JP2006248982A - Heteroacene compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heteroacene compound higher in solubility to organic solvents than conventional ones. <P>SOLUTION: The heteroacene compound is represented by formula(1a) or (1b)( wherein, E is a sulfur atom, selenium atom or tellurium atom; R<SP>1</SP>is a trialkylsilyl, 1-18C alkyl or 1-18C alkyl being a fluoroalkyl with part or the whole of hydrogen atoms substituted by fluorine atom(s), or the like; Ar<SP>1</SP>, Ar<SP>2</SP>and Ar<SP>3</SP>are each a chalcogen-containing condensed ring with benzene, naphthalene, anthracene, thiophene, selenophene, tellurophene or multiple thiophenes or selenophenes or tellurophenes condensed into a ring ). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heteroacene compound and a method for producing the same.

  In the field of organic electronics such as organic thin film transistors (FET) and organic electroluminescent devices (EL devices), the development of materials exhibiting excellent charge transport properties is one of the important issues. As a molecular design of such a material, it is promising to construct a highly planar π-conjugated skeleton in consideration of effective intermolecular interactions. In fact, pentacene, which is an acene compound having such a structure, exhibits high charge transporting properties and has been a subject of extensive research. In contrast, heteroacenes in which heteroatoms are introduced into a highly planar π-conjugated skeleton and condensed polycyclic aromatic compounds having similar dichalcogenide bonds are also expected as materials exhibiting promising charge transport properties.

As examples of the synthesis of heteroacenes, oligothiophene ladder compounds having up to 5 condensed rings and polythiophene ladder compounds crosslinked with a sulfonyl group have been reported (see, for example, Patent Document 1 and Non-Patent Document 1). As a method for synthesizing benzothio [3,2-b] [1] benzothiophene, which is a compound in which two benzothiophenes are condensed, o-bromoiodobenzene and acetylene are reacted in the presence of a palladium catalyst. A route has been reported in which 2-disubstituted acetylenes are synthesized, lithiated using tert-BuLi, and then treated with sulfur (Non-patent Document 2).
JP 2001-261794 A Tetrahedron Letters, Vol.30, No.25, pp3315-3318, 1989 J. Heterocyclic Chem., Vol25, p725, 1998

  However, since the heteroacenes synthesized so far have low solubility in organic solvents, it is difficult to purify them by column chromatography or the like, and it is difficult to sufficiently increase the purity. For this reason, it was not easy to apply to FETs and EL devices in which the purity of the compound is said to greatly affect the performance. In addition, when applied to an FET or EL element, it may be possible to form a film by dissolving a heteroacene in an organic solvent. However, if the solubility is low, such film formation becomes difficult.

  The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a heteroacene compound having higher solubility in an organic solvent than conventional ones. Another object of the present invention is to provide a method for efficiently producing such a heteroacene compound.

  As a result of intensive studies to solve the above-described problems, the present inventors have completed the present invention.

（式（１ａ）及び式（１ｂ）において、
Ｅは硫黄、セレン又はテルルであり、
Ｒ^１はアリール基、オリゴアリール基、１価の複素環基、１価のオリゴ複素環基、トリアルキルシリル基、炭素数１〜１８のアルキル基、炭素数１〜１８のアルキル基であって全部又は一部の水素がフッ素に置換されたフルオロアルキル基、アルコキシ基、アルキルチオ基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリル基、アミノ基、N−アルキルアミド基、アルカンカルボキサミド基、アゾ基、カルボキシル基、アシル基、アルコキシカルボニル基、ホルミル基、ニトロ基、シアノ基、ボリル基、ホスフィノ基、シリルオキシ基、アリールスルホニルオキシ基、アルキルスルホニルオキシ基、またはハロゲン原子であり、
Ａｒ^１Ａｒ^２及びＡｒ^３はそれぞれ独立してベンゼン、ナフタレン、アントラセン、チオフェン、セレノフェン、テルロフェン又は複数のチオフェンかセレノフェンかテルロフェンの縮環した含カルコゲン縮環体である） That is, the first heteroacene compound of the present invention is represented by the formula (1a) or (1b).

(In Formula (1a) and Formula (1b),
E is sulfur, selenium or tellurium;
R ¹ is an aryl group, oligoaryl group, monovalent heterocyclic group, monovalent oligoheterocyclic group, trialkylsilyl group, alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 18 carbon atoms, Fluoroalkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, allyl group, in which all or part of hydrogen is substituted with fluorine, Amino group, N-alkylamide group, alkanecarboxamide group, azo group, carboxyl group, acyl group, alkoxycarbonyl group, formyl group, nitro group, cyano group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkyl A sulfonyloxy group or a halogen atom,
Ar ¹ Ar ² and Ar ³ are each independently benzene, naphthalene, anthracene, thiophene, selenophene, tellurophene, or a thiophene, selenophene or tellurophene-containing chalcogen-condensed ring)

（式（２ａ），（２ｂ），（３ａ）及び（３ｂ）において、
Ｅは硫黄、セレン又はテルルであり、
ｍ，ｎはｍ＝１のときｎ＝２でｍ＝２のときｎ＝１であり、
Ｒ^１はアリール基、オリゴアリール基、１価の複素環基、１価のオリゴ複素環基、トリアルキルシリル基、炭素数１〜１８のアルキル基、炭素数１〜１８のアルキル基であって全部又は一部の水素がフッ素に置換されたフルオロアルキル基、アルコキシ基、アルキルチオ基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリル基、アミノ基、N−アルキルアミド基、アルカンカルボキサミド基、アゾ基、カルボキシル基、アシル基、アルコキシカルボニル基、ホルミル基、ニトロ基、シアノ基、ボリル基、ホスフィノ基、シリルオキシ基、アリールスルホニルオキシ基、アルキルスルホニルオキシ基、またはハロゲン原子であり、
Ａｒ^１Ａｒ^２及びＡｒ^３はそれぞれ独立してベンゼン、ナフタレン、アントラセン、チオフェン、セレノフェン、テルロフェン又は複数のチオフェンかセレノフェンかテルロフェンの縮環した含カルコゲン縮環体である） The second heteroacene compound of the present invention is a condensed polycyclic aromatic compound having a dichalcogenide bond represented by the formula (2a), (2b), (3a) or the formula (3b).

(In equations (2a), (2b), (3a) and (3b)
E is sulfur, selenium or tellurium;
m and n are n = 2 when m = 1 and n = 1 when m = 2,
R ¹ is an aryl group, oligoaryl group, monovalent heterocyclic group, monovalent oligoheterocyclic group, trialkylsilyl group, alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 18 carbon atoms, Fluoroalkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, allyl group, in which all or part of hydrogen is substituted with fluorine, Amino group, N-alkylamide group, alkanecarboxamide group, azo group, carboxyl group, acyl group, alkoxycarbonyl group, formyl group, nitro group, cyano group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkyl A sulfonyloxy group or a halogen atom,
Ar ¹ Ar ² and Ar ³ are each independently benzene, naphthalene, anthracene, thiophene, selenophene, tellurophene, or a thiophene, selenophene or tellurophene-containing chalcogen-condensed ring)

（式（４）において、
Ｅは硫黄、セレン又はテルルであり、
Ｒ^１はアリール基、オリゴアリール基、１価の複素環基、１価のオリゴ複素環基、トリアルキルシリル基、炭素数１〜１８のアルキル基、炭素数１〜１８のアルキル基であって全部又は一部の水素がフッ素に置換されたフルオロアルキル基、アルコキシ基、アルキルチオ基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリル基、アミノ基、N−アルキルアミド基、アルカンカルボキサミド基、アゾ基、カルボキシル基、アシル基、アルコキシカルボニル基、ホルミル基、ニトロ基、シアノ基、ボリル基、ホスフィノ基、シリルオキシ基、アリールスルホニルオキシ基、アルキルスルホニルオキシ基，またはハロゲン原子であり、
Ａｒ^１及びＡｒ^２はそれぞれ独立してベンゼン、ナフタレン、アントラセン、チオフェン、セレノフェン、テルロフェン又は複数のチオフェンかセレノフェンかテルロフェンの縮環した含カルコゲン縮環体である） The third heteroacene compound of the present invention is represented by the formula (4).

(In Formula (4),
E is sulfur, selenium or tellurium;
R ¹ is an aryl group, oligoaryl group, monovalent heterocyclic group, monovalent oligoheterocyclic group, trialkylsilyl group, alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 18 carbon atoms, Fluoroalkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, allyl group, in which all or part of hydrogen is substituted with fluorine, Amino group, N-alkylamide group, alkanecarboxamide group, azo group, carboxyl group, acyl group, alkoxycarbonyl group, formyl group, nitro group, cyano group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkyl A sulfonyloxy group or a halogen atom,
Ar ¹ and Ar ² are each independently benzene, naphthalene, anthracene, thiophene, selenophene, tellurophene, or a chalcogen-condensed ring in which a plurality of thiophene, selenophene, or tellurophene are condensed.

（式（５）及び式（６）において、
Ｅは硫黄、セレン又はテルルであり、
Ｒ^１はアリール基、オリゴアリール基、１価の複素環基、１価のオリゴ複素環基、トリアルキルシリル基、炭素数１〜１８のアルキル基、炭素数１〜１８のアルキル基であって全部又は一部の水素がフッ素に置換されたフルオロアルキル基、アルコキシ基、アルキルチオ基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリル基、アミノ基、N−アルキルアミド基、アルカンカルボキサミド基、アゾ基、カルボキシル基、アシル基、アルコキシカルボニル基、ホルミル基、ニトロ基、シアノ基、ボリル基、ホスフィノ基、シリルオキシ基、アリールスルホニルオキシ基、アルキルスルホニルオキシ基、またはハロゲン原子であり、
Ａｒ^１及びＡｒ^２はそれぞれ独立してベンゼン、ナフタレン、アントラセン、チオフェン、セレノフェン、テルロフェン又は複数のチオフェンかセレノフェンかテルロフェンの縮環した含カルコゲン縮環体である） The fourth heteroacene compound of the present invention is a condensed polycyclic aromatic compound having a dichalcogenide bond represented by formula (5) or formula (6).

(In Formula (5) and Formula (6),
E is sulfur, selenium or tellurium;
R ¹ is an aryl group, oligoaryl group, monovalent heterocyclic group, monovalent oligoheterocyclic group, trialkylsilyl group, alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 18 carbon atoms, Fluoroalkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, allyl group, in which all or part of hydrogen is substituted with fluorine, Amino group, N-alkylamide group, alkanecarboxamide group, azo group, carboxyl group, acyl group, alkoxycarbonyl group, formyl group, nitro group, cyano group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkyl A sulfonyloxy group or a halogen atom,
Ar ¹ and Ar ² are each independently benzene, naphthalene, anthracene, thiophene, selenophene, tellurophene, or a chalcogen-condensed ring in which a plurality of thiophene, selenophene, or tellurophene are condensed.

  Since the 1st-4th heteroacene compound of this invention is a pi-electron type compound which has high planarity, it can be utilized as organic electronics materials, such as FET and an EL element. In addition, since both compounds have a trialkylsilyl group, an alkyl group, or a fluoroalkyl group at both ends, the solubility in organic solvents is higher than conventional heteroacene compounds that do not have such a terminal group. . For this reason, purification operations such as column chromatography can be performed, and the purity can be sufficiently increased. In addition, it has become easy to apply to FETs and EL devices in which the purity of the compound is said to greatly affect the performance. In addition, when applied to an FET or EL element, it may be possible to form a film by dissolving a heteroacene in an organic solvent, which is also suitable for such film formation. In addition, in this specification, the chalcogen-condensed ring is a product obtained by condensing a plurality of thiophenes, selenophene, or tellurophene so that the directions of the chalcogens are staggered, and also so that the directions of the chalcogens are the same. And those with random chalcogen orientations.

In the first to fourth heteroacene compounds of the present invention, Ar ¹ , Ar ² , and Ar ³ may be selected from the following group, for example. That is, Ar ¹ , Ar ² , Ar ³ contained in the formulas (1a), (2a), (3a), (4), (5), (6) may be selected from the group of , Ar ¹ , Ar ² , and Ar ³ included in the formulas (1b), (2b), and (3b) may be selected from the group of Formula 8. In the chemical formulas 7 and 8, E represents sulfur, selenium or tellurium.

In the first to fourth heteroacene compounds of the present invention, R ¹ is a trialkylsilyl group, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, and all or part of hydrogen is fluorine. It may be substituted. Among these, as the trialkylsilyl group, all three alkyl groups may be the same, or all may be different, or only one may be different. For example, a trimethylsilyl (TMS) group, triisopropylsilyl ( TIPS) group, tri-tert-butylsilyl (TTBS) group, tert-butyldimethylsilyl (TBDMS) group and the like. In addition, the alkyl group having 1 to 18 carbon atoms may be linear or branched, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl. Group, tert-butyl group, hexyl group, octyl group, dodecyl group and the like. In addition, such an alkyl group having 1 to 18 carbon atoms in which all or part of hydrogen is substituted with fluorine includes a perfluoroalkyl group in which all hydrogen is substituted with fluorine, or only terminal hydrogen is fluorine. Examples include substituted alkyl groups. In addition, you may use the above-mentioned C1-C18 alkyl group as alkyl of a trialkylsilyl group.

  The second and fourth heteroacene compounds of the present invention are condensed polycyclic aromatic compounds having a dichalcogenide bond, and can be used as organic electronic materials, and the first and third heteroacene compounds of the present invention, respectively. It can also be used as a synthetic intermediate.

The second heteroacene compound of the present invention is a bisacetylene represented by the following formula (7) (in the formula (7), X is chlorine, bromine or iodine, and Ar ¹ , Ar ² , Ar ³ and R ¹ Can be produced by substituting X with metal and reacting with sulfur, selenium or tellurium alone. Here, in order to substitute X with a metal, it is preferable to use an organometallic reagent. As such an organometallic reagent, for example, organic lithium (such as n-BuLi, sec-BuLi, tert-BuLi), organic magnesium halide, or the like can be used. Moreover, after manufacturing the 2nd heteroacene compound of this invention as mentioned above, the 1st heteroacene compound of this invention is converted into -E- in the ring of the ring of this heteroacene compound. Can be manufactured. This conversion reaction proceeds, for example, in the presence of copper. In addition, what is necessary is just to set reaction conditions, such as the reaction solvent, reaction temperature, reaction time, the number of moles of the used substrate and reagent, according to the reagent etc. to be used.

The fourth heteroacene compound of the present invention is a monoacetylene represented by the following formula (8) (in the formula (8), X is chlorine, bromine or iodine, and Ar ¹ , Ar ² and R ¹ are the same as those described above. And the like, and then reacting with a simple substance of sulfur, selenium or tellurium. Here, in order to substitute X with a metal, it is preferable to use an organometallic reagent. As such an organometallic reagent, for example, organic lithium (such as n-BuLi, sec-BuLi, tert-BuLi), organic magnesium halide, or the like can be used. In addition, after producing the fourth heteroacene compound of the present invention as described above, the third heteroacene compound of the present invention is converted by converting the -EE- site in the ring of the heteroacene compound to -E-. Can be manufactured. This conversion reaction proceeds, for example, in the presence of copper. In addition, what is necessary is just to set reaction conditions, such as the reaction solvent, reaction temperature, reaction time, the number of moles of the substrate to be used, and a reagent, according to the reagent etc. to be used.

Next, an example of a method for producing an organic thin film transistor using the pentaacene compound of the present invention will be described. First, an n-type silicon substrate having a silicon oxide film as an insulating layer is subjected to ultrasonic cleaning with a neutral detergent diluted with pure water, and then the detergent is removed by ultrasonic cleaning in pure water. Thereafter, ultraviolet irradiation cleaning is performed with an ultraviolet-ozone cleaner. A thin film of the heteroacene compound of the present invention is formed on the cleaned substrate by a vacuum deposition method. As the heteroacene compound, it is preferable to use a high-purity compound obtained by repeating the purification operation several times. The vacuum deposition conditions are such that the substrate is fixed above the deposition boat, the substrate temperature is adjusted to −100 to −150 ° C., and the degree of vacuum is reduced to the order of 10 ⁻⁶ Torr. Thereafter, vacuum deposition is performed so that a desired thickness (for example, 50 nm) is obtained at a rate of several nm to several tens of nm per minute. Subsequently, a gold electrode is vacuum deposited as a source electrode and a drain electrode. Furthermore, N-methyl-3,4,9,10-tetracarboxylic acid diimide is vacuum-deposited at a rate of several nm per minute so as to have a desired thickness (for example, 50 nm). Although an organic thin film transistor can be manufactured in this manner, it may be manufactured by other methods.

  The best mode for carrying out the present invention will be described below with reference to examples.

[Example 1]
First, monoacetylene represented by the compound 1 of the following chemical formula 11 is a Sonogashira coupling reaction between 3-bromo-2-iodothiophene and 3-bromo-2-ethynylthiophene, followed by presence of trimerylsilyl chloride. This was synthesized by reacting with lithium diisopropylamide. Next, Compound 1 (5.0 g, 10.2 mmol) dissolved in anhydrous THF (100 mL) under an argon atmosphere was cooled to −78 ° C. with a dry ice-acetone bath, and tert-BuLi (1.53 M heptane solution, 26.5 mL, 40.6 mmol, 4.0 mol amt.) Was added dropwise over 10 minutes. After stirring at −78 ° C. for 60 minutes, sulfur (crystal) (976 mg, 30.5 mmol, 3.0 mol. Amt.) Was added, and after 5 minutes, the bath was removed and the temperature was raised. Two hours later, potassium ferricinated sodium hydroxide aqueous solution was added to the reaction solution, extracted with diethyl ether, washed with distilled water, dried over magnesium sulfate, and the solvent was distilled off. The red residue was separated and purified with a silica gel column (hexane) to obtain Compound 2 (2.83 g, 65%) (see Chemical Formula 11 below) as a red solid. The spectral data of Compound 2 is as follows. C ₁₆ H ₂₀ S ₅ Si ₂ ; red powders; ¹ H NMR (270 MHz, CDCl ₃ ) δ 7.33 (s, 1H), 7.08 (s, 1H), 0.37 (s, 9H), 0.34 (s, 9H); MS (EI) / 428.

[Example 2]
Compound 2 (300 mg, 0.699 mmol) was heated at 300 ° C. for 20 minutes in the presence of copper (nanosize powder) (178 mg, 2.80 mmol, 4.0 mol amt.) Under an argon atmosphere. After allowing to cool, dichloromethane was added, insoluble matter was filtered off, and the filtrate was concentrated. The obtained solid was separated and purified using a silica gel column (hexane) to obtain Compound 3 (155 mg, 56%) (see the following chemical formula 12) as colorless crystals. As for this compound 3, a compound having a terminal hydrogen instead of TMS (referred to as compound 3 ′) was synthesized, and the solubility in each hexane was examined. As a result, the solubility of compound 3 ′ was 0.16 mg / mL. The solubility of Compound 3 was 4.0 mg / mL. That is, it was found that compound 3 was 25 times more soluble in hexane than compound 3 ′. In addition, the spectrum data of the compound 3 are as follows. C ₁₆ H ₂₀ S ₄ Si ₂ ; colorless powders; ¹ H NMR (270 MHz, CDCl ₃ ) δ 7.38 (s, 2H), 0.38 (s, 18H).

[Example 3]
First, bisacetylene represented by the compound 4 shown below is converted into 2,3,5,6-tetrabromothienyl [3,2-b] thiophene and 3-bromo-2-ethynyl-5-triisopropylsilylthiophene. And the Sonogashira coupling reaction. Next, Compound 4 (200 mg, 0.204 mmol) dissolved in anhydrous THF (4 mL) under an argon atmosphere was cooled to −78 ° C. in a dry ice-acetone bath, and tert-BuLi (1.49 M heptane solution, 1. 10 mL, 1.63 mmol, 8.0 mol amt.) Was added dropwise over 5 minutes. After stirring at −78 ° C. for 30 minutes, the temperature was raised to 0 ° C. The reaction solution was added to a sulfur toluene solution (0.306 M, 4.0 mL, 1.22 mmol, 6.0 mol amt.), Stirred at 0 ° C. for 15 minutes, then the ice bath was removed and the temperature was raised. After 4 hours, a potassium ferricinated sodium hydroxide aqueous solution was added to the reaction solution, extracted with dichloromethane, washed with distilled water, dried over magnesium sulfate, and the solvent was distilled off. The reddish purple residue was subjected to a short column (dichloromethane) with silica gel, and further separated and purified using GPC (chloroform) to give compound 5 (42 mg, 24%) as a regioisomer mixture (see the following chemical formula 13). Got. The spectral data of Compound 5 is as follows. C ₃₆ H ₄₄ S ₁₀ Si ₂ ; purple powders; ¹ H NMR (270 MHz, CDCl ₃ ) δ 7.41 (s), 7.37 (s), 7.35 (s), 7.10 (s), 1.47-1.34 (m), 1.16 -1.13 (m); MS (MALDI) / 852.

[Example 4]
Compound 5 (50 mg, 0.0586 mmol) was heated at 320 ° C. for 2 hours and 30 minutes in the presence of copper (nanosize powder) (150 mg, 2.36 mmol, 40 mol. Amt.) Under an argon atmosphere. After allowing to cool, dichloromethane was added and insolubles were filtered off. The insoluble matter was washed with hot orthodichlorobenzene, filtered while hot, and the filtrate was concentrated to obtain the target compound 6 (23.7 mg, 51%) (see the following chemical formula 14) as a yellow solid. The measurement result of the cyclic voltammetry of this compound 6 is shown in FIG. As shown in FIG. 1, in Compound 6, reversible two-stage oxidation peaks (E _1/2 = + 0.43 V, +0.82 V vs Fc / Fc +) were observed. This result shows that Compound 6 can be expected as a p-type charge transport material. Moreover, the spectrum data of the compound 6 are as follows. C ₃₆ H ₄₄ S ₈ Si ₂ ; yellow needles; ¹ H NMR (400 MHz, C ₆ D ₄ Cl ₂ ) δ 7.28 (s, 2H), 1.28-1.19 (m, 6H), 1.08 (d, 36H, J = 7.2Hz); MS (MALDI) / 788.

  In addition, this invention is not limited to the above Example at all, As long as it belongs to the technical scope of this invention, it can implement in a various aspect.

  For example, in Examples 1 to 4 described above, the production example of polythiophene has been described, but polyselenophene and polytellurophene can be produced in the same manner.

6 is an explanatory diagram of a cyclic voltammetry measurement result of Compound 6. FIG.

Claims (10)

A heteroacene compound represented by the following formula (1a) or (1b).

(In Formula (1a) and Formula (1b),
E is sulfur, selenium or tellurium;
R ¹ is an aryl group, oligoaryl group, monovalent heterocyclic group, monovalent oligoheterocyclic group, trialkylsilyl group, alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 18 carbon atoms, Fluoroalkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, allyl group, in which all or part of hydrogen is substituted with fluorine, Amino group, N-alkylamide group, alkanecarboxamide group, azo group, carboxyl group, acyl group, alkoxycarbonyl group, formyl group, nitro group, cyano group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkyl A sulfonyloxy group or a halogen atom,
Ar ¹ Ar ² and Ar ³ are each independently benzene, naphthalene, anthracene, thiophene, selenophene, tellurophene, or a thiophene, selenophene or tellurophene-containing chalcogen-condensed ring) A heteroacene compound represented by the following formula (2a), (2b), (3a) or formula (3b).

(In equations (2a), (2b), (3a) and (3b)
E is sulfur, selenium or tellurium;
m and n are n = 2 when m = 1 and n = 1 when m = 2,
R ¹ is an aryl group, oligoaryl group, monovalent heterocyclic group, monovalent oligoheterocyclic group, trialkylsilyl group, alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 18 carbon atoms, Fluoroalkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, allyl group, in which all or part of hydrogen is substituted with fluorine, Amino group, N-alkylamide group, alkanecarboxamide group, azo group, carboxyl group, acyl group, alkoxycarbonyl group, formyl group, nitro group, cyano group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkyl A sulfonyloxy group or a halogen atom,
Ar ¹ Ar ² and Ar ³ are each independently benzene, naphthalene, anthracene, thiophene, selenophene, tellurophene, or a thiophene, selenophene or tellurophene-containing chalcogen-condensed ring) A heteroacene compound represented by the following formula (4).

(In Formula (4),
E is sulfur, selenium or tellurium;
R ¹ is an aryl group, oligoaryl group, monovalent heterocyclic group, monovalent oligoheterocyclic group, trialkylsilyl group, alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 18 carbon atoms, Fluoroalkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, allyl group, in which all or part of hydrogen is substituted with fluorine, Amino group, N-alkylamide group, alkanecarboxamide group, azo group, carboxyl group, acyl group, alkoxycarbonyl group, formyl group, nitro group, cyano group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkyl A sulfonyloxy group or a halogen atom,
Ar ¹ and Ar ² are each independently benzene, naphthalene, anthracene, thiophene, selenophene, tellurophene, or a chalcogen-condensed ring in which a plurality of thiophene, selenophene, or tellurophene are condensed. The heteroacene compound represented by following formula (5) or formula (6).

(In Formula (5) and Formula (6),
E is sulfur, selenium or tellurium;
R ¹ is an aryl group, oligoaryl group, monovalent heterocyclic group, monovalent oligoheterocyclic group, trialkylsilyl group, alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 18 carbon atoms, Fluoroalkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, allyl group, in which all or part of hydrogen is substituted with fluorine, Amino group, N-alkylamide group, alkanecarboxamide group, azo group, carboxyl group, acyl group, alkoxycarbonyl group, formyl group, nitro group, cyano group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkyl A sulfonyloxy group or a halogen atom,
Ar ¹ and Ar ² are each independently benzene, naphthalene, anthracene, thiophene, selenophene, tellurophene, or a chalcogen-condensed ring in which a plurality of thiophene, selenophene, or tellurophene are condensed. Bisacetylenes represented by the following formula (7) (in formula (7), X is chlorine, bromine or iodine, and Ar ¹ , Ar ² , Ar ³ and R ¹ are as defined in claim 2) The process for producing a heteroacene compound according to claim 2, wherein X is substituted with a metal and then reacted with a simple substance of sulfur, selenium or tellurium.

Bisacetylenes represented by the following formula (7) (in formula (7), X is chlorine, bromine or iodine, and Ar ¹ , Ar ² , Ar ³ and R ¹ are as defined in claim 2) After substituting X with a metal, sulfur, selenium, or tellurium is reacted with each other to form a heteroacene compound according to claim 2, and then the -EE- site in the ring of the heteroacene compound is changed to -E-. A method for producing a heteroacene compound, wherein the heteroacene compound according to claim 1 is obtained by conversion.

  The method for producing a heteroacene compound according to claim 6, wherein copper is used when converting the -EE- site in the ring of the heteroacene compound according to claim 2 to -E-. X of monoacetylene represented by the following formula (8) (wherein X is chlorine, bromine or iodine, and Ar ¹ , Ar ² and R ¹ are as defined in claim 4) The process for producing a heteroacene compound according to claim 4, wherein the heteroacene compound according to claim 4 is reacted with a simple substance of sulfur, selenium or tellurium after substitution.

X of monoacetylene represented by the following formula (8) (wherein X is chlorine, bromine or iodine, and Ar ¹ , Ar ² and R ¹ are as defined in claim 4) The heteroacene compound according to claim 4 is reacted by reacting with a simple substance of sulfur, selenium or tellurium after being substituted with, and then converting the -EE- site in the ring of the heteroacene compound to -E-. A process for producing a heteroacene compound, wherein the heteroacene compound according to claim 3 is obtained.

  The method for producing a heteroacene compound according to claim 9, wherein copper is used when converting the -EE- site in the ring of the heteroacene compound according to claim 4 to -E-.

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