JP5404865B2 - Novel condensed polycyclic aromatic compounds - Google Patents

Description

  The present invention relates to a novel condensed polycyclic aromatic compound. The present invention also relates to methods for synthesizing and using such novel condensed polycyclic aromatic compounds.

  Various studies have been made on organic semiconductor compounds for use in organic semiconductor layers for organic thin film transistors (TFTs), organic carrier transport layers, organic light emitting devices, and the like. In particular, a thin film transistor having an organic semiconductor layer made of an organic semiconductor compound is expected to replace the current silicon-based transistor as a low-cost and lightweight device. In addition, the organic semiconductor layer is expected to be applied to smart tags, lightweight displays, and the like by utilizing advantages specific to organic materials such as being lightweight and flexible.

  Therefore, many studies have been made on organic semiconductor compounds for forming an organic semiconductor layer (Patent Documents 1 to 5 and Non-Patent Documents 1 to 3).

  Among these organic semiconductor compounds, condensed polycyclic aromatic compounds, particularly dinaphthothienothiophene (DNTT) represented by the following formula, or a substituted polycyclic aromatic compound having a similar structure or a similar structure, It has been found that material stability, carrier mobility, semiconductor properties, etc. are preferred.

  However, since the condensed polycyclic aromatic compound has strong aromaticity and high crystallinity, the solubility in an organic solvent or the like is extremely low, and it has been difficult to use in a coating method. Therefore, when obtaining an organic semiconductor film using a condensed polycyclic aromatic compound, it has been common to obtain an organic semiconductor thin film made of a condensed polycyclic aromatic compound by vapor deposition.

  Further, although the above-mentioned DNTT has a slight solubility in an organic solvent due to the small number of condensed rings, it still achieves sufficient solubility for industrial use in a solution method. There was not (patent document 4).

  In addition, in order to obtain an organic semiconductor thin film by using a condensed polycyclic aromatic compound such as DNTT in a coating method, a precursor that has high solubility and decomposes to generate such a condensed polycyclic aromatic compound is used. Have also been proposed (Patent Document 5, Non-Patent Documents 2 and 3).

JP 2006-89413 A JP 2008-290963 A International Publication WO2006 / 077788 International Publication WO2008 / 050726 International Publication WO2011 / 024804

“Facile Synthesis of Highly π-Extended Heteroarenes, Dinaphtho [2,3-b: 2 ′, 3′-f] charcogenopheno [3,2-b] charcogenophenes, and Tyrapt Applied”. Kazuo Takimiya, J.A. Am. Chem. Soc. , 2007, 129 (8), pp 2224-2225. H. Uno et a1. , Photoprecursor for pentacene, Tetrahedron Letters, 2005, Vol. 46, no. 12, PP. 1981-1983 WANG, Y.M. etal, Synthesis, charactrization, and reactionsof 6,13-disclosed 2, 3, 9, 10-tetrakis (trimethylsylly 1) pentacene derivatives, Tetrahedron V, 1 7 63, no. 35, pp. 8586-8597

  As described above, DNTT has a slight solubility in organic solvents due to the small number of condensed rings, but still achieves sufficient solubility for industrial use in solution processes. (Patent Document 4).

Accordingly, the present invention provides a condensed polycyclic aromatic compound having a relatively high solubility and a method for synthesizing and using such a novel condensed polycyclic aromatic compound. In particular, in the present invention, a condensed polycyclic aromatic compound (first present invention) that can be used as an organic semiconductor compound, and a condensed compound that can be used as a precursor for the synthesis of this condensed polycyclic aromatic compound. A polycyclic aromatic compound (second invention) is provided.

(First invention)
The inventors of the present invention, in a condensed polycyclic aromatic compound having a structure similar to DNTT, introduces a substituent into the aromatic ring adjacent to the central heterocyclic ring portion, whereby the solubility of the condensed polycyclic aromatic compound is improved. Was found to be improved, and the present invention was reached.

  The condensed polycyclic aromatic compound of the first invention is represented by the following formula (I):

(Q ₁ and Q ₂ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of Q ₁ and Q ₂ is a group other than a hydrogen atom and a halogen atom,
B is a substituted or unsubstituted fused ring having at least one benzene ring moiety;
Y is independently selected from chalcogen, and A _{1 to} A ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and two adjacent groups are bonded to each other to form an aromatic group. Group may be formed).

  The condensed polycyclic aromatic compound represented by the formula (I) can be used as an organic semiconductor compound.

  Further, the condensed polycyclic aromatic compound represented by the formula (I) can have a relatively high solubility when the benzene ring adjacent to the central condensed heterocycle has a substituent (Q). . This is because the presence of a substituent at a position close to the center of the condensed polycyclic aromatic compound adjacent to the central condensed heterocyclic ring reduces the crystallinity of the compound. This is considered to be due to the fact that the polarity of the entire compound increases depending on the polarity.

  In addition, although the general formula of Patent Document 4 includes DNTT in which hydrogen of the condensed benzene ring is substituted, specifically, DNTT in which the position farthest from the central condensed heterocycle is substituted It is only disclosed, and the embodiment in which the benzene ring adjacent to the central condensed heterocycle is substituted is not specifically disclosed. Further, Patent Document 4 does not disclose a specific method for synthesizing DNTT in which a benzene ring adjacent to a central condensed heterocycle is substituted.

  The first aspect of the present invention also relates to a solution, an organic semiconductor film, an organic semiconductor device and the like using the condensed polycyclic aromatic compound of the first aspect of the present invention.

(Second invention)
The inventors of the present invention have found that the condensed polycyclic aromatic compound of the first present invention can be easily synthesized by using a specific condensed polycyclic aromatic compound, and have arrived at the second present invention. .

  The condensed polycyclic aromatic compound of the second invention is represented by the following formula (II):

(X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of X ₁ and X ₂ is a halogen atom,
B is a fused ring having at least one benzene ring moiety;
Y is independently selected from chalcogen, and A _{1 to} A ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and two adjacent groups are bonded to each other to form an aromatic group. Group may be formed).

  The condensed polycyclic aromatic compound of the second invention can be used as a precursor for the synthesis of the condensed polycyclic aromatic compound of the first invention. Specifically, for example, according to the condensed polycyclic aromatic compound of the second aspect of the present invention, various coupling methods using aromatic halides, Mizorogi / Heck reaction, Negishi coupling, Ueda / Kosugi / Still cup Ring, Sonogashira coupling, Suzuki-Miyaura coupling, Buchwald-Hartwig reaction, Kumada-Tamao-Colour coupling makes it possible to synthesize the condensed polycyclic aromatic compound of the first invention. .

  Further, the condensed polycyclic aromatic compound represented by the formula (II) can have a relatively high solubility when the benzene ring adjacent to the central condensed heterocycle has a halogen atom (X). . This is because the presence of a halogen group at a position close to the center of the condensed polycyclic aromatic compound due to the presence of a benzene ring adjacent to the central condensed heterocycle reduces the crystallinity of the compound. This is thought to be due to the fact that the polarity of the entire halogen compound increases due to the polarity of the halogen group.

  The second aspect of the present invention also relates to a method for synthesizing and using the condensed polycyclic aromatic compound of the second aspect of the present invention.

It is the molecular structure ORTEP figure based on the single crystal structure analysis about TIPS2 substitution DNTT obtained in Example 2. FIG. FIG. 3 is a crystal packing (stereo) diagram for the TIPS2-substituted DNTT obtained in Example 2. It is a figure which shows the transfer characteristic of FET characteristic about the organic-semiconductor element obtained in Example 3. FIG.

(Definition)
In the description of this specification, in order to simplify the description, “an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and the number of carbon atoms” A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms The description of “an imide group, a sulfide group having 1 to 20 carbon atoms, and an alkylsilylalkynyl group having 1 to 40 carbon atoms” is expressed as “an alkyl group or the like”.

Here, the “aromatic group” in the “substituted or unsubstituted aromatic group having 4 to 20 carbon atoms” is a benzene aromatic group, a heterocyclic aromatic group, or a non-benzene aromatic group. Good. Specific examples of the benzene aromatic group include a benzene group and a naphthalene group. Specific examples of the heterocyclic aromatic group include a furan group, a thiophene group, a pyrrole group, and an imidazole group. Specific examples of the non-benzene aromatic group include annulene and azulene. When these aromatic groups are substituted, examples of the substituent include alkyl groups, alkenyl groups, alkynyl groups, aromatic groups, ketone groups, amino groups, amide groups, imide groups, and sulfide groups.

  For example, when the “substituted or unsubstituted aromatic group having 4 to 20 carbon atoms” is a substituted or unsubstituted thiophene group, the thiophene group is further substituted or unsubstituted thiophene group as shown below. May be replaced by:

（ｕは０〜４の整数）

(U is an integer from 0 to 4)

  In addition, when an aromatic group such as a thiophene group is substituted, the substituent is a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a substituted or unsubstituted aromatic group, a ketone group, an amino group, an amide group, It may be an imide group, a sulfide group, an alkylsilylalkynyl group, or the like.

  Further, the “alkylsilylalkynyl group having 1 to 40 carbon atoms” may be a trialkylsilylalkynyl group having 1 to 40 carbon atoms, particularly a trialkylsilylalkynyl group having the following formula:

(R _{1 to} R ₃ are each independently an alkyl group having 1 to 10 carbon atoms, particularly a group consisting of a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. Group selected).

  In the description herein, “chalcogen” means oxygen, sulfur, selenium, tellurium and polonium, especially sulfur and selenium, more particularly sulfur.

  In the description herein, “halogen” means fluorine, chlorine, bromine, iodine, and astatine, especially chlorine, bromine, and iodine, more particularly bromine.

  In the description of the present specification, a “substituted or unsubstituted aromatic group having 4 to 20 carbon atoms” formed by bonding two adjacent groups to each other is, for example, a substituted or unsubstituted group having the following structure: May be an aromatic group of:

  In the description of the present specification, Patent Document 5 can be referred to as the diene-type alkene with respect to “substituent (D) having 2 to 20 carbon atoms added to the benzene ring by the diene-type alkene”. For a method for adding such a diene-type alkene to the benzene ring of the condensed polycyclic aromatic compound, Patent Document 5 can be referred to.

  In addition, as described in Patent Document 5, such a diene-type alkene added to the benzene ring of the condensed polycyclic aromatic compound reduces the crystallinity of the condensed polycyclic aromatic compound to reduce the condensed polycyclic aromatic compound. The solubility of the group compound can be increased. Further, when a semiconductor film is produced by using a condensed polycyclic aromatic compound to which such a diene-type alkene is added in a solution method, the solvent from the solution is obtained by heating the coating film of the solution containing the compound. In conjunction with the removal of the diene, the diene-type alkene can be eliminated and removed.

  Specifically, the “substituent (D) having 2 to 20 carbon atoms added to the benzene ring by a diene-type alkene” is, for example, the following formulas (B-1a) and (B-2a), particularly the following formula ( Mention may be made of compounds of the following formulas (B-1c) and (B-2c): B-1b) and (B-2b), more particularly:

(R _a , R _b , R _c and R _d are each independently a bond, hydrogen, halogen, hydroxyl group, amide group, mercapto group, cyano group, alkyl group having 1 to 10 carbon atoms, or 2 to 10 carbon atoms. An alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, An ether group having 1 to 10 carbon atoms, a ketone group having 1 to 10 carbon atoms, an amino group having 1 to 10 carbon atoms, an amide group having 1 to 10 carbon atoms, an imide group having 1 to 10 carbon atoms, And selected from the group consisting of C 1-10 sulfide groups,
R _a and R _b may be bonded to each other to form a ring,
R _c and R _d may be bonded to each other to form a ring,
n is an integer of 1 to 5; and Z is a bond (-), oxygen (-O-), methylene carbon (-C (R _r ) _2- ), ethylenic carbon (-C (R _r ) =), Carbonyl group (—C (═O) —), nitrogen (—N (R _r ) —), and sulfur (—S—), and n is 2 or greater Sometimes each may be different (R _r is independently hydrogen, halogen, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, carbon An alkoxy group having 1 to 10 atoms, a substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, an ether group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms; 10 ketone groups, 1-10 carbon atom amino groups, 1-10 carbon atoms Selected from the group consisting of an amide group, an imide group having 1 to 10 carbon atoms, and a sulfide group having 1 to 10 carbon atoms)).

  More specifically, examples of the diene-type alkene include compounds represented by the following formulas (B-1-1) to (B-2-3):

(R and R _r are each independently hydrogen, halogen, hydroxyl group, amide group, mercapto group, cyano group, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, or 2 to 2 carbon atoms. 10 alkynyl groups, alkoxy groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic groups having 4 to 10 carbon atoms, ester groups having 1 to 10 carbon atoms, ether groups having 1 to 10 carbon atoms A ketone group having 1 to 10 carbon atoms, an amino group having 1 to 10 carbon atoms, an amide group having 1 to 10 carbon atoms, an imide group having 1 to 10 carbon atoms, and a sulfide having 1 to 10 carbon atoms Selected from the group consisting of groups).

(First invention)
(First invention-condensed polycyclic aromatic compound)
The condensed polycyclic aromatic compound of the first invention is represented by the following formula (I):

(Q ₁ and Q ₂ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of Q ₁ and Q ₂ is a group other than a hydrogen atom and a halogen atom,
B is a substituted or unsubstituted fused ring having at least one benzene ring moiety;
Y is each independently selected from chalcogen, and A _{1 to} A ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _4. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

  The condensed polycyclic aromatic compound of the first present invention is represented, for example, by the following formula (I-1):

(Q _{1 to} Q ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and at least one of Q _{1 to} Q ₄ is a group other than a hydrogen atom and a halogen atom,
Y is each independently selected from chalcogens, and A _{1 to} A ₈ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _8. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

Here, in the compound of formula (I-1), for example, Q ₂ and Q ₃ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and Q ₂ and Q ₃ At least one is a group other than a hydrogen atom and a halogen atom, and Q ₁ and Q ₄ are a hydrogen atom.

  This compound of formula (I-1) may in particular be a compound of the following formula (I-1-1):

(R _{1 to} R ₃ are each independently an alkyl group having 1 to 10 carbon atoms).

  The condensed polycyclic aromatic compound of the first invention is represented by, for example, the following formula (I-2):

(Q ₁ and Q ₂ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of Q ₁ and Q ₂ is a group other than a hydrogen atom and a halogen atom,
D is a substituent having 2 to 20 carbon atoms added to the benzene ring by a diene-type alkene,
Y is each independently selected from chalcogens, and A _{1 to} A ₈ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _8. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

Here, in the compound of formula (I-2), for example, Q ₁ and Q ₂ are each independently selected from the group consisting of an alkyl group and the like.

  This compound of formula (I-2) may in particular be a compound of the following formula (I-2-1):

(R _{1 to} R ₃ are each independently an alkyl group having 1 to 10 carbon atoms, and R _r is as described above).

In the compounds of formula (I), in particular of formula (I-1) or (I-2), A ₁ , A ₄ , A ₅ and A ₈ , in particular A _{1 to} A ₈ , may be hydrogen atoms. In the compound of formula (I), particularly of formula (I-1) or (I-2), Y may be a sulfur atom.

(First Invention-Condensed Polycyclic Aromatic Compound-Containing Solution)
The condensed polycyclic aromatic compound-containing solution of the first aspect of the present invention contains an organic solvent and the condensed polycyclic aromatic compound of the first aspect of the present invention that is at least partially dissolved in the organic solvent.

  This condensed polycyclic aromatic compound-containing solution can contain the condensed polycyclic aromatic compound of the first invention at an arbitrary concentration. For example, the condensed polycyclic aromatic compound of the first invention can contain 0 0.01 to 10% by mass, 0.05 to 5% by mass, and 0.1 to 3% by mass.

  Examples of the organic solvent that can be used here include any organic solvent that can dissolve and dissolve the condensed polycyclic aromatic compound of the first invention. Specifically, examples of the organic solvent include aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, and ethyl acetate; diethyl ether, tetrahydrofuran, diisopropyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, and the like. Ether solvents; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene (ie 1,3,5-trimethylbenzene); aliphatic hydrocarbons such as hexane and heptane; and dichloromethane, chloroform, dichloroethane, etc. Halogen-containing solvents can be considered.

(First Invention-Method for Producing Organic Semiconductor Film)
The method of the present invention for producing an organic semiconductor film includes a step of applying the condensed polycyclic aromatic compound-containing solution of the first invention to a substrate, and an organic solvent from the solution applied to the substrate. Removing.

  Application of the solution to the substrate can be performed in any manner, for example, by a casting method, a spin coating method, a printing method, or the like. Moreover, application | coating to the base material of a solution can also be performed only by dripping a solution on a base material.

  The removal of the organic solvent from the solution may be performed simultaneously with the coating step.

  Removal of the organic solvent from the solution can also be facilitated by heating. In this case, any temperature that does not substantially decompose the condensed polycyclic aromatic compound of the first invention, for example, 80 ° C. or higher, 100 ° C. or higher, 120 ° C. or higher, or 140 ° C. or higher, and 200 ° C. or lower, Heating can be performed at a temperature of 220 ° C or lower, 240 ° C or lower, and 260 ° C or lower. Such heating includes, for example, bringing the substrate coated with the solution into direct contact with a heated object such as a heated electric heater, introducing it into a heated region such as a heated furnace, infrared It can be achieved by irradiation with electromagnetic waves such as microwaves.

  In addition, in the compound of the first present invention intended to constitute an organic semiconductor film by desorbing an addition compound, for example, the compound of the formula (I-2), for example, in combination with removing the organic solvent. , D can be removed by elimination. This elimination reaction can be accelerated by heating.

(First Invention-Method for Manufacturing Organic Semiconductor Device)
The first inventive method for producing an organic semiconductor device includes the step of producing an organic semiconductor film by the first inventive method for producing an organic semiconductor film.

  The method may optionally further comprise forming an electrode layer and / or a dielectric layer above or below the organic semiconductor film.

(First Invention-Organic Semiconductor Device)
The organic semiconductor device of the first invention has an organic semiconductor film containing the condensed polycyclic aromatic compound of the first invention.

  Here, the fact that the organic semiconductor film contains the compound of the first invention means that the organic semiconductor film contains the compound of the first invention in at least a detectable amount.

  Thus, for example, in the first compound of the present invention which is intended to constitute the organic semiconductor film as it is, such as the compound of formula (I-1), this compound constitutes a substantial part of the organic semiconductor. That is, the organic semiconductor film is substantially composed of the first compound of the present invention.

  In addition, in the first compound of the present invention that is intended to form an organic semiconductor film by desorbing an addition compound, for example, a compound of the formula (I-2), In some cases, it is contained as a minor component of an organic semiconductor. In this case, the molar ratio of the compound as added to the addition compound may be greater than 1 ppm, greater than 10 ppm, greater than 100 ppm, greater than 1,000 ppm, or greater than 10,000 ppm (1%). Moreover, the ratio of the compound with this addition compound added may be 10 mol% or less, 5 mol% or less, 3 mol% or less, 1 mol% or less, 0.1 mol% or less, or 0.01 mol% or less.

  In particular, the organic semiconductor device of the present invention is a thin film transistor having a source electrode, a drain electrode, a gate electrode, a gate insulating film, and an organic semiconductor film, wherein the source electrode, the drain electrode, and the gate electrode are insulated by the gate insulating film, The thin film transistor controls the current flowing through the organic semiconductor from the source electrode to the drain electrode by a voltage applied to the gate electrode. In particular, the organic semiconductor device of the present invention is a solar cell having an organic semiconductor film as an active layer. In the context of the present invention, “organic semiconductor device” means a device having an organic semiconductor film, and other layers such as an electrode layer and a dielectric layer are made of an inorganic material or an organic material. It may be made.

(Second invention)
(Second Invention-Condensed Polycyclic Aromatic Compound)
The condensed polycyclic aromatic compound of the second invention is represented by the following formula (II):

(X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of X ₁ and X ₂ is a halogen atom,
B is a fused ring having at least one benzene ring moiety;
Y is each independently selected from chalcogen, and A _{1 to} A ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _4. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

  The condensed polycyclic aromatic compound of the second present invention is represented, for example, by the following formula (II-1):

(X _{1 to} X ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of X _{1 to} X ₄ is a halogen atom,
Y is each independently selected from chalcogens, and A _{1 to} A ₈ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _8. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

Here, in the compound of the formula (II-1), for example, X ₂ and X ₃ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group and the like, and among X ₂ and X ₃ At least one of them is a halogen atom, and X ₁ and X ₄ are hydrogen atoms.

  This compound of formula (II-1) may in particular be a compound of the following formula (II-1-1):

  This compound of formula (II-1) may in particular be a compound of the following formula (II-1-2):

  The condensed polycyclic aromatic compound of the second invention is represented by, for example, the following formula (II-2):

(X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of X ₁ and X ₂ is a halogen atom,
D is a substituent having 2 to 20 carbon atoms added to the benzene ring by a diene-type alkene,
Y is each independently selected from chalcogens, and A _{1 to} A ₈ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _8. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

Here, in the compound of the formula (II-2), for example, both X ₁ and X ₂ are halogen atoms.

  This compound of formula (II-2-1) may in particular be a compound of formula (I-2-1)

(R _r is as described above).

In the compounds of formula (I), in particular of formula (I-1) or (I-2), A ₁ , A ₄ , A ₅ and A ₈ , in particular A _{1 to} A ₈ , may be hydrogen atoms. In the compound of formula (I), particularly of formula (I-1) or (I-2), Y may be a sulfur atom.

(Second Invention-Method for Synthesizing the Condensed Polycyclic Aromatic Compound of the Second Invention)
The method for synthesizing the condensed polycyclic aromatic compound of the second invention includes the following steps:
(A) Providing a composition containing an organic solvent and a condensed polycyclic aromatic compound represented by the following formula (III):

(E ₁ and E ₂ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of E ₁ and E ₂ is a hydrogen atom,
B is a fused ring having at least one benzene ring moiety;
Y is each independently selected from chalcogen, and A _{1 to} A ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _4. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms),
(B) adding a halogen to the composition;

  Examples of the organic solvent that can be used here include any organic solvent capable of dissolving and / or dispersing the condensed polycyclic aromatic compound represented by the following formula (III). Specifically, examples of the organic solvent include aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, and ethyl acetate; diethyl ether, tetrahydrofuran, diisopropyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, and the like. Ether solvents; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene (ie 1,3,5-trimethylbenzene); aliphatic hydrocarbons such as hexane and heptane; and dichloromethane, chloroform, dichloroethane, etc. Halogen-containing solvents can be considered.

  The addition of the halogen to the composition containing the condensed polycyclic aromatic compound represented by the formula (III) can be performed by any method, for example, fluorine or chlorine can be added by bubbling, bromine, Iodine and astatine can be added as liquids or solids. Moreover, in order to accelerate | stimulate reaction with the compound and halogen which are represented by Formula (III), you may heat.

  The compound of the above formula (III) is represented by, for example, the following formula (III-1):

(E _{1 to} E ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of E _{1 to} E ₄ is a hydrogen atom,
Y is each independently selected from chalcogens, and A _{1 to} A ₈ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _8. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

Here, in the compound of formula (III-1), for example, E _{1 to} E ₄ are all hydrogen atoms.

  The compound of the above formula (III) is represented by the following formula (III-2), for example:

(E ₁ and E ₂ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, etc., and at least one of E ₁ and E ₂ is a hydrogen atom,
D is a substituent having 2 to 20 carbon atoms added to the benzene ring by a diene-type alkene,
Y is each independently selected from chalcogens, and A _{1 to} A ₈ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and the like, and are adjacent to each other among A _{1 to} A _8. Two may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

Here, in the compound of the formula (III-2), for example, E ₁ and E ₂ are both hydrogen.

  This compound of formula (III-2) may in particular be a compound represented by the following formula (III-2-1):

(R _r is as described above)

(Second Invention-Method of Using Compound of Second Invention (Synthesis Method of Condensed Polycyclic Aromatic Compound of First Invention))
The method of using the second present invention, that is, the method of synthesizing the condensed polycyclic aromatic compound of the first present invention from the second present invention includes the following steps:
(A) providing a composition containing an organic solvent and the second condensed polycyclic aromatic compound of the present invention;
(B) A step of substituting at least one halogen atom of X _{1 to} X ₄ with a substituent selected from the group consisting of an alkyl group and the like.

  As an organic solvent which can be used here, the arbitrary organic solvent which can melt | dissolve and / or disperse | distribute the compound of 2nd this invention, ie, the compound of Formula (II), can be mentioned. Specifically, examples of the organic solvent include aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, and ethyl acetate; diethyl ether, tetrahydrofuran, diisopropyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, and the like. Ether solvents; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene (ie 1,3,5-trimethylbenzene); aliphatic hydrocarbons such as hexane and heptane; and dichloromethane, chloroform, dichloroethane, etc. Halogen-containing solvents can be considered.

The reaction of substituting at least one halogen atom among X _{1 to} X ₄ of the compound represented by the formula (II) with a substituent selected from the group consisting of an alkyl group and the like can be carried out by using various aromatic halides. Coupling method, Mizorogi / Heck reaction, Negishi coupling, Ueda / Kosugi / Still coupling, Shantou coupling, Suzuki / Miyaura coupling, Buchwald / Heart wig reaction, Kumada / Tamao / Colleu coupling Can do. Heating may be performed to promote this coupling reaction.

The outline of each coupling reaction is as follows (Ar is an aromatic moiety, X is a halogen, R is hydrogen, an alkyl group, etc.):
(1) Mizorogi-Heck reaction Ar-X + H ₂ C = CHR (+ Pd catalyst) → Ar-HC = CHR
(2) Negishi coupling Ar-X + R-Zn-X (+ Pd catalyst) → Ar-R
(3) Ueda / Kosugi / Still coupling Ar-X + R-Sn-R ' ₃ (+ Pd catalyst) → Ar-R
(4) Sonogashira coupling Ar-X + R-C≡C-H (+ Pd catalyst) + base → Ar-C≡C-R
(5) Suzuki-Miyaura coupling Ar-X + R-B (OH) ₂ (+ Pd catalyst) + base → Ar-R
(6) Buchwald-Hartwig reaction Ar-X + R-NH ₂ (+ Pd catalyst) + base → Ar-NHR
(7) Kumada, Tamao, Collie coupling Ar-X + R-Mg-X (+ Ni catalyst) → Ar-R

  In the following examples, the structure of the target compound is determined by 1H nuclear magnetic resonance spectrum (1H-NMR spectrum), mass spectrometry spectrum (MS), single crystal structure analysis, and gel permeation chromatography (GPC) as necessary. Were determined.

The equipment used is as follows.
¹ H-NMR: JEOL ECA-500 (500 MHz)
MS: Bruker Autoflex III (MALDI)
Single crystal structure analysis: Rigaku RAXIS RAPIDS
GPC: Nippon Analytical Industrial Co., Ltd. LC-9101 (Column: JAIGEL-2H, JAIGEL-1H)

<Example 1>
Dinaphthothienothiophene (DNTT (Dinaphthothenothiophene)) (the following structural formula, MW = 340.46) is obtained by the method shown in Patent Document 2 (Japanese Patent Laid-Open No. 2008-290963 (Nippon Kayaku Co., Ltd., Hiroshima University)). Synthesized.

To 100 mL of mesitylene (ie, 1,3,5 trimethylbenzene) containing 1000 mg (2.93 mmol) of the above DNTT, 2341 mg (14.65 mmol) of bromine (Br ₂ , MW = 159.8) was added, and the reaction temperature was 40 ° C. And then allowed to cool to obtain bromine disubstituted dinaphthothienothiophene (Br2 substituted DNTT) (the following structural formula, Mw = 498.25, 1431 mg, 2.87 mmol, yield 98.1%). It was. The reaction product was purified with chloroform.

  The position of bromine substitution in Br2-substituted DNTT was determined by the position of triisopropylsilyl (TIPS) group by single crystal structure analysis of TIPS2-substituted DNTT in Example 2.

¹ H-NMR and MS results for the obtained Br2-substituted DNTT are shown below.

¹ H-NMR (500 MHz, CDCl 3, 50 ° C.): δ 8.47 (d, J = 8.3 Hz, 2H), 8.44 (s, 2H), 7.97 (d, J = 8.3 Hz, 2H) ), 7.66 (t, J = 8.3 Hz, 2H), 7.59 (t, J = 8.3 Hz, 2H)

  MS (m / z): 497.513 (positive ion observation) (ExactMass: 495.86)

<Example 1A>
100.7 mg (0.296 mmol) of DNTT synthesized as in Example 1A and 17.7 mg (0.133 mmol) of aluminum chloride were added to the flask and purged with nitrogen three times. Next, 5.0 ml of chloroform was added and cooled to 0 ° C. 78.7 mg (0.589 mmol) of N-chlorosuccinimide was added and stirred for 1.5 hours.

  After confirming the disappearance of the raw material N-chlorosuccinimide by mass spectrometry spectrum (MS), 5.0 ml of water was added to complete the reaction. The reaction product was filtered to obtain chlorine 2-substituted dinaphthothienothiophene (Cl2-substituted DNTT) (the following structural formula, Mw = 409.35, 116.0 mg, 0.28 mmol, yield 95.8%). The reaction product was purified with chloroform.

  The MS results for the resulting Cl2-substituted DNTT are shown below.

  MS (m / z): 407.822 (positive ion observation) (ExactMass: 407.96)

<Example 2>
A triisopropylsilyl (TIPS) group was introduced into the Br2 substituted DNTT synthesized in Example 1 by the Sonogashira coupling method.

Specifically, 191.3 mg of Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90) and CuI (Mw = 190.25) with respect to 500 mg (1.0 mmol) of Br 2 -substituted DNTT (Mw = 498.25). 45) 134.1 mg, diisopropylamine (Mw = 101.20) 0.706 mL, CsCO ₃ (Mw = 325.82) 791.6 mg, triisopropylsilylacetylene (Mw = 182.38) 1.698 mL were added, and the pressure was reduced. After degassing and nitrogen replacement 3 times, 35 mL of N, N-dimethylformamide (N, N-DMF) was introduced, vacuum degassing and nitrogen replacement were again performed 3 times at 120 ° C. for 20 hours. The reaction was carried out with stirring.

  As a result, 479.1 mg (68.3 mmol, yield 68.0%) of triisopropylsilylacetylene 2-substituted dinaphthothienothiophene (TIPS2-substituted DNTT, the following structural formula) (Mw = 701.19) was obtained. The solubility of the obtained TIPS2-substituted DNTT in chloroform was 0.2 wt%. DNTT used as a raw material did not substantially dissolve in chloroform.

¹ H-NMR and MS results for the obtained TIPS2-substituted DNTT are shown below.

¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.61 (d, J = 8.0 Hz, 2H), 8.41 (s, 2H), 7.97 (d, J = 8.0 Hz, 2H), 7.63 (dd, J = 8.0 Hz, 8.0 Hz 2H), 7.57 (dd, J = 8.0 Hz, 8.0 Hz, 2H), 1.40 to 1.47 (m, 6H), 1 .34 (d, J = 6.9 Hz, 36H)

  MS (m / z): 700.3 (ExactMass: 700.30)

  The single crystal structure analysis results for the obtained TIPS2-substituted DNTT are shown below.

a = 8.2044 (5) Å
b = 8.4591 (6) Å
c = 14.488 (1) Å
α = 88.475 (4) °
β = 89.336 (3) °
γ = 89.555 (4) °
V = 1005.1 (1) ^{３ 3}

  In addition, a molecular structure ORTEP (Oak Ridge Thermal Ellipsoid Plot) diagram and a crystal packing (stereo) diagram based on the single crystal structure analysis of this TIPS2-substituted DNTT body are shown in FIGS. 1 and 2, respectively.

<Example 2A>
Triisopropylsilyl acetylene disubstituted DNTT (TIPS2 substituted DNTT) synthesized according to Example 2 was reduced with hydrogen to synthesize triisopropylsilylethane disubstituted DNTT.

  Specifically, 304.6 mg (0.43 mmol) of triisopropylsilylacetylene disubstituted DNTT (Mw = 701.18), 60 ml of toluene, and 79.2 mg of 10% Pd / C were added to a 200 ml flask to perform hydrogen substitution. I went twice. The reaction was allowed to stir at 60 ° C. for 15 hours under a hydrogen atmosphere.

  As a result, triisopropylsilylethane disubstituted DNTT (the following structural formula, Mw = 709.37, 296.1 mg, 0.42 mmol, yield 96.1%) was obtained. The solubility of the obtained triisopropylsilylethane disubstituted DNTT in chloroform was 0.51 wt%. DNTT used as a raw material did not substantially dissolve in chloroform.

¹ H-NMR and MS results for the resulting triisopropylsilylethane disubstituted DNTT are shown below.

¹ H-NMR (500 MHz, CDCl 3, 50 ° C.): δ 8.33 (s, 2H), 7.26 (d, J = 8.6 Hz, 2H), 7.97 (d, J = 8.6 Hz, 2H) ), 7.57 (dd, J = 8.6 Hz, 8.6 Hz, 2H), 7.53 (dd, J = 8.3 Hz, 8.3 Hz, 2H), 3.76-3.72 (m, 8H), 1.39-1.32 (m, 6H), 1.30-1.19 (m, 36H)

  MS (m / z): 708.322 (positive ion observation) (ExactMass: 708.367)

<Example 3>
The TIPS2-substituted DNTT (Mw = 701.19) obtained in Example 2 was dissolved in chloroform at a concentration of 0.2 wt% to prepare a semiconductor element manufacturing solution.

Next, UV-ozone treatment for 20 minutes (eye UV-ozone cleaning apparatus OC-250615-D + A, iGraphics) on 300 nm n-doped silicon wafer with SiO ₂ oxide film (surface resistance 1 ⁻¹⁰ Ω · cm) Ltd.). Further, a 1,1,1,3,3,3-hexamethyldisilazane ((HMDS) 1,1,1,3,3,3-hexylmethyldisilazane) 10 mmol / toluene solution was prepared, The silicon substrate that had been subjected to UV ozone treatment was immersed for 24 hours to hydrophobize the silicon substrate. Thereafter, a source / drain gold electrode having a channel width of 50 μm and a channel length of 1.5 mm was produced by vacuum deposition (Sanyu Electronics, resistance heating deposition apparatus: SVC-700TM / 700-2).

  While heating the silicon substrate to 40 ° C., a solution for forming a semiconductor element was dropped on the channel portion to evaporate the solvent, thereby forming a thin layer made of TIPS2-substituted DNTT. The device thus fabricated was heat-treated at 70 ° C. for 1 hour under vacuum to remove the chloroform solvent by drying, thereby fabricating an organic semiconductor device.

When the organic semiconductor characteristics of the obtained organic semiconductor element were measured, a p-type semiconductor was shown. Further, this organic semiconductor element had a carrier mobility of 1 × 10 ⁻³ cm ² / Vs, an on / off ratio of 10 ⁵ , and a threshold voltage of −26V. FIG. 3 shows the transfer characteristics of FET characteristics for this organic semiconductor element. Here, in FIG. 3, when the drain voltage (V _D ) is −80 V, the drain current (I _D (A) or I _D ^1/2 (A ^1/2 )) (vertical axis) and the gate voltage (V _G (V)) (horizontal axis).

<Example 4>
In the same manner as in Example 1, dinaphthothienothiophene (DNTT (Dinaphthothienothiophene)) (MW = 340.46) was synthesized.

  To 500 mL of mesitylene (ie, 1,3,5 trimethylbenzene) containing 5000 mg (14.65 mmol) of the above DNTT, 12.68 g (73.25 mmol) of N-phenylmaleimide (MW = 173.17) is added, and the reaction temperature is increased. It was kept at 160 ° C. for 4 hours, then allowed to cool, preparatively purified, and dinaphthothienothiophene-N-phenylmaleimide 1 adduct (DNTT-PMI1 adduct, steric form) in which one N-phenylmaleimide was added to DNTT A mixture of an isomer and an Endo isomer and an Exo isomer) (the following structural formula, Mw = 513.63) and 376 mg (0.73 mmol, yield 4.9%) were obtained. In addition, the reaction product fractionated the stereoisomer by HPLC, and obtained 132 mg of Endo forms and 151 mg of Exo forms.

To 50 mL of mesitylene containing 151 mg (0.29 mmol) of DNTT-PMI1 adduct (Exo isomer), 235 mg (1.47 mmol) of bromine (Br ₂ , MW = 159.8) was added, and the reaction temperature was brought to 40 ° C. 1 time, and then allowed to cool to 186 mg of bromine 2-substituted dinaphthothienothiophene-N-phenylmaleimide 1-adduct (Br2-substituted DNTT-PMI1 adduct) (the following structural formula, Mw = 673.44). 276 mmol, yield 95.2%).

¹ H-NMR and MS results for the obtained Br2-substituted DNTT-1PMI adduct are shown below.

¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.39 (d, J = 7.7 Hz, 1H), 8.29 (d, J = 7.7 Hz, 1H), 7.67 (dd, J = 7 .7 Hz, 1H), 7.64 (dd, J = 7.7 Hz, 1H), 7.41-7.44 (m, 2H), 7.31-7.32 (m, 3H), 7.27 ˜7.29 (m, 2H), 6.52 to 6.54 (m, 2H), 5.25 (d, J = 3.2 Hz, 1H), 5.23 (d, J = 3.2 Hz, 1H), 3.59 (dd, J = 3.2 Hz, 8.3 Hz, 1H), 3.55 (dd, J = 3.2 Hz, 8.3 Hz, 1H)

  MS (m / z): 497.513 (ExactMass: 670.92)

  In MS, it is presumed that Br2-substituted DNTT (ExactMass: 497.86) in which N-phenylmaleimide was eliminated from the Br2-substituted DNTT-PMI1 adduct was estimated.

<Example 5>
The triisopropylsilyl (TIPS) group was introduced into the Br2 substituted DNTT-PMI1 adduct synthesized in Example 4 by the Sonogashira coupling method.

Specifically, Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90) 28.1 mg, CuI (Br2 substituted DNTT-PMI1 adduct (Mw = 673.44) 100 mg (0.148 mmol)) Mw = 190.45) 20.0 mg, diisopropylamine (Mw = 101.20) 0.11 mL, triisopropylsilylacetylene (Mw = 182.38) 0.1 mL were added, and vacuum degassing and nitrogen substitution were performed three times. After that, 7 mL of N, N-dimethylformamide (N, N-DMF) was introduced, vacuum degassing and nitrogen substitution were again performed three times, and the reaction was performed by stirring at 120 ° C. for 20 hours.

  Thereby, triisopropylsilylacetylene 2 substituted dinaphthothienothiophene-phenylmaleimide 1 adduct (exo form) (TIPS2 substituted DNTT-PMI1 adduct (exo form)) (the following structural formula, Mw = 876.37) 74.9 mg (85.4 mmol, yield 57.7%) was obtained.

¹ H-NMR and MS results for the obtained TIPS2-substituted DNTT-PMI1 adduct (exo form) are shown below.

¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.52 to 8.54 (m, 1H), 8.43 to 8.45 (m, 1H), 7.60 to 7.64 (m, 2H), 7.43 to 7.46 (m, 2H), 7.31 to 7.33 (m, 3H), 7.25 to 7.29 (m, 2H), 6.52 to 6.54 (m, 2H) ), 5.29 (d, J = 3.4 Hz, 1H), 5.21 (d, J = 3.4 Hz, 1H), 3.62 (dd, J = 3.4 Hz, 8.3 Hz, 1H) 3.56 (dd, J = 3.4 Hz, 8.3 Hz, 1H), 1.36 to 1.43 (m, 6H), 1.31 (d, J = 2.9 Hz, 12H), 1. 30 (d, J = 4.0Hz, 24H)

  MS (m / z): 873.078 (Exact Mass: 875.37)

<Example 6>
The Br2-substituted DNTT synthesized in Example 1 was reacted with 1-decyne by the Sonogashira coupling method to synthesize 1-decine 2-substituted DNTT.

Specifically, Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90) 761.1 mg (1.08 mmol), CuI with respect to Br2 substituted DNTT (Mw = 498.25) 1000 mg (2.01 mmol) (Mw = 190.45) 577 mg (3.03 mmol) and Cs ₂ CO ₃ (Mw = 325.8) 3.20 g (9.82 mmol) were added, and vacuum degassing and nitrogen substitution were performed 5 times.

Thereafter, 70 ml of dimethylformamide, 1.41 ml (10.0 mmol) of diisopropylamine (Mw = 101.2, d = 0.72 g / cm ³ ), 1-decyne (Mw = 138.25, d = 0.77 g / cm) ³ ) 2.78 ml (15.4 mmol) was added, vacuum degassing and nitrogen substitution were again performed 5 times, and the reaction was performed by stirring at 120 ° C. for 15.5 hours.

  Thereby, 1-decyne disubstituted DNTT (the following structural formula, Mw = 612.93, 20.5 mg, 0.033 mmol, yield 1.6%) was obtained. The solubility of the obtained 1-decyne 2-substituted DNTT in chloroform was 2.3 wt%. DNTT used as a raw material did not substantially dissolve in chloroform.

¹ H-NMR and MS results for the resulting ¹ -decyne disubstituted DNTT are shown below.

¹ H-NMR (500 MHz, CDCl 3, 50 ° C.): δ 8.45 (d, J = 8.3 Hz, 2H), 8.25 (s, 2H), 7.86 (d, J = 8.3 Hz, 2H) ), 7.54 (dd, J = 8.3 Hz, 6.9 Hz, 2H), 7.48 (dd, J = 8.3 Hz, 6.9 Hz, 2H), 2.81 (t, J = 7. 2 Hz, 4H), 1.90 (tt, J = 7.2 Hz, 7.2 Hz, 4H), 1.65 (tt, J = 7.2 Hz, 7.2 Hz, 4H), 1.31-1.48 (M, 16H), 0.89 (t, J = 7.2 Hz, 6H)

  MS (m / z): 612.284 (positive ion observation) (ExactMass: 612.288)

<Example 7>
The Br2-substituted DNTT synthesized in Example 1 was reacted with 1-tetradecine by the Sonogashira coupling method to synthesize 1-tetradecine 2-substituted DNTT.

Specifically, for 1000 mg (2.01 mmol) of Br2-substituted DNTT (Mw = 498.25), 830.0 mg (1.17 mmol) of Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90), CuI (Mw = 190.45) 590.0 mg (3.12 mmol) and Cs ₂ CO ₃ (Mw = 325.8) 1.62 g (4.98 mmol) were added, and vacuum degassing and nitrogen substitution were performed 5 times.

Thereafter, 70 ml of dimethylformamide, 1.41 ml (10.0 mmol) of diisopropylamine (Mw = 101.2, d = 0.72 g / cm ³ ), 1-tetradecine (Mw = 194.36, d = 0.79 g / cm) ³ ) 4.19 ml (17.0 mmol) was added, vacuum degassing and nitrogen replacement were again performed 5 times, and the reaction was performed by stirring at 120 ° C. for 12 hours.

  As a result, 1-tetradecine disubstituted DNTT (the following structural formula, Mw = 612.93, 156.04 mg, 0.207 mmol, yield 10.3%) was obtained. The solubility of the obtained 1-tetradecine disubstituted DNTT in chloroform was 6.5 wt%. DNTT used as a raw material did not substantially dissolve in chloroform.

¹ H-NMR and MS results for the obtained 1-tetradecine disubstituted DNTT are shown below.

¹ H-NMR (500 MHz, CDCl 3, 50 ° C.): δ 8.38 (d, J = 8.3 Hz, 2H), 8.14 (s, 2H), 7.78 (d, J = 8.3 Hz, 2H) ), 7.48 (dd, J = 8.3 Hz, 6.6 Hz, 2H), 7.42 (dd, J = 8.3 Hz, 6.6 Hz, 2H), 2.76 (t, J = 7. 2 Hz, 4H), 1.86 (tt, J = 7.2 Hz, 7.2 Hz, 4H), 1.62 (tt, J = 7.2 Hz, 7.2 Hz, 4H), 1.24-1.46 (M, 32H), 0.86 (t, J = 7.2 Hz, 6H)

  MS (m / z): 724.411 (positive ion observation) (ExactMass: 724.414)

<Example 7A>
1-tetradecin 2-substituted DNTT was synthesized by reacting Br2-substituted DNTT synthesized in Example 1 with 1-tetradecin using Negishi coupling instead of the Sonogashira coupling method used in Example 7. .

Specifically, 0.21 ml (0.85 mmol) of 1-tetradecine (Mw = 194.36, d = 0.79 g / cm ³ ) and 3.5 ml of toluene were added to a 10 ml flask, and vacuum degassing and nitrogen were added. The substitution was performed 3 times. After cooling to 0 ° C. and adding 0.53 ml (0.859 mmol) of a hexane solution of n-BuLi, the temperature was raised to room temperature.

ZnCl ₂ (TMEDA) (Mw = 252.50) 215.3 mg (0.853 mmol), Br 2 -substituted DNTT (Mw = 498.25) 50 mg (0.10 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701) .90) 35.2 mg (0.05 mmol) was added, and vacuum degassing and nitrogen substitution were performed three times. The reaction was allowed to stir at 100 ° C. for 12 hours.

  As a result, 1-tetradecyne disubstituted DNTT (the above structural formula, Mw = 612.93, 8.9 mg, 0.012 mmol, yield 12.2%) was obtained.

<Example 8>
The Br2-substituted DNTT synthesized in Example 1 was reacted with 1-octadecine by Sonogashira coupling method to synthesize 1-octadecine 2-substituted DNTT.

Specifically, Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90) 820.0 mg (1.17 mmol), CuI with respect to Br2 substituted DNTT (Mw = 498.25) 1010 mg (2.02 mmol) (Mw = 190.45) 590.0 mg (3.12 mmol) and Cs ₂ CO ₃ (Mw = 325.8) 1.58 g (4.85 mmol) were added, and vacuum degassing and nitrogen substitution were performed 5 times. It was.

Thereafter, 70 ml of dimethylformamide, 1.41 ml (10.0 mmol) of diisopropylamine (Mw = 101.2, d = 0.72 g / cm ³ ), 1-octadecine (Mw = 250.46, d = 0.79 g / cm) ³ ) 5.34 ml (16.8 mmol) was added, vacuum degassing and nitrogen substitution were again performed 5 times, and the reaction was performed by stirring at 120 ° C. for 14 hours.

  Thereby, 1-octadecin 2-substituted DNTT (the following structural formula, Mw = 836.54, 54.2 mg, 0.064 mmol, yield 3.2%) was obtained.

<Example 8A>
1-octadecin 2-substituted DNTT was synthesized by reacting Br2-substituted DNTT synthesized in Example 1 with 1-octadecine using Negishi coupling instead of the Sonogashira coupling method used in Example 8. .

Specifically, 1-octadecin (Mw = 250.46, d = 0.80 g / cm ³ ) 0.26 ml (0.85 mmol) and toluene 3.5 ml were added to a 10 ml flask, Nitrogen replacement was performed three times. After cooling to 0 ° C. and adding 0.53 ml (0.859 mmol) of a hexane solution of n-BuLi, the temperature was raised to room temperature.

ZnCl ₂ (TMEDA) (Mw = 252.50) 216.1 mg (0.856 mmol), Br 2 -substituted DNTT (Mw = 498.25) 49.7 mg (0.10 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90) 35.6 mg (0.05 mmol) was added, and vacuum degassing and nitrogen substitution were performed three times. The reaction was allowed to stir at 100 ° C. for 12 hours.

  As a result, 1-octadecin disubstituted DNTT (the above structural formula, Mw = 836.54, 3.8 mg, 0.004 mmol, yield 4.5%) was obtained. The solubility of the obtained 1-tetradecine disubstituted DNTT in chloroform was 1.67 wt%. DNTT used as a raw material did not substantially dissolve in chloroform.

¹ H-NMR and MS results for the obtained 1-octadecine disubstituted DNTT are shown below.

¹ H-NMR (500 MHz, CDCl 3, 50 ° C.): δ 8.48 (d, J = 8.3 Hz, 2H), 8.30 (s, 2H), 7.89 (d, J = 8.3 Hz, 2H) ), 7.56 (dd, J = 8.3 Hz, 6.6 Hz, 2H), 7.51 (dd, J = 8.3 Hz, 6.6 Hz, 2H), 2.83 (t, J = 7. 2 Hz, 4H), 1.91 (tt, J = 7.2 Hz, 7.2 Hz, 2H), 1.66 (tt, J = 7.2 Hz, 7.2 Hz, 2H), 1.24-1.46 (M, 48H), 0.87 (t, J = 7.2 Hz, 6H)

  MS (m / z): 836.539 (positive ion observation) (ExactMass: 836.5537)

<Example 9>
The Br2 substituted DNTT synthesized in Example 1 was reacted with trimethylsilylacetylene (TMS) by the Negishi coupling method to synthesize TMS2 substituted DNTT.

To a 200 ml flask, 1.68 g (17.10 mmol) of trimethylsilylacetylene (Mw = 98.22, d = 0.70 g / cm ³ ) and 70 ml of toluene were added, and vacuum degassing and nitrogen substitution were performed three times. After cooling to 0 ° C. and adding 10.3 ml (16.68 mmol) of hexane solution of n-BuLi, the temperature was raised to room temperature.

ZnCl ₂ (TMEDA) (Mw = 252.50) 4.31 g (17.06 mmol), Br 2 -substituted DNTT (Mw = 498.25) 1.0 g (2.00 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90) 702.5 mg (1.00 mmol) was added, and vacuum degassing and nitrogen substitution were performed three times. The reaction was allowed to stir at 100 ° C. for 12 hours.

  As a result, trimethylsilylacetylene 2-substituted DNTT (TMS2-substituted DNTT) (the following structural formula, Mw = 532.87, 536.30 mg, 1.00 mmol, yield 50.1%) was obtained. The solubility of the obtained trimethylsilylacetylene disubstituted DNTT in chloroform was 0.05 wt%. DNTT used as a raw material did not substantially dissolve in chloroform.

¹ H-NMR and MS results for the obtained TMS2-substituted DNTT are shown below.

¹ H-NMR (500 MHz, CDCl 3, 50 ° C.): δ 8.53 (d, J = 8.3 Hz, 2H), 8.43 (s, 2H), 7.96 (d, J = 8.3 Hz, 2H) ), 7.63 (dd, J = 8.3 Hz, 8.3 Hz, 2H), 7.57 (dd, J = 8.3 Hz, 8.3 Hz, 2H), 0.52 (s, 18H)

  MS (m / z): 532.008 (positive ion observation) (ExactMass: 532.111)

<Example 10>
Triethylsilylacetylene (TES) was reacted with the Br2 substituted DNTT synthesized in Example 1 by the Negishi coupling method to synthesize TES2 substituted DNTT.

To a 200 ml flask, 2.25 g (16.03 mmol) of triethylsilylacetylene (Mw = 140.30, d = 0.78 g / cm ³ ) and 70 ml of toluene were added, and vacuum degassing and nitrogen substitution were performed three times. After cooling to 0 ° C. and adding 10.3 ml (16.68 mmol) of a hexane solution of n-BuLi, the temperature was raised to room temperature.

ZnCl ₂ (TMEDA) (Mw = 252.50) 4.31 g (17.06 mmol), Br 2 -substituted DNTT (Mw = 498.25) 1.0 g (2.00 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90) 704.8 mg (1.00 mmol) was added, and vacuum degassing and nitrogen substitution were performed three times. The reaction was allowed to stir at 100 ° C. for 12 hours.

  As a result, triethylsilylacetylene 2-substituted DNTT (TES2-substituted DNTT) (the following structural formula, Mw = 617.03, 321.40 mg, 0.52 mmol, yield 26.0%) was obtained. The solubility of the obtained triethylsilylacetylene disubstituted DNTT in chloroform was 0.10 wt%. DNTT used as a raw material did not substantially dissolve in chloroform.

¹ H-NMR and MS results for the obtained TES2-substituted DNTT are shown below.

¹ H-NMR (500 MHz, CDCl 3, 50 ° C.): δ 8.56 (d, J = 8.3 Hz, 2H), 8.42 (s, 2H), 7.96 (d, J = 8.3 Hz, 2H) ), 7.63 (dd, J = 8.3 Hz, 8.3 Hz, 2H), 7.57 (dd, J = 8.3 Hz, 8.3 Hz, 2H), 1.25 (t, J = 8. 0Hz, 18H), 0.94-0.98 (m, 12H)

  MS (m / z): 616.057 (positive ion observation) (ExactMass: 616.211)

<Example 11>
The Br2 substituted DNTT synthesized in Example 1 was reacted with thiophene by a Still coupling method to synthesize thiophene 2-substituted DNTT.

In a 100 ml flask, 500 mg (1.00 mmol) of Br2 substituted DNTT (Mw = 498.25), 351.6 mg (0.501 mmol) of PdCl ₂ (PPh ₃ ) ₂ (Mw = 701.90), tributyl (2-thienyl) ) Tin (Mw = 373.18) 3.23 g (8.64 mmol) and dry toluene 35 ml were added. Nitrogen replacement was performed 3 times, and the mixture was stirred at 100 ° C. overnight.

  After confirming that the peak of Br2-substituted DNTT disappeared from MALDI, the mixture was cooled to room temperature. Chloroform and water were added and the precipitate was filtered. The solvent was distilled off from the filtrate, and the target peak was confirmed by MS only from the filtrate. 10 ml of ether was added to the black oily substance and washed twice. The solid was filtered to give a dark green solid. The dark green solid was then purified on a column to give the product as a yellow solid.

  Thiophene 2-substituted DNTT (the following structural formula, Mw = 504.71, 158.80 mg, 0.31 mmol, yield 31.4%) was obtained. The solubility of the obtained triethylsilylacetylene disubstituted DNTT in chloroform was 0.13 wt%. DNTT used as a raw material did not substantially dissolve in chloroform.

¹ H-NMR and MS results for the resulting thiophene 2-substituted DNTT are shown below.

  1H-NMR (500 MHz, CDCl3, 50 ° C.): δ 8.31 (s, 2H), 7.92 (d, J = 6.5, 2H), 7.87 (d, J = 7.0 Hz, 2H) 7.76 (dd, J = 1.0 Hz, 1.0 Hz, 2H), 7.52-7.49 (m, 2H), 7.47-7.46 (m, 2H), 7.43- 7.41 (m, 2H), 7.28-7.26 (m, 2H)

  MS (m / z): 503.838 (positive ion observation) (ExactMass: 504.013)

<Example 12>
The Br2-substituted DNTT synthesized in Example 1 was reacted with 1-bromodecane by the Negishi coupling method to synthesize decane 2-substituted DNTT.

Specifically, 548.2 mg (22.5 mmol) of magnesium was added to a 10 ml flask, and vacuum degassing and nitrogen substitution were performed three times. 2.5 ml of THF and 4.39 ml (21.3 mmol) of 1-bromodecane (Mw = 221.18, d = 1.07 g / cm ³ ) were added and refluxed at 60 ° C. for 1 hour with stirring.

After cooling to room temperature, 100 ml of toluene and 5.32 g (21.31 mmol) of ZnCl ₂ (TMEDA) (Mw = 252.50) were added and stirred for 10 minutes. Br2 substituted DNTT (Mw = 498.25) 1.25 g (2.50 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (Mw = 701.90) 881.5 mg (1.25 mmol), toluene 77.5 ml were added. Then, vacuum degassing and nitrogen substitution were performed three times. The reaction was allowed to stir at 100 ° C. for 12 hours.

  Thereby, decane 2-substituted DNTT (the following structural formula, Mw = 620.99, 44.3 mg, 0.089 mmol, yield 2.8%) was obtained. The solubility of the obtained decane 2-substituted DNTT in chloroform was 0.05 wt%. DNTT used as a raw material did not substantially dissolve in chloroform.

¹ H-NMR and MS results for the obtained decane 2-substituted DNTT are shown below.

¹ H-NMR (500 MHz, CDCl 3, 50 ° C.): δ 8.33 (s, 2H), 8.26 (d, J = 8.30 Hz, 2H), 7.95 (d, J = 8.3 Hz, 2H) ), 7.56 (dd, J = 8.3 Hz, 8.3 Hz, 2H), 7.53 (dd, J = 8.3 Hz, 8.3 Hz, 2H), 3.67-3.64 (m, 4H), 1.93-1.86 (m, 4H), 1.76-1.71 (m, 4H), 1.49-1.45 (m, 4H), 1.41-1.29 ( m, 20H), 0.88 (t, J = 6.8 Hz, 6H)

  MS (m / z): 620.083 (positive ion observation) (ExactMass: 620.288)

Claims (16)

Fused polycyclic aromatic compound represented by the following formula (II):

(X ₁ and X ₂ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a carbon atom. A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Selected from the group consisting of an imide group, a sulfide group having 1 to 20 carbon atoms, and an alkylsilylalkynyl group having 1 to 40 carbon atoms, and at least one of X ₁ and X ₂ is a halogen atom,
B is a fused ring having at least one benzene ring moiety;
Y is independently selected from chalcogen, and A _{1 to} A ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon C2-C20 alkynyl group, C4-C20 substituted or unsubstituted aromatic group, C2-C10 ketone group, C1-C20 amino group, C1-C1 Selected from the group consisting of 20 amide groups, imide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, and alkylsilylalkynyl groups having 1 to 40 carbon atoms, and A _{1 to} A ₄ Adjacent two of them may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms). The compound of Claim 1 represented by a following formula (II-1):

(X _{1 to} X ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a carbon atom. A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Selected from the group consisting of an imide group, a sulfide group having 1 to 20 carbon atoms, and an alkylsilylalkynyl group having 1 to 40 carbon atoms, and at least one of X _{1 to} X ₄ is a halogen atom,
Y is independently selected from chalcogen, and A _{1 to} A ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon C2-C20 alkynyl group, C4-C20 substituted or unsubstituted aromatic group, C2-C10 ketone group, C1-C20 amino group, C1-C1 Selected from the group consisting of 20 amide groups, imide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, and alkylsilylalkynyl groups having 1 to 40 carbon atoms, and A _{1 to} A _8. Adjacent two of them may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms). X ₂ and X ₃ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or the number of carbon atoms A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Selected from the group consisting of an imide group, a sulfide group having 1 to 20 carbon atoms, and an alkylsilylalkynyl group having 1 to 40 carbon atoms, and at least one of X ₂ and X ₃ is a halogen atom, and X ₁ and X ₄ are hydrogen atoms,
The compound according to claim 2. The compound of Claim 2 represented by a following formula (II-1-1):

The compound of Claim 2 represented by a following formula (II-1-2):

The compound of Claim 1 represented by following formula (II-2):

(X ₁ and X ₂ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a carbon atom. A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Selected from the group consisting of an imide group, a sulfide group having 1 to 20 carbon atoms, and an alkylsilylalkynyl group having 1 to 40 carbon atoms, and at least one of X ₁ and X ₂ is a halogen atom,
D is a substituent having 2 to 20 carbon atoms added to the benzene ring by a diene-type alkene,
Y is independently selected from chalcogen, and A _{1 to} A ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon C2-C20 alkynyl group, C4-C20 substituted or unsubstituted aromatic group, C2-C10 ketone group, C1-C20 amino group, C1-C1 Selected from the group consisting of 20 amide groups, imide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, and alkylsilylalkynyl groups having 1 to 40 carbon atoms, and A _{1 to} A _8. Adjacent two of them may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms). The compound according to claim 6, wherein X ₁ and X ₂ are both halogen atoms. The compound according to claim 6, which is represented by the following formula (II-2-1):

(R _r is independently hydrogen, halogen, hydroxyl group, amide group, mercapto group, cyano group, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, or 2 to 10 carbon atoms. Alkynyl group, alkoxy group having 1 to 10 carbon atoms, substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, ester group having 1 to 10 carbon atoms, ether group having 1 to 10 carbon atoms, carbon From a ketone group having 1 to 10 atoms, an amino group having 1 to 10 carbon atoms, an amide group having 1 to 10 carbon atoms, an imide group having 1 to 10 carbon atoms, and a sulfide group having 1 to 10 carbon atoms Selected from the group). (A) Providing a composition containing an organic solvent and a condensed polycyclic aromatic compound represented by the following formula (III):

(E ₁ and E ₂ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a carbon atom. A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Selected from the group consisting of an imide group, a sulfide group having 1 to 20 carbon atoms, and an alkylsilylalkynyl group having 1 to 40 carbon atoms, and at least one of E ₁ and E ₂ is a hydrogen atom,
B is a fused ring having at least one benzene ring moiety;
Y is independently selected from chalcogen, and A _{1 to} A ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon C2-C20 alkynyl group, C4-C20 substituted or unsubstituted aromatic group, C2-C10 ketone group, C1-C20 amino group, C1-C1 Selected from the group consisting of 20 amide groups, imide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, and alkylsilylalkynyl groups having 1 to 40 carbon atoms, and A _{1 to} A ₄ Adjacent two of them may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms),
(B) adding a halogen to the composition;
The synthetic | combination method of the condensed polycyclic aromatic compound as described in any one of Claims 1-8 containing these. The method according to claim 9, wherein the compound of the formula (III) is represented by the following formula (III-1):

(E _{1 to} E ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a carbon atom. A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Selected from the group consisting of an imide group, a sulfide group having 1 to 20 carbon atoms, and an alkylsilylalkynyl group having 1 to 40 carbon atoms, and at least one of E _{1 to} E ₄ is a hydrogen atom,
Y is independently selected from chalcogen, and A _{1 to} A ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon C2-C20 alkynyl group, C4-C20 substituted or unsubstituted aromatic group, C2-C10 ketone group, C1-C20 amino group, C1-C1 Selected from the group consisting of 20 amide groups, imide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, and alkylsilylalkynyl groups having 1 to 40 carbon atoms, and A _{1 to} A _8. Adjacent two of them may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms). The method according to claim 10, wherein E _{1 to} E ₄ are all hydrogen atoms. The method according to claim 10, wherein the compound of the formula (III-1) is represented by the following formula (III-1-1):

The method according to claim 9, wherein the compound of the formula (III) is represented by the following formula (III-2):

(E ₁ and E ₂ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a carbon atom. A substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, a ketone group having 2 to 10 carbon atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Selected from the group consisting of an imide group, a sulfide group having 1 to 20 carbon atoms, and an alkylsilylalkynyl group having 1 to 40 carbon atoms, and at least one of E ₁ and E ₂ is a hydrogen atom,
D is a substituent having 2 to 20 carbon atoms added to the benzene ring by a diene-type alkene,
Y is independently selected from chalcogen, and A _{1 to} A ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon C2-C20 alkynyl group, C4-C20 substituted or unsubstituted aromatic group, C2-C10 ketone group, C1-C20 amino group, C1-C1 Selected from the group consisting of 20 amide groups, imide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, and alkylsilylalkynyl groups having 1 to 40 carbon atoms, and A _{1 to} A _8. Adjacent two of them may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms). E ₁ and _{E 3} are both hydrogen, A method according to claim 13. The method according to claim 13, wherein the compound of the formula (III-2) is represented by the following formula (III-2-1):

(R _r is independently hydrogen, halogen, hydroxyl group, amide group, mercapto group, cyano group, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, or 2 to 10 carbon atoms. Alkynyl group, alkoxy group having 1 to 10 carbon atoms, substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, ester group having 1 to 10 carbon atoms, ether group having 1 to 10 carbon atoms, carbon From a ketone group having 1 to 10 atoms, an amino group having 1 to 10 carbon atoms, an amide group having 1 to 10 carbon atoms, an imide group having 1 to 10 carbon atoms, and a sulfide group having 1 to 10 carbon atoms Selected from the group). (A) providing the composition containing the organic solvent and the compound as described in any one of Claims 1-8,
(B) at least one halogen atom of X _{1 to} X _{4 is} an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or the number of carbon atoms Substituting with a substituent selected from the group consisting of a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms and an alkylsilylalkynyl group having 1 to 40 carbon atoms ;
A method for synthesizing a condensed polycyclic aromatic compound represented by the following formula (I):

(Q ₁ and Q ₂ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a carbon atom. number 4-20 substituted or unsubstituted aromatic group, selected from the group consisting of alkyl silyl alkynyl group 及 beauty having 1 to 40 carbon atoms, and Q ₁ and Q ₂ of at least one hydrogen atom and a halogen atom Is a group other than
B is a substituted or unsubstituted fused ring having at least one benzene ring moiety;
Y is independently selected from chalcogen, and A _{1 to} A ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon C2-C20 alkynyl group, C4-C20 substituted or unsubstituted aromatic group, C2-C10 ketone group, C1-C20 amino group, C1-C1 Selected from the group consisting of 20 amide groups, imide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, and alkylsilylalkynyl groups having 1 to 40 carbon atoms, and A _{1 to} A ₄ Adjacent two of them may be bonded to each other to form a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms).

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