3,7-bis [(trimethylsilyl) ethynyl] anthracene are shown below.
Mp 227-228 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.11 (s, 2H), 8.05 (s, 2H), 7.67 (s, 2H), 2.46 (s, 6H), 0.33 (s, 18H); ¹³ C NMR ( 100 MHz, CDCl ₃ ) δ 132.8, 132.7, 131.6, 130.6, 125.3, 124.9, 122.2, 103.4, 101.3, 6.84, 0.25;
EI-MS (70 eV) m / z = 558 (M ⁺ ); HRMS: Calcd for C ₂₆ H ₃₀ Se ₂ Si ₂ : 558.02110, [M ⁺ ]. Found: 558.02063.

Subsequently, 3,9-diiodo-2,8-bis (trimethylsilyl) anthra [2,3-b: 6,7-b ′] diselenophene was synthesized as shown in the following reaction formula.

To a solution of 2,6-bis (methylseleno) -3,7-bis [(trimethylsilyl) ethynyl] anthracene (0.557 g, 1.0 mmol) in dichloromethane (60 mL) was added iodine (1.01 g, 4 mmol). Added at 0 ° C.
Stir at room temperature for 3 hours. Thereafter, the reaction solution was poured into a saturated aqueous solution of sodium hydrogensulfate (5 mL) with stirring for about 10 minutes.
The formed precipitate was collected by filtration, washed successively with water (100 mL) and ethanol (100 mL), and dried under reduced pressure to give 3,9-diiodo-2,8-bis (trimethylsilyl) anthra [2,3-b : 6,7-b ′] diselenophene (0.694 g, 89%) was obtained as a dark red solid.

The measurement results of the obtained 3,9-diiodo-2,8-bis (trimethylsilyl) anthra [2,3-b: 6,7-b ′] diselenophene are shown below.
Mp> 300 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.76 (s, 2H), 8.59 (s, 2H), 8.54 (s, 2H), 0.55 (s, 18H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 164.6, 137.7, 130.7, 127.9, 126.7, 124.0, 114.4, 99.8, 98.6, 0.28;
EI-MS (70 eV) m / z = 782 (M ⁺ ). HRMS: Calcd for C ₂₄ H ₂₄ I ₂ Se ₂ Si ₂ : 781.78302, [M ⁺ ]. Found: 781.78308.

Subsequently, anthra [2,3-b: 6,7-b ′] diselenophene was synthesized as shown in the following reaction formula.

3,9-Diiodo-2,8-bis (trimethylsilyl) anthra [2,3-b: 6,7-b ′] diselenophene (0.500 g, 0.64 mmol) was added to 1,4-dioxane (100 mL). LiAlH ₄ (0.5 g, 13.2 mmol) was added to the resulting suspension, refluxed for 24 hours, and then ethyl acetate (50 mL) was added at 0 ° C. over about 10 minutes with stirring.
The formed precipitate was collected by filtration, washed successively with water (100 mL) and ethanol (100 mL), dried under reduced pressure, and anthra [2,3-b: 6,7-b ′] diselenophene (0.212 g, 86%) as an orange solid.
The obtained solid was purified by a temperature gradient thermal sublimation method (ca. 310 ° C. at <10 ⁻² Pa) in a nitrogen atmosphere, and washed with a solvent (chloroform) to obtain a sample for analysis.

The measurement results of the obtained anthra [2,3-b: 6,7-b ′] diselenophene are shown below.
Mp> 300 ° C;
¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.76 (s, 2H), 8.74 (s, 2H), 8.61 (s, 2H), 8.17 (d, J = 5.2 Hz, 2H), 7.71 (d, J = 5.2 Hz, 2H);
EI-MS (70 eV) m / z = 386 (M ⁺ ); HRMS: Calcd for C ₁₈ H ₁₀ Se ₂ : 385.91075, [M ⁺ ]. Found: 385.91040. The solubility of ADS was not sufficient for measuring ¹³ C NMR spectra.

(Synthesis of 3,9-diiodo-2,8-diphenylanthra [2,3-b: 6,7-b ′] diselenophene)
3,9-Diiodo-2,8-diphenylanthra [2,3-b: 6,7-b ′] diselenophene was synthesized stepwise as follows.

First, as shown in the following reaction formula, 2,6-bis (methylseleno) -3,7-bis (phenylethynyl) anthracene was synthesized.

To a degassed solution of 2,6-bis (trifluoromethanesulfonyloxy) -3,7-bis (methylseleno) anthracene (1.50 g, 2.27 mmol) in DMF (40 mL), tributyl (phenylethynyl) was added. Tin (2.22 g, 5.68 mmol), (Pd (PPh ₃ ) ₂ Cl ₂ (161 mg, 0.0031 mmol, 5 mol%)) was added.
After stirring at 60 ° C. for 2 hours, the mixture was diluted with water (10 mL) and hydrochloric acid (4M, 2.0 mL).
The resulting precipitate was collected by filtration and washed with water.
The solid collected by filtration was separated and purified by silica gel column chromatography (Rf = 1.0, chloroform), and 2,6-bis (methylseleno) -3,7-bis (phenylethynyl) anthracene (0.91 g, 71%) Was obtained as a pale yellow solid.

The measurement results of the obtained 2,6-bis (methylseleno) -3,7-bis (phenylethynyl) anthracene are shown below.
Mp 227-228 ° C;
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.18 (s, 2H), 8.13 (s, 2H), 7.74 (s, 2H), 7.66-7.64 (m, 2H), 7.40-7.38 (m, 2H), 2.51 (s, 6H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 131.2, 132.5, 132.3, 131.9, 130.9, 129.2, 129.0, 125.6, 125.2, 123.5, 122.6, 95.6, 88.6, 7.06;
EI-MS (70 eV) m / z = 564 (M ⁺ ); HRMS: Calcd for C ₃₂ H ₂₂ Se ₂ : 566.00465, [M ⁺ ]. Found: 566.00598.

Subsequently, 3,9-diiodo-2,8-diphenylanthra [2,3-b: 6,7-b ′] diselenophene was synthesized as shown in the following reaction formula.

To a solution of 2,6-bis (methylseleno) -3,7-bis (phenylethynyl) anthracene (0.566 g, 1.0 mmol) dissolved in dichloromethane (60 mL) at 0 ° C., iodine (1.01 g, 4 mmol) was added.
After stirring at room temperature for 3 hours, the mixture was poured into a saturated aqueous sodium hydrogensulfite solution (5 mL) with stirring (approximately 10 minutes).
The formed precipitate was collected by filtration, washed successively with water (100 mL) and ethanol (100 mL), dried under reduced pressure, and 3,9-diiodo-2,8-diphenylanthra [2,3-b: 6, 7-b ′] diselenophene (0.788 g, quantitative yield) was obtained as a dark red solid.

The measurement results of the obtained 3,9-diiodo-2,8-diphenylanthra [2,3-b: 6,7-b ′] diselenophene are shown below.
Mp> 300 ° C;
EI-MS (70 eV) m / z = 788 (M ⁺ ). HRMS: Calcd for C ₂₄ H ₂₄ I ₂ Se ₂ Si ₂ : 789.76663, [M ⁺ ]. Found: 789.76819.
The solubility of 3,9-Diiodo-2,8-diphenylanthra [2,3-b: 6,7-b '] diselenophene was not sufficient for measuring ¹ H and ¹³ C NMR spectra.

Subsequently, as shown in the following reaction formula, 2,8-diphenylanthra [2,3-b: 6,7-b ′] diselenophene was synthesized.

To a suspension of 3,9-diiodo-2,8-diphenylanthra [2,3-b: 6,7-b ′] diselenophene (0.504 g, 0.64 mmol) in THF (100 mL) was added LiAlH. ₄ (0.5 g, 13.2 mmol) was added and refluxed for 24 hours.
After cooling, ethyl acetate (50 mL) was added at 0 ° C. while stirring the reaction solution (approximately 10 minutes).
The formed precipitate was collected by filtration, washed successively with water (100 mL) and ethanol (100 mL), dried under reduced pressure, and 2,8-diphenylanthra [2,3-b: 6,7-b ′] diselenophene ( 0.343 g (quantitative yield) was obtained as a dark red solid.
This solid was purified by a temperature gradient thermal sublimation method (ca. 360 ° C. at <10 ⁻² Pa) in a nitrogen atmosphere, and washed with a solvent (chloroform) to obtain a sample for analysis.

The measurement results of the obtained 2,8-diphenylanthra [2,3-b: 6,7-b ′] diselenophene are shown below.
Mp> 300 ° C;
EI-MS (70 eV) m / z = 536 (M ⁺ ); Anal.Calcd for; HRMS: Calcd for C ₃₀ H ₁₉ Se ₂ : 538.98117, [MH ⁺ ]. Found: 538.98096.
The solubility of DPh-ADS was not sufficient for measuring ¹ H and ¹³ C NMR spectra.

Anthra [2,3-b: 6,7-b ′] dithiophene (hereinafter referred to as ADT), anthra [2,3-b: 6,7-b ′] diselenophene (hereinafter referred to as ADS), 2, 8-diphenylanthra [2,3-b: 6,7-b ′] difuran (hereinafter referred to as DPh-ADF), 2,8-diphenylanthra [2,3-b: 6,7-b ′] dithiophene (hereinafter referred to as “DPh-ADF”) , DPh-ADT) was used to fabricate transistor elements, and the transistor characteristics were evaluated.

The SiO ₂ substrate was cut into a size of 1 cm × 1 cm in area, the back surface was treated with hydrofluoric acid, and silica oxidized in air was removed, and then Au was vacuum deposited to form a gate electrode. Next, an ADT organic thin film was formed on the surface of the SiO ₂ substrate by vacuum deposition. The SiO ₂ substrate was used after being surface-treated with octyltrichlorosilane. Au was vacuum-deposited on the formed organic thin film using a shadow mask to form a source electrode and a drain electrode having a channel length of 50 μm and a channel width of 1.5 mm, and a top contact type transistor element was manufactured. Hereinafter, this transistor element is referred to as an FET element ADT.

Further, similarly to the above, a transistor element was manufactured using ADS, DPh-ADF, and DPh-ADT. These transistor elements are referred to as FET element ADS, FET element DPh-ADF, and FET element DPh-ADT.

The transistor characteristics (output characteristics and transfer characteristics) were measured by changing the source-drain voltage Vd from 0 to −60 V and the gate voltage Vg from 20 to −60 V for each of the fabricated transistor elements.

1A and 1B show the output characteristics and transfer characteristics of the FET element ADT, respectively. Further, the output characteristics and transfer characteristics of the FET element ADS are shown in FIGS. 2A and 2B, respectively. The output characteristics and transfer characteristics of the FET element DPh-ADF are shown in FIG. 3 (A) and FIG. 3 (B), respectively. The output characteristics and transfer characteristics of the FET element DPh-ADT are shown in FIG. 4 (A) and FIG. 4 (B), respectively.

Then, these output characteristics from the transfer characteristics, the carrier mobility of the FET device ADT is 0.3cm ² V ^-1 s ^-1, carrier mobility of the FET device ADS is 0.7cm ² V ^-1 s ^-1, FET The carrier mobility of the element DPh-ADF was calculated as 0.6 cm ² V ⁻¹ s ⁻¹ , and the carrier mobility of the FET element DPh-ADT was calculated as 1.3 cm ² V ⁻¹ s ⁻¹ .

In a FET device that is a mixture of anti-anthradithiophene and syn-anthradithiophene and is manufactured under substantially the same conditions as described above, it is 0.09 cm ² V ⁻¹ s ⁻¹ (Non-patent Document 1). As reported, the carrier mobilities of the FET element ADT, the FET element ADS, the FET element DPh-ADF, and the FET element DPh-ADT were significantly higher.

From the above results, it was confirmed that an antiant radical cogenophene having good semiconductor properties could be synthesized.

It should be noted that the present invention can be variously modified and modified without departing from the scope of the present invention. Further, the above-described embodiment is for explaining the present invention, and does not limit the scope of the present invention.

This application is based on Japanese Patent Application No. 2012-177435 filed on August 9, 2012. In this specification, the specification, claims, and entire drawings of Japanese Patent Application No. 2012-177435 are incorporated by reference.

As described above, the anti-anthra chalcogenophene synthesis method according to the present invention makes it possible to selectively synthesize an anti-chalcogenogen ant. Since anti-anthra chalcogenophene has excellent semiconductor properties, it can be used for the synthesis of organic semiconductor materials.

Claims (4)

1. Reacting a compound represented by Formula 1 with a halogenating agent to obtain a compound represented by Formula 2;
   

   

   Reacting the compound represented by Formula 2 with a dealkylating agent to obtain a compound represented by Formula 3;
   

   

   Reacting the compound represented by Formula 3 with an acetylating agent to obtain a compound represented by Formula 4,
   

   

   Reacting the compound represented by Formula 4 with a terminal acetylene compound to obtain a compound represented by Formula 5;
   

   

   Cyclizing the compound represented by Formula 5 by allowing a base to act to obtain a compound represented by Formula 6;
   

   

   A method for synthesizing an anti-ant radical cogenofen.
   (In formulas 1 and 2, R ¹ represents an alkyl group, in formulas 2 to 4, X represents a halogen, in formulas 4 and 5, Ac represents an acetyl group, and in formula 5, R ² represents trimethylsilyl, phenyl or alkyl group, in the formula 6, R ³ is hydrogen, phenyl or an alkyl group.)
2. Reacting a compound represented by Formula 11 with a sulfur compound or a selenium compound to obtain a compound represented by Formula 12;
   

   

   Reacting the compound represented by Formula 12 with a dealkylating agent to obtain a compound represented by Formula 13;
   

   

   Reacting the compound represented by Formula 13 with trifluoromethanesulfonic anhydride to obtain a compound represented by Formula 14;
   

   

   Reacting the compound represented by Formula 14 with a terminal acetylene compound to obtain a compound represented by Formula 15;
   

   

   Cyclizing the compound represented by Formula 15 with iodine to obtain a compound represented by Formula 16;
   

   

   A method for synthesizing an anti-ant radical cogenofen.
   (In Formula 11 and Formula 12, R ¹¹ represents an alkyl group; in Formula 12 to Formula 15, R ¹² represents an alkyl group; in Formula 12 to Formula 16, Y represents sulfur or selenium; Tf represents a trifluoromethanesulfonyl group, and in formulas 15 and 16, R ¹³ represents a trimethylsilyl group, a phenyl group, or an alkyl group.)
3. After obtaining the compound represented by the formula 16 wherein R ¹³ is a trimethylsilyl group, the compound is reduced to anthrac [2,3-b: 6,7-b ′] dithiophene or anthra [2,3-b: 6,7-b ′] diselenophene,
   The method for synthesizing an anti-ant radical cogenophene according to claim 2.
4. After obtaining the compound represented by the formula 16 wherein R ¹³ is a phenyl group, it is reduced to 2,8-diphenylanthra [2,3-b: 6,7-b ′] dithiophene or 2,8- Diphenylanthra [2,3-b: 6,7-b ′] diselenophene is obtained,
   The method for synthesizing an anti-ant radical cogenophene according to claim 2.

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