JP5269825B2 - Novel addition compounds and organic semiconductor devices - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new adduct compound enabling to form organic semiconductor layers made from a condensed polycyclic aromatic compound, using a solution method easier, in general, than a vacuum deposition method. <P>SOLUTION: The new adduct compound having such a structure that a double-bond-bearing compound such as hexachlorocyclopentadiene is eliminably added to a compound such as dinaphthothienothiophene, is provided. Besides, using such a new compound, methods for producing organic semiconductor films and organic semiconductor devices are provided. Further, a method for synthesizing such new adduct compound is provided. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to novel addition compounds and organic semiconductor devices, and methods for producing them. The invention also relates to intermediates for such novel adducts, as well as solutions containing such novel adducts and methods of use thereof.

  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 Document 1). Among these organic semiconductor compounds, it has been found that condensed polycyclic aromatic compounds are preferable in terms of material stability, carrier mobility, and the like.

  In addition, a reaction called Diels-Alder reaction is known in the field of organic synthesis. In this reaction, a compound having a double bond or a triple bond is added to the 1-position and 4-position of a compound having a conjugated double bond to form a 6-membered cyclic compound. In addition, it has been proposed to add hexachlorocyclopentadiene to naphthalene using this Diels-Alder reaction (Non-patent Documents 2 and 3).

JP 2006-89413 A JP 2008-290963 A International Publication WO2006 / 077788 JP 2008-290963 A International Publication No. 2008/050726

“Facile Synthesis of Highly π-Extended Heteroarenes, Dinaphtho [2,3-b: 2 ′, 3′-f] charcogenopheno [3,2-b] charcogenophenes, and theratio-applied. Kazuo Takimiya, J.A. Am. Chem. Soc. , 2007, 129 (8), pp 2224-2225. “Dienophilic Reactions of Aromatic Double Bonds in the Synthesis of β-Substituted Naphthalenes”, A.M. A. Danish, M.M. Silverman, Y.M. A. Tajima, J .; Am. Chem. Soc. , 1954, 76 (23), pp 6144-6150 "Tandem Diels-Alder-Diels-Alder Reaction Displaying High Stereoselectivity:. Reaction of Hexachlorocyclopentadiene with Naphthalene", Lacourcelle, Claire; Poite, Jean Claude; Baldy, Andre; Jaud, Joel; Negrel, Jean Claude; Chanon, Michel, Acta Chemica Scandinavica 47, 0092-0094

  In the formation of the organic semiconductor layer, a solution method (casting, spin coating, printing, etc.) for applying a solution containing the organic semiconductor compound to the substrate and removing the solvent, and vapor deposition for depositing the organic semiconductor compound on the substrate. The law is known. It is known that the solution method is generally preferable with respect to production cost, production rate, and the like.

  However, a condensed polycyclic aromatic compound known to be preferable as an organic semiconductor compound is nonpolar and has high crystallinity, so that it is difficult to dissolve in a solution. Therefore, in the formation of the organic semiconductor layer from the condensed polycyclic aromatic compound, particularly the formation of the organic semiconductor layer from the low molecular weight condensed polycyclic aromatic compound, it is common to use a vapor deposition method.

  Therefore, the present invention provides a novel addition compound and a novel addition compound-containing solution that make it possible to form an organic semiconductor layer composed of a condensed polycyclic aromatic compound using a solution method. Moreover, in this invention, the organic-semiconductor film (organic-semiconductor layer) and organic-semiconductor device obtained using such a novel addition compound are provided. Furthermore, the present invention provides a method for synthesizing such a novel addition compound.

  The inventor of the present invention has found that an addition compound having a structure in which a specific compound is added to a compound such as dinaphthothienothiophene can solve the above problems, and has come up with the present invention.

In the addition compound of the present invention, the compound (II) having a double bond such as hexachlorocyclopentadiene is removed from the condensed polycyclic aromatic compound of the following formula (I) such as dinaphthothienothiophene via this double bond. It has a structure that is detachably added:
Ar ₁ Ar ₂ Ar ₃ (I)
(Ar _{1 to} Ar ₃ are as described below).

  The addition compound-containing solution of the present invention is a solution in which the addition compound of the present invention is dissolved in an organic solvent.

  The method of the present invention for producing an organic semiconductor film comprises the steps of applying the addition compound-containing solution of the present invention to a substrate to produce a film, and subjecting the film to reduced pressure and / or heating to form the film from the addition compound. A step of removing and removing the compound (II) having a double bond to obtain an organic semiconductor film made of the condensed polycyclic aromatic compound of the formula (I) is included.

  The method of the present invention for producing an organic semiconductor device includes the step of producing an organic semiconductor film by the method of the present invention for producing an organic semiconductor film.

  The organic semiconductor device of the present invention has an organic semiconductor film, and the organic semiconductor film has a structure in which the compound (II) having a double bond is eliminated from the addition compound of the present invention. The organic semiconductor film is made of a ring aromatic compound and contains the addition compound of the present invention. The organic semiconductor device of the present invention has an organic semiconductor film, and the organic semiconductor film has a crystal of the condensed polycyclic aromatic compound of the formula (I) having a major axis diameter of more than 5 μm.

  Another novel addition compound (intermediate addition compound) of the present invention can be used as an intermediate for synthesizing the addition compound of the present invention, and compound (II) having a double bond is added. A compound.

  The method of the present invention for synthesizing the adduct of the present invention comprises the step of mixing the condensed polycyclic aromatic compound of formula (I) with compound (II) having a double bond. In addition, another method of the present invention for synthesizing the adduct of the present invention includes a step of reacting two molecules of the intermediate adduct of the present invention.

  The “addition compound” of the present invention has a structure in which the compound (II) having a double bond is detachably added to the condensed polycyclic aromatic compound of the formula (I) via the double bond. It means any compound having, and is not limited by the specific synthesis method. The addition compound of the present invention includes not only an addition compound having a structure in which one molecule of compound (II) having a double bond is added to the condensed polycyclic aromatic compound of formula (I), but also of formula (I) The compound may be an addition compound having a structure in which the compound (II) having a double bond is added to the condensed polycyclic aromatic compound in two molecules, three molecules, four molecules, or more.

  In the context of the present invention, an “aromatic ring” means a ring that is conjugated in the same manner as a benzene ring. For example, along with a benzene ring, a heteroaromatic such as a furan ring, a thiophene ring, a pyrrole ring, and an imidazole ring. A family ring can be mentioned. In the context of the present invention, the term “stereoisomer” means isomerism that occurs when compounds having the same structural formula differ in the configuration of atoms or atomic groups therein, and includes optical isomers, geometric isomers, And rotamers.

  The novel addition compound of the present invention is a compound (II) having a double bond such as hexachlorocyclopentadiene to a condensed polycyclic aromatic compound of the formula (I) such as dinaphthothienothiophene using Diels-Alder reaction. Is removably added via a double bond. This novel addition compound of the present invention can increase the solubility in a solvent by increasing the polarity and / or decreasing the crystallinity caused by the addition of the compound (II) having a double bond. Therefore, according to the novel addition compound of the present invention, it is possible to form an organic semiconductor layer made of a condensed polycyclic aromatic compound by using a solution method that is generally easier than the vapor deposition method.

FIG. 1 is a schematic diagram of the structure of a field effect transistor (FET) used in Example 1A and Comparative Example 1A. FIG. 2 is a graph showing the output characteristics of the field effect transistor obtained in Example 1A. FIG. 3 is a graph showing the transfer characteristics of the field effect transistor obtained in Example 1A. FIG. 4 is a diagram showing the thermal desorption characteristics of the addition compound of Example 10A. FIG. 5 is a diagram showing the output characteristics of the field effect transistor obtained in Example 10A. FIG. 6 is a diagram showing the transfer characteristics of the field effect transistor obtained in Example 10A. FIG. 7 is a diagram showing NMR results for the residual addition compound in the organic semiconductor film obtained in Example 10A. FIG. 8 is a photomicrograph showing the crystal state of DNTT in the channel portion of the organic semiconductor film obtained in Example 10A. FIG. 9 is a polarization micrograph showing the crystal state of DNTT in the organic semiconductor film obtained in Example 10C. FIG. 10 is a polarization micrograph showing the crystal state of DNTT in the organic semiconductor film obtained in Example 10D. FIG. 11 is a polarization micrograph showing the crystal state of DNTT in the organic semiconductor film obtained in Example 10E. FIG. 12 is a polarization micrograph showing the crystal state of DNTT in the organic semiconductor film obtained in Example 10F. FIG. 13 is a polarizing micrograph showing the crystal state of DNTT in the organic semiconductor film obtained in Example 10G.

《Addition compound》
The addition compound of the present invention has a structure in which a compound (II) having a double bond is detachably added to a condensed polycyclic aromatic compound of the following formula (I) via a double bond:
Ar ₁ Ar ₂ Ar ₃ (I)
(Ar ₁ and Ar ₃ are each independently selected from substituted or unsubstituted fused aromatic ring moieties fused with 2 to 5 aromatic rings;
Ar ₂ is selected from a substituted or unsubstituted aromatic ring moiety consisting of one aromatic ring, and a substituted or unsubstituted fused aromatic ring moiety fused with 2 to 5 aromatic rings;
Ar ₁ and Ar ₂ share at least two carbon atoms to form a condensed aromatic ring, and Ar ₂ and Ar ₃ share at least two carbon atoms to form a condensed aromatic ring ).

  In the addition compound of the present invention, the compound (II) having a double bond is added to the condensed polycyclic aromatic compound of the formula (I) so as to be “detachable”. The compound (II) having a double bond is removed by depressurization and / or heating without decomposing the condensed polycyclic aromatic compound of the formula (I), in particular the compound (II) having a double bond. It means that it can be desorbed and removed.

  For example, the addition compound of the present invention is an example of the compound (II) having a double bond to the compound of the following formula (I-4) which is an example of the condensed polycyclic aromatic compound of the formula (I). Is a compound having the following formula (III-1) or a stereoisomer thereof:

(Y is each independently an element selected from chalcogen, and the fused benzene ring moiety is substituted or unsubstituted)

(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 alkynyl having 2 to 10 carbon atoms. Group, 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, and a carbon atom It consists of a C1-C10 ketone group, a C1-C10 amino group, a C1-C10 amide group, a C1-C10 imide group, and a C1-C10 sulfide group. Selected from the group);

(Y and R and the fused benzene ring moiety are as described above).

  Further, for example, the addition compound of the present invention is an example of the compound (II) having a double bond to the compound of the following formula (I-4) which is an example of the condensed polycyclic aromatic compound of the formula (I). A compound of the following formula (II-6) is added, whereby a compound having the following formula (III-6) or a stereoisomer thereof:

(Y is each independently an element selected from chalcogen and the fused benzene ring moiety is substituted or unsubstituted);

(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);

(Y, R and R _r and the fused benzene ring moiety are as described above).

<< First Synthesis Method of Addition Compound >>
The addition compound of the present invention can be produced by a method comprising the step of mixing the condensed polycyclic aromatic compound of the formula (I) with the compound (II) having a double bond. At this time, the compound (II) having a double bond can be used by dissolving in a solvent, but can also be used alone. Here, as this solvent, any solvent capable of dissolving the compound (II) having a double bond can be used. For example, usable solvents include aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile and ethyl acetate; ether solvents such as diethyl ether, tetrahydrofuran, diisopropyl ether, diethylene glycol dimethyl ether and 1,4-dioxane; Consider aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene (ie 1,3,5-trimethylbenzene); aliphatic hydrocarbons such as hexane and heptane; and halogen-containing solvents such as dichloromethane, chloroform and dichloroethane can do.

  In the synthesis of the addition compound of the present invention, the reaction is accelerated by heating and / or light irradiation when mixing the condensed polycyclic aromatic compound of formula (I) and the compound (II) having a double bond. You can also The reaction temperature in the synthesis of the addition compound of the present invention can be determined in consideration of the production rate, the stability of the component, the boiling point of the component, etc., for example, 20 ° C. or higher, 50 ° C. or higher, 100 ° C. or higher. The temperature can be 180 ° C. or lower, 200 ° C. or lower, or 220 ° C. or lower. The reaction time is, for example, 1 minute or more, 10 minutes or more, 30 minutes or more, 1 hour or more, and can be 1 day or less, 3 days or less, 5 days or less, or 10 days or less.

<< Intermediate addition compound and second synthesis method of addition compound >>
The intermediate addition compound of the present invention has a structure in which a compound (II) having a double bond is added to the following compound (I ′) via this double bond:
Ar ₁ Q (I ′)
{Ar ₁ is selected from a substituted or unsubstituted fused aromatic ring moiety to which 2 to 5 aromatic rings are fused, and Q has the following formula and Ar ₁ fused aromatic ring Part of:
(Y is an element selected from chalcogen)}.

Specifically, for example, the compound of formula (I ′) may be a compound of the following formula:

  This intermediate addition compound of the present invention can be obtained by adding a compound (II) having a double bond to a compound of the formula (I '). For the reaction conditions for this addition reaction, reference can be made to the description relating to the reaction in which compound (II) having a double bond is added to the compound of formula (I).

The method of synthesizing the above adduct of the present invention from the above intermediate adduct includes the following steps (a) and (b):
(A) Reaction of two molecules of the intermediate addition compound of the present invention to obtain a compound of the following formula:
Ar ₁ Q = QAr ₁
(Q = Q represents the following structure:
And (b) reacting the resulting compound of formula Ar ₁ Q = QAr ₁ with iodine.

According to this method, a structure in which a compound (II) having a double bond is detachably added to the condensed polycyclic aromatic compound of the following formula (I (a1)) via this double bond. An addition compound of the present invention can be prepared:
Ar ₁ Ar _{2 (a1)} Ar ₁ (I (a1))
(Ar ₁ is selected from a substituted or unsubstituted fused aromatic ring moiety to which 2 to 5 aromatic rings are fused,
Ar _{2 (a1)} is a fused aromatic ring moiety of the following formula (a1), and
Ar ₁ and Ar _{2 (a1)} share at least two carbon atoms to form a condensed aromatic ring).

In addition, regarding the conditions of the method for synthesizing the above-described addition compound of the present invention from the above intermediate addition compound, the description in Non-Patent Document 1 can be referred to. That is, for example, the reaction of two molecules of the intermediate addition compound in the step (a) can be performed in tetrahydrofuran using a tetrachlorotitanium / zinc (TiCl ₄ / Zn) catalyst. Also, the reaction of formula Ar ₁ (Q = Q) Ar ₁ with iodine in step (b) can be carried out in trichloromethane (ie chloroform) (CHCl ₃ ).

<< Condensed Polycyclic Aromatic Compound of Formula (I) >>
With respect to the condensed polycyclic aromatic compound of formula (I), Ar ₁ and Ar ₃ are each independently substituted or unsubstituted, wherein 2 to 5 aromatic rings, particularly 2 to 4 aromatic rings are condensed Selected from the fused aromatic ring moieties. When Ar ₁ and Ar ₃ are subjected to a Diels-Alder reaction, a compound (II) having a double bond can be removably added to this part as a diene part or a diene part. Can be selected. Here, the aromatic ring is in particular a substituted or unsubstituted benzene ring. Ar ₁ and Ar ₃ may be the same or different.

Accordingly, Ar ₁ and Ar ₃ may each independently be a substituted or unsubstituted benzene ring moiety selected from the group consisting of the following (b1) to (b4):

Also, with respect to the fused polycyclic aromatic compound of formula (I), Ar ₂ is a substituted or unsubstituted aromatic ring moiety consisting of one aromatic ring, or 2 to 5, especially 2 to 3 aromatics A substituted or unsubstituted fused aromatic ring moiety to which an aromatic ring is fused.

Thus, Ar ₂ may be a substituted or unsubstituted aromatic ring moiety or fused aromatic ring moiety selected from the group consisting of (a1) to (a4) below:
(Y is each independently a chalcogen, in particular an element selected from oxygen (O), sulfur (S), selenium (Se) and tellurium (Te)), more particularly sulfur, May be different).

  Preferably, the condensed polycyclic aromatic compound of formula (I) is an organic semiconductor compound, that is, an organic compound exhibiting properties as a semiconductor. Further, the condensed polycyclic aromatic compound of the formula (I) can be selected from the group consisting of substituted or unsubstituted condensed polycyclic aromatic compounds of the following formulas (I-1) to (I-5). These fused polycyclic aromatic compounds are highly stable, and therefore elimination of the compound (II) having a double bond from the addition compound of the present invention, in particular, elimination by heat, more particularly at relatively high temperatures and / or lengths. It can be stably maintained even during the desorption due to heat of time. Therefore, when these compounds are used, the compound (II) having a double bond from the addition compound of the present invention can be eliminated at a high rate.

(Y is each independently an element selected from chalcogens, especially elements selected from oxygen (O), sulfur (S), selenium (Se) and tellurium (Te), more particularly sulfur, all Y being the same) But some may be different).

  Although it does not specifically limit regarding the condensed polycyclic aromatic compound of a formula (I), and its synthesis | combination, patent documents 1-5 and nonpatent literature 1 can be referred.

  In addition, the substitution of the aromatic ring part and / or the condensed aromatic ring part of the condensed polycyclic aromatic compound of the formula (I) is, for example, halogen, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. An alkenyl group, an alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, an ether group having 1 to 20 carbon atoms, carbon From a ketone group having 1 to 20 atoms, an amino group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, an imide group having 1 to 20 carbon atoms, and a sulfide group having 1 to 20 carbon atoms By a substituent selected from the group consisting of

<< Compound (II) having a double bond >>
Compound (II) having a double bond may be any compound that can be removably added to the condensed polycyclic aromatic compound of formula (I). Thus, for example, compound (II) having a double bond is detachably added as a diene isomer (dienophile) or a conjugated diene isomer to the condensed polycyclic aromatic compound of formula (I), particularly by Diels-Alder reaction. It may be any compound. In addition, the compound (II) having a double bond is particularly an aromatic ring part or a condensed aromatic ring part of at least one of Ar ₁ , Ar ₂ and Ar ₃ of the condensed polycyclic aromatic compound of the formula (I). , More particularly any compound that can be removably added to at least one fused aromatic ring moiety of Ar ₁ and Ar ₃ of the fused polycyclic aromatic compound of formula (I).

When the compound (II) having a double bond is a diene, the compound (II) having a double bond is any one of the following formulas (II-A1) and (II-B1) Good:
(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, and R _c and R _d may be bonded to each other to form a ring).

  Here, in the compound of the above formula (II-A1), due to the presence of the carbon-oxygen double bond portion, the carbon-carbon double bond portion adjacent to the carbon atom is relatively electrophilic. It may be preferable as a diene to promote the Diels-Alder reaction. Similarly, in the compound of the above formula (II-B1), due to the presence of oxygen, the carbon-carbon double bond portion adjacent to this oxygen atom is relatively electrophilic, and therefore the Diels-Alder reaction as a diene isomer. May be preferred to promote

In addition, when the compound (II) having a double bond is a diophile, the compound (II) having a double bond is any one of the following formulas (II-A2) and (II-B2): May be:
(R _b , R _c , R _d and R _e 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 _e and R _b may be bonded to each other to form a ring, and R _c and R _d may be bonded to each other to form a ring).

  Here, in the compound of the above formula (II-A2), the presence of two carbon-oxygen double bond moieties makes the carbon-carbon double bond moiety between those carbon atoms relatively electrophilic. Therefore, it may be preferable as a diene isomer to promote the Diels-Alder reaction. Similarly, the compound of formula (II-B2) above has a relatively electrophilic carbon-carbon double bond moiety between their oxygen atoms due to the presence of two oxygens, and thus Diels as diene isomers. -May be preferred to promote Alder reaction.

Furthermore, when the compound (II) having a double bond is a diene isomer, the compound (II) having a double bond is any one of the following formulas (II-A3) and (II-B3): May be:
(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, alkenyl group having 2 to 10 carbon atoms, or carbon atom. C2-C10 alkynyl group, C1-C10 alkoxy group, C4-C10 substituted or unsubstituted aromatic group, C1-C10 ester group, C1-C10 Ether groups, ketone groups having 1 to 10 carbon atoms, amino groups having 1 to 10 carbon atoms, amide groups having 1 to 10 carbon atoms, imide groups having 1 to 10 carbon atoms, and 1 to 1 carbon atoms Selected from the group consisting of 10 sulfide groups;
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)).

  Here, in the compound of the above formula (II-A3), the presence of two carbon-oxygen double bond moieties makes the carbon-carbon double bond moiety between those carbon atoms relatively electrophilic. Therefore, it may be preferable as a diene isomer to promote the Diels-Alder reaction. Similarly, the compound of formula (II-B3) above has a relatively electrophilic carbon-carbon double bond moiety between their oxygen atoms due to the presence of two oxygens, and thus Diels as a diene isomer. -May be preferred to promote Alder reaction. In addition, the compounds of the above formula (II-A3) or (II-B3) are structurally stable because the double bond is part of the cyclic structure, and therefore these compounds are eliminated. It may be preferred for possible addition to the fused polycyclic aromatic compound of formula (I).

  The compound (II) having a conjugated diene-type double bond is converted into a condensed polycyclic aromatic compound of the formula (I) according to the combination with the condensed polycyclic aromatic compound of the formula (I) in the Diels-Alder reaction. To a group compound as a diene isomer and / or a conjugated diene isomer.

  Compound (II) having a double bond may be a compound having a cyclic moiety. The fact that the double bond is a part of the cyclic structure means that the compound (II) having a double bond is structurally stabilized, whereby the compound (II) having a double bond can be eliminated. It may be preferred for addition to the condensed polycyclic aromatic compound of I).

  Thus, for example, the compound (II) having a double bond may be any compound of the following formulas (II-1) to (II-12):

(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).

  The compound (II) having a double bond may be a conjugated diene type compound, for example, any compound of the formula (II-1) to the formula (II-3) and the formula (II-8). Further, the compound (II) having a double bond is a diene-type compound, for example, the formula (II-4) to the formula (II-6), the formula (II-9), and the formula (II-10) to the formula It may be any compound of (II-12). Furthermore, the compound (II) having a double bond is a compound having a cyclic moiety, for example, the formula (II-1) to the formula (II-6), the formula (II-8), and the formula (II-10) to It may be any compound of formula (II-12).

In addition, regarding R and R _r of any one of the compounds of formulas (II-1) to (II-12), regarding the substituent of the aromatic group having 4 to 10 carbon atoms, the condensed polycycle of formula (I) Reference can be made to substituents that may be substituted on the aromatic ring portion or fused aromatic ring portion of the aromatic compound.

  Below, the compound in any one of following formula (II-1)-(II-12) is demonstrated in detail.

<< Compound of Formula (II-1) >>
(R is as above)

  In particular, for the compound of formula (II-1), each R is independently selected from the group consisting of hydrogen and halogen. When R is halogen, each R is independently an element selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and combinations thereof, particularly fluorine (F) , An element selected from the group consisting of chlorine (Cl) and combinations thereof, more particularly chlorine. Thus, the compound of formula (II-1) is, for example, hexafluorocyclopentadiene, hexachlorocyclopentadiene, hexabromocyclopentadiene, 5,5-difluorotetrachlorocyclopentadiene, or 5,5-dibromotetrachlorocyclopentadiene, especially hexachloro It may be cyclopentadiene. When all R are hydrogen, the compound of formula (II-1) is cyclopentadiene.

<< Compound of Formula (II-2) >>
(R is as above)

  In particular, for the compound of formula (II-2), each R is independently selected from the group consisting of hydrogen and halogen. When all R are hydrogen, the compound of formula (II-2) is furan.

<< Compound of Formula (II-3) >>
(R and R _r are as described above)

In particular, for the compound of formula (II-3), each R is independently selected from the group consisting of hydrogen and halogen. In particular, R _r is an ester group having 1 to 10 carbon atoms, such as a methyl ester. Therefore, in particular, the compound of the above formula (II-3) is a compound in which R is hydrogen and R _r is an alkyl ester group having 1 to 10 carbon atoms, that is, an alkyl pyrrole carboxylate, for example, R is hydrogen and It may be a methyl pyrrole carboxylate in which R _r is a methyl ester group.

<< Compound of Formula (II-4) >>
(R and R _r are as described above)

In particular, for the compound of formula (II-4), R _r is a group other than hydrogen, ie a relatively bulky group, indicating that the condensed polycyclic aromatic compound of formula (I) and the compound of formula (II-4) In order to promote the elimination of the compound of the formula (II-4) from the addition product with, for example, by heating.

<< Compound of Formula (II-5) >>
(R is as above)

  In particular, with respect to the compound of formula (II-5), the compound where all R is hydrogen is maleic anhydride. Accordingly, the compound of formula (II-5) can be considered as a compound in which maleic anhydride or its hydrogen group is substituted.

<< Compound of Formula (II-6) >>
(R and R _r are as described above)

In particular, for the compound of formula (II-6), each R is independently selected from the group consisting of hydrogen and halogen. In particular, R _r is an alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, such as a hydroxyphenyl group.

Thus, for example, compounds of formula (II-6) is, R is hydrogen and R _r is a methyl group N- methylmaleimide, R is hydrogen and R _r is an ethyl group N- ethylmaleimide It may be. For example, the compound of the above formula (II-6) is a compound in which R is hydrogen and R _r is a substituted or unsubstituted aromatic group having 4 to 10 carbon atoms, that is, an aromatic maleimide, particularly R N-phenylmaleimide in which R is hydrogen and R _r is a phenyl group, or hydroxyphenylmaleimide in which R is hydrogen and R _r is a hydroxyphenyl group.

<< Compound of Formula (II-7) >>
(R _r is as described above)

In particular, for the compound of formula (II-7), R _r is selected from the group consisting of alkyl groups having 1 to 10 carbon atoms. In particular, the compounds of formula (II-7) thus the compound R _r is an alkyl group, i.e. N- sulfonyl amides, for example R _r may be a N- sulfonyl acetamide is a methyl group.

<< Compound of Formula (II-8) >>
(R is as above)

  In particular, for the compound of formula (II-8), each R is independently selected from the group consisting of hydrogen and halogen. When R is halogen, each R is independently an element selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and combinations thereof. When all R are hydrogen, the compound of formula (II-8) is anthracene.

<< Compound of Formula (II-9) >>
(R _r is as described above)

In particular, for the compound of formula (II-9), R _r is selected from the group consisting of alkyl groups having 1 to 10 carbon atoms. Therefore, in particular, the compound of the above formula (II-9) is a compound in which R _r is an alkyl group, that is, alkyl-ethylene tricyanocarboxylate, for example, methyl-ethylene tricyanocarboxylate in which R _r is a methyl group. Good.

<< Compound of Formula (II-10) >>
(R and R _r are as described above)

<< Compound of Formula (II-11) >>
(R is as above)

  In particular, for the compound of formula (II-11), each R is independently selected from the group consisting of hydrogen and halogen. When all R are hydrogen, the compound of formula (II-2) is vinylene carbonate.

<< Compound of Formula (II-12) >>
(R and R _r are as described above)

<< Addition compound-containing solution >>
The addition compound-containing solution of the present invention is obtained by dissolving the addition compound of the present invention in a solvent, particularly an organic solvent.

  This addition compound-containing solution can contain the addition compound of the present invention at an arbitrary concentration. For example, the addition compound of the present invention is 0.01 to 20% by mass, 0.05 to 10% by mass, 0.1%. It can be contained at a concentration of ˜5% by mass.

  As a solvent that can be used in the addition compound-containing solution, any solvent that can dissolve the addition compound of the present invention can be used. For example, usable solvents include aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile and ethyl acetate; ether solvents such as diethyl ether, tetrahydrofuran, diisopropyl ether, diethylene glycol dimethyl ether and 1,4-dioxane; Consider aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene (ie 1,3,5-trimethylbenzene); aliphatic hydrocarbons such as hexane and heptane; and halogen-containing solvents such as dichloromethane, chloroform and dichloroethane can do.

  In the case where the addition compound of the present invention has a stereoisomer, the solution of the present invention includes, for example, the addition compound of the present invention and at least one stereoisomer thereof dissolved in a solvent, and the addition compound and the stereoisomer thereof. The ratio of the stereoisomer with the lowest thermal desorption temperature to the total of {addition compound and its stereoisomer with the lowest thermal desorption temperature / addition compound and its stereoisomer} is more than 50 mol%, It may be more than 70 mol%, more than 90 mol%, more than 95 mol%.

  In addition, when the addition compound of the present invention has an Exo form and an Endo form as stereoisomers, the solution of the present invention contains, for example, the Exo form and Endo form of the addition compound of the present invention in a solvent, and Ratio of Stereoisomer with Lower Thermal Desorption Temperature to Total of Exo and Endo Forms of Addition Compound of Invention {Stereoisomer with Lower Thermal Desorption Temperature of Exo Form and Endo Form / (Exo Body + Endo body)} may be more than 50 mol%, more than 70 mol%, more than 90 mol%, more than 95 mol%. Therefore, the solution of the present invention comprises, for example, an Exo isomer and an Endo isomer of the addition compound of the formula (III-6) dissolved in a solvent, and the Exo isomer with respect to the sum of the Exo isomer and Endo isomer of the addition compound. The ratio {Exo isomer / (Exo isomer + Endo isomer)} may be greater than 50 mol%, greater than 70 mol%, greater than 90 mol%, greater than 95 mol%, or greater than 99 mol%.

  Here, when the addition compound-containing solution of the present invention contains a stereoisomer having a relatively low thermal desorption temperature in a relatively large proportion, the compound (II) having a double bond is heated from this solution. When an organic semiconductor film made of the condensed polycyclic aromatic compound of formula (I) is obtained by desorption and removal, this desorption can be started from a relatively low temperature. Therefore, in this case, the generation of the organic semiconductor film at a relatively low temperature can be promoted.

  In the Diels-Alder reaction, a reaction product having a substituent on the opposite side of the main bridge is defined as an Endo isomer, and a reaction product having a substituent on the same side as the main bridge is defined as an Exo isomer. The

<< Method for producing organic semiconductor film >>
The method of the present invention for producing an organic semiconductor film comprises the steps of applying the additive compound-containing solution of the present invention to a substrate to produce a film, and subjecting the film to reduced pressure and / or heating to form an organic compound film. A step of removing and removing the compound (II) having a double bond to obtain an organic semiconductor film made of the condensed polycyclic aromatic compound of the formula (I) is included.

  Application of this solution to the substrate can be performed in an arbitrary manner, for example, by a casting method, a spin coating method, a printing method, or the like. The application of the solution to the substrate can be performed simply by dropping the solution onto the substrate.

  When the compound (II) is eliminated and removed by heating and / or reduced pressure, any conditions that do not substantially decompose the condensed polycyclic aromatic compound of the formula (I) can be used. Accordingly, desorption and removal of compound (II) is, for example, 80 ° C. or higher, 100 ° C. or higher, 120 ° C. or higher, or 140 ° C. or higher, and a temperature of 200 ° C. or lower, 220 ° C. or lower, 240 ° C. or lower, 260 ° C. or lower. Can be heated. In addition, desorption and removal of compound (II) can be performed, for example, under vacuum or atmospheric pressure. Furthermore, desorption and removal of the compound (II) can be performed, for example, in a nitrogen atmosphere or an air atmosphere. In particular, the elimination and removal of the compound (II) in an atmospheric atmosphere at atmospheric pressure is preferable in order to facilitate the production of the condensed polycyclic aromatic compound of the formula (I).

  In the method of the present invention for producing an organic semiconductor film, the elimination and removal of the compound (II) having a double bond is performed by rapid heating, for example, 100 ° C./min, 200 ° C./min, 400 ° C./min, 600 It can be carried out by heating at a heating rate in excess of ° C / min, 800 ° C / min or 1000 ° C / min. Such rapid heating can be achieved, for example, by directly contacting a substrate having a film with a heated object such as a heated electric heater, and heating the substrate having a film to a heated furnace or the like. It can be achieved by introducing into the region, radiating electromagnetic waves such as infrared rays and microwaves to the film side or substrate side, or simultaneously performing either of these. Moreover, this rapid heating can be performed up to 3 ° C. or more, 5 ° C. or more, or 10 ° C. or more higher than the temperature at which desorption and removal of the compound (II) having a double bond is started.

  When the elimination and removal of the compound (II) having a double bond is carried out by rapid heating in this way, large crystals of the condensed polycyclic aromatic compound of the formula (I), for example, the formula (I with a major axis diameter exceeding 5 μm ) Of an organic semiconductor film having a crystal of a condensed polycyclic aromatic compound.

  This is because when the compound (II) having a double bond is eliminated and removed by rapid heating, the compound (II) having the double bond is simultaneously removed and removed. Rearrangement due to thermal motion of the condensed polycyclic aromatic compound occurs, whereby the crystallinity of the condensed polycyclic aromatic compound of formula (I) promotes crystallization of the condensed polycyclic aromatic compound of formula (I). It is thought that it depends. On the other hand, when the compound (II) having a double bond is removed and removed by slow heating, the compound (II) having a double bond is desorbed from the addition compound. Crystallization of the condensed polycyclic aromatic compound of I) proceeds at a large number of locations to generate a large number of crystal nuclei, and in the finally obtained organic semiconductor film, individual condensed polycycles of the formula (I) It is thought that the crystals of the aromatic compound become fine.

<< Method for Manufacturing Organic Semiconductor Device >>
The inventive method of manufacturing an organic semiconductor device includes the step of producing an organic semiconductor film by the inventive method of 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.

《Organic semiconductor device》
The organic semiconductor device of the present invention is an organic semiconductor device having an organic semiconductor film, wherein the organic semiconductor film has a structure in which the compound (II) having a double bond is eliminated from the addition compound of the present invention. And the organic semiconductor film contains the addition compound of the present invention.

  Here, the fact that the organic semiconductor film contains the addition compound of the present invention means that the organic semiconductor film contains the addition compound of the present invention in a detectable amount. Thus, for example, the molar ratio of the addition compounds of the present invention 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 addition compound of this invention 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.

  Such an organic semiconductor device of the present invention may have characteristics as an organic semiconductor device despite containing the addition compound of the present invention along with the condensed polycyclic aromatic compound of the formula (I). it can. That is, when the organic semiconductor film of the organic semiconductor device of the present invention is produced from the addition compound of the present invention, the organic semiconductor device of the present invention can be obtained even if the thermal desorption reaction of the addition compound of the present invention does not proceed completely. It can have characteristics as a semiconductor device. This is preferable for facilitating the production of the organic semiconductor device of the present invention or the organic semiconductor film thereof.

Another organic semiconductor device of the present invention is an organic semiconductor device having an organic semiconductor film, wherein the organic semiconductor film has a major axis diameter of more than 5 μm, more than 10 μm, more than 20 μm, more than 30 μm, more than 40 μm, more than 50 μm, Having crystals of condensed polycyclic aromatic compounds of the following formula (I) of more than 60 μm, more than 70 μm, more than 80 μm, more than 90 μm or more than 100 μm:
Ar ₁ Ar ₂ Ar ₃ (I)
(Ar ₁ , Ar ₂ , and Ar ₃ are as described above).

  In such an organic semiconductor device of the present invention, when the organic semiconductor film has a large crystal, semiconductor characteristics such as carrier mobility and on / off ratio of the organic semiconductor film can be improved.

  These organic semiconductor films for the organic semiconductor devices of the present invention can be produced, for example, by a solution method, ie, a method of forming an organic semiconductor film comprising the steps of applying the solution to a substrate and removing the solvent from the solution. It can be obtained by the method of the present invention for producing a membrane.

  Still another organic semiconductor device of the present invention is an organic semiconductor device having an organic semiconductor film, wherein the organic semiconductor film has a structure in which the compound (II) having a double bond is eliminated from the addition compound of the present invention. The organic semiconductor film contains the addition compound of the present invention, and the organic semiconductor film has a major axis diameter of more than 5 μm. Of condensed polycyclic aromatic compounds.

  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.

The structure of the target compound was determined by 1H-NMR (1H-nuclear magnetic resonance spectrum), MS (mass spectrometry spectrum), and elemental analysis as necessary. The equipment used is as follows.
¹ H-NMR: JEOL ECA-500 (500 MHz)
MS: Shimazu QP-5050A
Elemental analysis: Parkin Elmer2400 CHN type elemental analyzer

  Moreover, the conditions in the computer simulation performed about addition reaction are as follows.

<Semi-experience method>
Program: MOPAC3.0
Hamiltonian: AM1
Structural optimization: Structural optimization by EF method

<Non-experience method>
Program: Gaussian03
Correlation exchange function: B3LYP
Basis set: 6-31G (d)
Structural optimization: Berny algorithm

  In this computer simulation, the heat of formation of the raw material compounds and the heat of formation of the addition products of these compounds were determined, thereby evaluating the feasibility of the reaction to produce this addition product. Here, when the difference between the total heat of formation of the raw material compounds and the heat of formation of the addition products of these compounds (relative heat of formation) is greater than −20 kcal / mol (endothermic), that is, the addition reaction In the case of an exothermic reaction or a slightly endothermic reaction, a reaction that produces this addition product is considered feasible. In addition, when this relative heat of formation is relatively small, for example, when the endothermic reaction is an endothermic reaction greater than −20 kcal / mol or an exothermic reaction of 20 kcal / mol or less, this addition reaction is reversible. It is believed that there is. Note that MOPAC is very reliable when only carbon and hydrogen are considered, but Gaussian's reliability is high when other elements are included.

<< Example 1A >>
To 100 mg (0.293 mmol) of dinaphthothienothiophene (DNTT, MW = 340.46, structural formula shown below) synthesized by the method shown in Patent Document 2, hexachlorocyclopentadiene (HCPPD, MW = 272.77, 20 g (47.66 mmol) of the structural formula are shown below and the reaction temperature was kept at 160 ° C. for 24 hours.

  Thereafter, the reaction product was allowed to cool, and hexachlorocyclopentadiene 2-added dinaphthothienothiophene (DNTT-2HCCPD (TTs), Mw. 886.00, 20 mg, 0.0225 mmol, yield = 7.7%, structural formula Was obtained).

  DNTT-2HCCPD (TTs) obtained as described above was purified by high performance liquid chromatography (Agilent 1100 Series HPLC: High Performance Liquid Chromatography, SHISEIDO CAPCELL PAK C18 TYPE 120), solvent: acetonitrile.

The analysis results for DNTT-2HCCPD (TTs) are shown below:
¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.43 (s, 1H), 8.39 (s, 1H), 8.33 (s, 1H), 8.24 (s, 1H), 8.05 (M, 1H), 7.96 (m, 1H), 7.55 (m, 2H), 4.20 (d, J = 9.5 Hz, 1H), 4.16 (d, J = 9.5 Hz) , 1H), 3.64 (d, J = 8.9 Hz, 2H)
Anal. _{Calcd for C 32 H 12 Cl 12} S 2: C, 43.37; H, 1.37
Found: C, 41.9; H, 1.3
MS (70 eV, DI): 340 m / z

  The detection value (340 m / z) of mass spectrometry (MS) is consistent with DNTT (molecular weight 340.46), and DNTT-2HCCPD (TTs) is exposed to the conditions of mass spectrometry (70 eV, DI). HCCPD is desorbed to regenerate DNTT.

  DNTT-2HCCPD (TTs) obtained by the above synthesis was dissolved in toluene so as to have a concentration of 0.2% by mass to prepare a solution for forming a semiconductor element.

Next, UV ozone treatment was performed on an n-doped silicon wafer with 300 nm SiO ₂ oxide film (surface resistance 0.005 Ω · cm) for 20 minutes (eye UV-ozone cleaning device OC-250615-D + A, eye Graphics Corporation). In addition, a 10 mmol / toluene solution of octadecyltrichlorosilane (ODTS, Shin-Etsu Chemical LS-6495) was prepared, and a silicon substrate subjected to UV ozone treatment was immersed in this solution for 24 hours. Thereafter, a source / drain gold electrode having a channel length of 50 μm and a channel width of 1.5 mm was formed on the silicon substrate by vacuum deposition (Sanyu Electronics, resistance heating deposition device: SVC-700TM / 700-2).

  While this silicon substrate was heated 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 DNTT-2HCCPD (TTs). The device thus fabricated was heat-treated at 180 ° C. for 1 hour under vacuum to produce an organic semiconductor device. The outline of the obtained organic semiconductor element is shown in FIG. In the organic semiconductor element shown in FIG. 1, a dielectric layer 5 made of silicon oxide is formed on a base material (gate electrode) 7 that is a silicon wafer, and source and drain electrodes are formed on the dielectric layer 5. 2 and 3, and the organic semiconductor 1 is laminated.

Measurement of organic semiconductor characteristics showed a p-type semiconductor. The carrier mobility was 2 × 10 ⁻⁵ cm ² / Vs, the on / off ratio was 113, and the threshold voltage was 14.4 V. The output characteristics and transfer characteristics of a field effect transistor (FET) are shown in FIGS. 2 and 3, respectively. Here, in FIG. 2, the vertical axis indicates the drain current (I _D (A)), and the horizontal axis indicates the drain voltage (V _D (V)). In FIG. 3, the vertical axis represents the drain current (I _D (A)), and the horizontal axis represents the gate voltage (V _G (V)).

<< Comparative Example 1A >>
A single DNTT without HCCPD added was added to toluene at a concentration of 0.2% by weight, but was hardly dissolved. Therefore, a single DNTT could not be used in the solution method.

<< Example 1B >>
The addition reaction of dinaphthothienothiophene (DNTT) and hexachlorocyclopentadiene (HCCPD) was confirmed by computer simulation using the semi-empirical method (MOPAC) described above.

  The results are shown in the table below. In the above semi-empirical method (MOPAC), the heat of formation of DNTT was 117.29 kcal / mol, and the heat of formation of HCCPD was 5.86 kcal / mol.

  For the addition positions in Table 1, as shown in the chemical formula below, “c” is the central position, “z” is the position of the end on the same side (zusammen) with respect to the nearby sulfur (S) atom, and “e”. Indicates that HCCPD is added to DNTT at the position of the end opposite to the close sulfur (S) atom.

  In Table 1, “anti” indicates that HCCPD is added from the opposite side to the conjugate surface of DNTT, and “iso” indicates that two HCCPDs are added to the end on the same side of DNTT. It shows that you are doing. Furthermore, “anti” when three or more HCCPDs are attached indicates that the binding conformation between HCCPDs between adjacent opposite ends is “anti”.

  From the results in Table 1, when only one HCCPD is added to DNTT, the position of the terminal on the same side with respect to the close sulfur (S) atom (addition position “z”, symbol “DNTT-1HCCPD (T) )) And the terminal position opposite the near sulfur (S) atom (addition position “e”, symbol “DNTT-1HCCPD (Tb)”), it is understood that HCCPD is added to DNTT. In addition, when another HCCPD is added to this addition product, it is understood that HCCPD is further added to the same end (addition position “iso”) as the end to which HCCPD has already been added. (Symbol “DNTT-2HCCPD (TTs)”).

  When two HCCPDs are added to DNTT, this result that HCCPD is further added to the same end (addition position “iso”) as the end already added with HCCPD corresponds to the result obtained in Example 1A. doing. Therefore, the validity of the application of computer simulation in the Diels-Alder reaction is understood.

<< Example 2A >>
1750 mg (5.14 mmol) of dinaphthothienothiophene (DNTT, MW = 340.46), 17.83 g (169.62 mmol, 3300 mol%) of N-sulfonylacetamide (NSAA, MW 105.12, the structural formula is shown below), And 12.81 mg (0.05 mmol) of metal catalyst reagent CH ₃ ReO ₃ (ACROS A0245387, MW 249.23) were mixed in chloroform solvent and refluxed at 63 ° C. for 15.5 hours under nitrogen. Thereby, Diels-Alder addition reaction of DNTT and NSAA was performed.

  Then, the solid substance was obtained by filtration and washed with chloroform. It was confirmed that 1.82 g of the obtained green solid was an impurity containing a raw material.

  Hexane was added to the filtrate for recrystallization, and 0.2636 g of a yellow solid (31.5 mg) was obtained by filtration. This solid was fractionated by HPLC to obtain 31.5 mg (DNTT-1NSAA, Mw = 445.58, yield 1.4 mol%) of an addition compound in which one molecule of NSAA was added to DNTT. The structural formula of this addition compound is shown below.

  The analysis result about obtained DNTT-1NSAA is shown below.

¹ H-NMR (600 MHz, CDCl ₃ ): δ 8.42 (s, 2H), 8.38 (s, 2H), 8.05 (m, 2H), 7.95 (m, 2H), 7.54 (M, 4H), 2.03 (s, 3H)
MS (70 eV, DI): 339.85 m / z

  The detection value (339.85 m / z) of mass spectrometry (MS) is consistent with DNTT (molecular weight 340.46), and DNTT-1NSAA is exposed to the conditions of mass spectrometry (70 eV, DI). It is shown that NSAA is desorbed and DNTT is regenerated.

<< Example 2B >>
The addition reaction of dinaphthothienothiophene (DNTT) and N-sulfonylacetamide (NSAA) was confirmed by computer simulation using the semi-empirical method (MOPAC) and non-experienced method (Gaussian) described above.

  The results are shown in the table below. In the above semi-empirical method (MOPAC), the heat of formation of DNTT was 117.56 kcal / mol, and the heat of formation of NSAA was −49.27 kcal / mol.

  Regarding the addition positions in Table 2, the carbons of DNTT were numbered as shown in the following chemical formula, and the carbons coordinated with the nitrogen (N) atoms and sulfur (S) atoms of NSAA were identified.

  From the results in Table 2, it can be understood that a reaction in which NSAA is added to DNTT is feasible, and in this case, NSAA is added to the central position of DNTT.

Example 3
The addition reaction between dinaphthothienothiophene (DNTT) and cyclopentadiene (CPD, structural formula shown below) was confirmed by computer simulation using the semi-empirical method (MOPAC) and the non-empirical method (Gaussian) described above.

  The results are shown in the table below. In the above semi-empirical method (MOPAC), the heat of formation of DNTT was 117.56 kcal / mol, and the heat of formation of CPD was 37.97 kcal / mol.

  The additional positions in Table 3 are exemplified below. The symbol “CPD-CPD” in Table 3 indicates an addition product obtained by adding two CPDs.

  From the results in Table 3, it is understood that an addition reaction for adding CPD to DNTT is feasible.

Example 4
The addition reaction of dinaphthothienothiophene (DNTT) and furan (FRN, structural formula shown below) was confirmed by computer simulation using the semi-empirical method (MOPAC) and the non-experienced method (Gaussian) described above.

  The results are shown in the table below. In the above semi-empirical method (MOPAC), the heat of formation of DNTT was 117.56 kcal / mol, and the heat of formation of FRN was 2.96 kcal / mol.

  The additional positions in Table 4 are exemplified below. In addition, the symbol “FRN-FRN” in Table 4 indicates an addition product obtained by adding two FRNs.

  From the results in Table 4, it is understood that an addition reaction for adding FRN to DNTT is feasible.

Example 5
The addition reaction between dinaphthothienothiophene (DNTT) and anthracene (ANTH, structural formula shown below) was confirmed by computer simulation using the semi-empirical method (MOPAC) and non-experiential method (Gaussian) described above.

  The results are shown in the table below. In the above semi-empirical method (MOPAC), the heat of formation of DNTT was 117.56 kcal / mol, and the heat of formation of ANTH was 62.92 kcal / mol.

  The additional positions in Table 5 are shown below.

  From the results in Table 5, it is understood that an addition reaction for adding ANTH to DNTT is feasible.

Example 6
Computer simulation of the addition reaction between dinaphthothienothiophene (DNTT) and methyl triethylene-carboxylate (TCPM, structural formula shown below) using the semi-empirical method (MOPAC) and the non-experiential method (Gaussian) described above. Confirmed by.

  The results are shown in the table below. In the above semi-empirical method (MOPAC), the heat of formation of DNTT was 117.56 kcal / mol, and the heat of formation of TCPM was 40.24 kcal / mol.

  “Light” and “heat” in the reaction conditions of the addition reaction in Table 6 mean that the addition reaction can proceed by light and heat, respectively. The additional positions in Table 6 are exemplified below.

  From the results of Table 6, it is understood that an addition reaction for adding TCPM to DNTT is feasible.

Example 7
The addition reaction between dinaphthothienothiophene (DNTT) and methylpyrrole carboxylate (NMPC, structural formula shown below) was confirmed by computer simulation using the semi-empirical method (MOPAC) and the non-empirical method (Gaussian) described above. .

  The results are shown in the table below. In the above semi-empirical method (MOPAC), the heat of formation of DNTT was 117.56 kcal / mol, and the heat of formation of NMPC was −30.46 kcal / mol.

  “Light” and “heat” in the reaction conditions of the addition reaction in Table 7 mean that the addition reaction can proceed by light and heat, respectively. The additional positions in Table 7 are exemplified below.

  From the results in Table 7, it is understood that an addition reaction for adding NMPC to DNTT is feasible.

Example 8
The addition reaction of dinaphthothienothiophene (DNTT) and hydroxyphenyl-maleimide (HOPMI, structural formula shown below) was confirmed by computer simulation using the semi-empirical method (MOPAC) and the non-empirical method (Gaussian) described above. .

  The results are shown in the table below. In the above semi-empirical method (MOPAC), the heat of formation of DNTT was 117.56 kcal / mol, and the heat of formation of HOPMI was −38.13 kcal / mol.

  “Light” and “heat” in the reaction conditions of the addition reaction in Table 8 mean that the addition reaction can proceed by light and heat, respectively. The additional positions in Table 8 are exemplified below.

  From the results in Table 8, it is understood that an addition reaction for adding HOPMI to DNTT is feasible.

Example 9
The addition reaction between dinaphthothienothiophene (DNTT) and vinylene carbonate (VC (vinylene carbonate), structural formula shown below) was performed by computer simulation using the above semi-empirical method (MOPAC) and non-experiential method (Gaussian). confirmed.

  The results are shown in the table below. In the above semi-empirical method (MOPAC), the heat of formation of DNTT was 117.56 kcal / mol, and the heat of formation of VC was −59.30 kcal / mol.

  “Light” and “heat” in the reaction conditions of the addition reaction in Table 9 mean that the addition reaction can proceed by light and heat, respectively.

  The addition position in Table 9 is as shown by the following chemical formula.

M position: 2-7
L place: 4-5
Z position: 3-6
T position: 3-4 or 5-6
C position: 7b-14b

  From the results in Table 9, it is understood that an addition reaction for adding VC to DNTT is feasible.

<< Example 10A >>
500 mg (1.47 mmol) of dinaphthothienothiophene (DNTT, MW = 340.46), N-phenylmaleimide (PMI, MW = 173.16, structural formula shown below) synthesized by the method shown in Patent Document 2 2.54 g (14.7 mmol, 1000 mol% based on DNTT), 16.2 mg hydroquinone (MW110.1) as a radical scavenger (1 mol% based on N-phenylmaleimide) were mixed in a mesitylene solvent and under nitrogen Stir at 160 ° C. for 2 hours. Thereby, Diels-Alder addition reaction of DNTT and PMI was performed.

  After the reaction, a solid was obtained by filtration and washed with chloroform. This solid was confirmed to be DNTT (raw material) by NMR (yield 422.3 mg, yield 84.5 mol%).

  The filtrate was fractionated by HPLC (high-performance liquid chromatography, Agilent 1100 Series HPLC: High Performance Liquid Chromatography, SHISEIDO CAPCELL PAK C18 TYPE UG120, solvent: acetonitrile / water). (DNTT-1PMI, Mw = 513.63, yield 15.0 mol%) was obtained.

  The obtained DNTT-1PMI was a mixture of two stereoisomers (referred to as “stereoisomer A” and “stereoisomer B”, respectively). The analysis results for these stereoisomers are shown below. From the NMR results, it is estimated that stereoisomer A is an endo isomer and stereoisomer B is an exo isomer.

DNTT-1PMI (stereoisomer A)
¹ H-NMR (600 MHz, CDCl ₃ ): δ 8.30 (S, 1H), 8.23 (S, 1H), 7.95 (m, 1H), 7.89 (m, 1H), 7.50 (M, 2H), 7.47 (m, 2H), 7.25 (m, 2H), 7.12 (t, J = 7.3 Hz, 1H), 7.07 (dd, J = 7.3 Hz) , 7.7 Hz, 2H), 6.50 (d, J = 7.7 Hz, 2H), 5.30 (d, J = 3.3 Hz, 1H), 5.22 (d, J = 3.3 Hz, 1H), 3.54 (dd, J = 3.3 Hz, 8.1 Hz, 1H), 3.51 (dd, J = 3.3 Hz, 8.1 Hz, 1H)
MS (70 eV, DI): 514.10 m / z

DNTT-1PMI (stereoisomer B)
¹ H-NMR (600 MHz, CDCl ₃ ): δ 8.33 (s, 1H), 8.25 (s, 1H), 7.97 (m, 1H), 7.90 (m, 1H), 7.49 (M, 2H), 7.42 (m, 1H), 7.40 (m, 1H), 7.31 (m, 1H), 7.30 (m, 2H), 7.26 (m, 2H) 6.53 (m, 2H), 5.22 (d, J = 3.3 Hz, 1H), 5.18 (d, J = 3.3 Hz, 1H), 3.59 (dd, J = 3. 3Hz, 8.4Hz, 1H), 3.56 (dd, J = 3.3Hz, 8.4Hz, 1H)
MS (70 eV, DI): 513.05 m / z

  All detected values of mass spectrometry (MS) are substantially in agreement with DNTT-1PMI (Mw = 513.63).

  The thermal desorption characteristics of DNTT-1PMI (stereoisomers A and B) were evaluated by differential temperature balance analysis (Rigaku TG-DTA TG8120) using a temperature rise analysis at 1 ° C./min under nitrogen. According to this, DNTT-1PMI (stereoisomer A) had a weight loss of 31.9 wt% in the temperature range of 195 ° C. to 260 ° C. In addition, DNTT-1PMI (stereoisomer B) had a weight loss of 32.7 wt% in the temperature range of 155 ° C. to 260 ° C. The results are shown in FIG. From DNTT-1PMI (MW = 513.63), when PMI is thermally desorbed by reverse Diels-Alder reaction, the weight loss is −33.7 wt% (calculated value), so DNTT-1PMI (stereoisomer A And the analysis results in B) show that PMI was desorbed by heating. Further, NMR confirmed that the sample after thermal desorption was consistent with DNTT.

  Using each of DNTT-1PMI (stereoisomers A and B), a bottom contact bottom gate type FET (Field effect Transistor) element was fabricated as follows.

The substrate, on SiO ₂ oxide film of 300 nm SiO ₂ oxide film with n-doped silicon wafer (surface resistance 0.005 · cm), to prepare a source / drain metal electrodes having a channel length of 50μm and the channel width 1.5mm Obtained (bottom contact).

  While heating this base material to 50 ° C., a 3 wt% chloroform solution of DNTT-1PMI (stereoisomers A and B) was dropped into the channel portion of the base material and quickly volatilized to obtain a film. Was heated to obtain an organic semiconductor film. Here, DNTT-1PMI (stereoisomer A) was heated from room temperature at a heating rate of about 20 ° C./min under nitrogen and heated at 200 ° C. for 2 hours. Further, DNTT-1PMI (stereoisomer B) was heated from room temperature at a heating rate of about 20 ° C./min under nitrogen or in the atmosphere and heated at 160 ° C. for 2 hours.

Evaluation of the characteristics of the obtained organic semiconductor film showed p-type semiconductor characteristics. The carrier mobility was 0.01 to 0.0001 cm ² / Vs, and the on / off ratio was 10 ³ to 10 ⁵ . That is, with respect to DNTT-1PMI (stereoisomer B), semiconductor characteristics were obtained not only when heated under nitrogen but also when heated under air. The output characteristics and transfer characteristics of a field effect transistor (FET) are shown in FIGS. 5 and 6, respectively. Here, in FIG. 5, the vertical axis represents the drain current (I _D (A)), and the horizontal axis represents the drain voltage (V _D (V)). In FIG. 6, the vertical axis represents the drain current (I _D (A)), and the horizontal axis represents the gate voltage (V _G (V)).

  FIG. 8 shows the results of observing the crystal state of DNTT in the channel portion of the organic semiconductor film obtained using DNTT-1PMI (stereoisomer B) with a polarizing microscope. According to the observation of the channel portion by this polarizing microscope, it was confirmed that fine crystal particles of about 1 μm were formed on the entire surface of the organic semiconductor film after heating to obtain the organic semiconductor film. Therefore, it was confirmed that PMI was desorbed from DNTT-1PMI by heating, and crystals of DNTT were generated.

  Regarding the FET element having an organic semiconductor film obtained from DNTT-1PMI (stereoisomer B), the presence or absence of residual DNTT-1PMI (stereoisomers A and B) in the organic semiconductor film was confirmed by NMR. The results are shown in FIG. In FIG. 7, “DNTT”, “DNTT-1PMI (A)”, “DNTT-1PMI (B)”, and “FET DNTT-1PMI (B)” are DNTT, DNTT-1PMI (stereoisomerism), respectively. The analysis result about the organic-semiconductor film obtained from the body A), DNTT-1PMI (stereoisomer B), and DNTT-1PMI (stereoisomer B) is shown.

  According to FIG. 7, in the organic semiconductor film obtained from DNTT-1PMI (stereoisomer B), not only the NMR peak corresponding to DNTT but also the NMR corresponding to both DNTT-1PMI (stereoisomers A and B) A peak is observed. That is, it was confirmed that sufficient semiconductor characteristics can be provided even when DNTT-1PMI (stereoisomers A and B) remains in the organic semiconductor film.

  Here, DNTT has low solubility, and therefore, peaks are hardly observed by NMR. On the other hand, since DNTT-1PMI (stereoisomers A and B) has high solubility, an NMR peak corresponding to the dissolved content is observed. For this reason, from this NMR result, the ratio of DNTT-1PMI and DNTT in the organic semiconductor film cannot be determined. Note that the peak of “DNTT” in FIG. 7 has a larger magnification than other peaks, as can be understood from the fact that the noise is large. Further, since the size of the NMR peak of DNTT-1PMI (stereoisomers A and B) detected in the organic semiconductor film is approximately the same as that of the DNTT peak, the residual component DNTT- It can be seen that 1 PMI (stereoisomers A and B) is very small.

<< Example 10B >>
The addition reaction between dinaphthothienothiophene (DNTT) and N-phenylmaleimide was confirmed by computer simulation using the semi-empirical method (MOPAC) and non-experienced method (Gaussian) described above.

  The results are shown in the table below. In the above semi-empirical method (MOPAC), the heat of formation of DNTT was 117.56 kcal / mol, and the heat of formation of PMI was 5.83 kcal / mol.

  The addition position in Table 10 is as shown in the following chemical formula.

M position: 2-7
C position: 7b-14b
Z position: 3-6
MM position: 2-7 and 9-14
ZZ position: 3-6 and 10-13
MZ position and ZM position: 2-7 and 10-13

  From the results of Table 10, it is understood that an addition reaction for adding one molecule of PMI to one molecule of DNTT and an addition reaction for adding two molecules of PMI to one molecule of DNTT are feasible.

<< Example 10C >>
A 1.5 wt% chloroform solution of DNTT-1PMI (stereoisomer A) synthesized in Example 10A was dropped on a base material and dried on a hot plate at 50 ° C. to thereby form DNTT-1PMI on the substrate. A thin film of (stereoisomer A) was formed. Here, the base material was an n-doped silicon wafer (surface resistance 0.005 Ω · cm, thickness about 0.5 mm) having a 300 nm SiO ₂ oxide film.

  The substrate having a thin film of DNTT-1PMI (stereoisomer A) was placed on a hot plate heated to 210 ° C. in the atmosphere using tweezers, rapidly heated, and held for 3 minutes. By this rapid heating, phenylmaleimide was eliminated from DNTT-1PMI (stereoisomer A), and DNTT was precipitated. In this rapid heating, it was visually observed that the thin film changed from colorless to yellow in about 15 seconds. Considering that the thermal desorption temperature of DNTT-1PMI (stereoisomer A) is 195 ° C., it can be said that the temperature has reached about 200 ° C. in about 15 seconds. Equivalent to.

  FIG. 9 shows the observation results of DNTT deposited on the substrate with a polarizing microscope. As shown in FIG. 9, DNTT crystal particles having a major axis diameter exceeding 100 μm were precipitated.

A source / drain gold electrode having a channel length of 50 μm and a channel width of 1.5 mm was produced on the substrate on which DNTT had been deposited to produce an organic semiconductor element (bottom gate top contact). Evaluation of the characteristics of the obtained organic semiconductor film showed p-type semiconductor characteristics. The carrier mobility was 0.2 to 0.001 cm ² / Vs, and the on / off ratio was 10 ⁴ to 10 ⁶ .

<< Example 10D >>
A substrate having a thin film of DNTT-1PMI (stereoisomer A) was placed on a hot plate heated to 205 ° C. using tweezers, rapidly heated and held for 5 minutes in the same manner as in Example 10C. Thus, DNTT was precipitated. In this rapid heating, it was visually observed that the thin film changed from colorless to yellow in about 15 seconds. Considering that the thermal desorption temperature of DNTT-1PMI (stereoisomer A) is 195 ° C., it can be said that the temperature has reached about 200 ° C. in about 15 seconds. Equivalent to.

  FIG. 10 shows the observation results of DNTT deposited on the substrate with a polarizing microscope. As shown in FIG. 10, DNTT crystal particles having a major axis diameter exceeding 100 μm were precipitated.

<< Example 10E >>
A substrate having a thin film of DNTT-1PMI (stereoisomer A) is placed on a hot plate at room temperature using tweezers, and the temperature is raised from room temperature to 210 ° C. in air for 10 minutes (about 20 ° C./minute). The DNTT was precipitated in the same manner as in Example 10C except that it was kept isothermally at 210 ° C. for 3 minutes.

  The observation result of DNTT deposited on the substrate with a polarizing microscope is shown in FIG. As shown in FIG. 11, fine DNTT crystal particles of about 1 μm were precipitated.

<< Example 10F >>
A substrate having DNTT-1PMI (stereoisomer B) synthesized in Example 10A in place of DNTT-1PMI (stereoisomer A) and having a thin film of DNTT-1PMI (stereoisomer B) were prepared. DNTT was deposited in the same manner as in Example 10C except that it was placed on a hot plate heated to ° C. using tweezers, rapidly heated, and held for 15 minutes. In this rapid heating, it was visually observed that the thin film changed from colorless to yellow in about 15 seconds. Considering that the thermal desorption temperature of DNTT-1PMI (stereoisomer B) is 155 ° C., it can be said that the temperature has reached about 160 ° C. in about 15 seconds, which is about 640 ° C./min. Equivalent to.

  FIG. 12 shows the observation results of DNTT deposited on the substrate with a polarizing microscope. As shown in FIG. 12, DNTT crystal particles having a major axis diameter exceeding 20 μm were precipitated.

<< Example 10G >>
Instead of DNTT-1PMI (stereoisomer A), DNTT-1PMI (stereoisomer B) synthesized in Example 10A was used, and a substrate having a thin film of DNTT-1PMI (stereoisomer B) was used at room temperature. Other than having been placed on a hot plate using tweezers and heated from room temperature to 170 ° C. over 8 minutes (heating rate of about 20 ° C./min) and kept isothermal at 170 ° C. for 15 minutes in an air atmosphere Produced DNTT in the same manner as in Example 10C.

  FIG. 13 shows the observation results of DNTT deposited on the substrate with a polarizing microscope. As shown in FIG. 13, fine DNTT crystal particles of about 1 μm were precipitated.

Example 11
For the addition reaction of naphthaldehyde (NAL, structural formula shown below) and N-phenylmaleimide (PMI, structural formula shown below), using the above semi-empirical method (MOPAC) and non-experiential method (Gaussian) Confirmed by computer simulation.

  Similarly, the addition reaction of 3-methylthio-2-naphthaldehyde (MTNAL, structural formula shown below) and N-phenylmaleimide (PMI, structural formula shown below) was confirmed by computer simulation.

  The results are shown in the table below. In the above semi-empirical method (MOPAC), the heat of NAL generation was 9.58 kcal / mol, the heat of MTNAL generation was 12.28 kcal / mol, and the heat of PMI generation was 5.83 kcal / mol. .

  “Heat” in the reaction conditions of the addition reaction in Table 9 means that the addition reaction can be advanced by heat.

The additional positions in Table 11 are as follows:
M position: 1-4
Z position: 8-5

  From the results in Table 11, it is understood that an addition reaction for adding PMI to NAL and an addition reaction for adding PMI to MTNAL are feasible. Moreover, it can be understood from the results of Table 11 that the following Endo body and Exo body are formed.

Example 12
Dinaphthothienothiophene (DNTT, MW = 340.46) 500 mg (1.47 mmol), N-methylmaleimide (MMI, MW = 111.1) 1.63 g (14.7 mmol, 1000 mol% based on DNTT), radical supplementation Hydroquinone (MW110.1) 16.2 mg (1 mol% based on N-methylmaleimide) as an agent was mixed in a mesitylene solvent and stirred at 160 ° C for 2 hours under nitrogen. Thereby, Diels-Alder addition reaction of DNTT and MMI was performed.

  Then, the solid substance was obtained by filtration and washed with chloroform. This solid was confirmed to be DNTT (raw material) by NMR (yield 343.5 mg, yield 68.7 mol%).

  The filtrate was fractionated by HPLC to obtain 113.2 mg (DNTT-1MMI, Mw = 451.56, yield 28.5 mol%) of an adduct compound in which MMI1 molecule was added to DNTT. The structural formula of this addition compound is shown below.

  The obtained DNTT-1MMP was a mixture of two types of stereoisomers (referred to as “stereoisomer A” and “stereoisomer B”, respectively). The analysis results for these stereoisomers are shown below. From the NMR results, it is estimated that stereoisomer A is an endo isomer and stereoisomer B is an exo isomer.

DNTT-1MMI (stereoisomer A)
¹ H-NMR (600 MHz, CDCl ₃ ): δ 8.28 (s, 1H), 8.19 (s, 1H), 7.94 (m, 1H), 7.88 (m, 1H), 7.47 (M, 2H), 7.46 (m, 1H), 7.42 (m, 1H), 7.21 (m, 2H), 5.18 (d, J = 2.9 Hz, 1H), 5. 11 (d, J = 2.9 Hz, 1H), 3.37 (dd, J = 2.9 Hz, 7.7 Hz, 1H), 3.35 (dd, J = 2.9 Hz, 7.7 Hz, 1H) , 2.53 (s, 3H)
MS (70 eV, DI): 451.00 m / z

DNTT-1MMI (stereoisomer B)
¹ H-NMR (600 MHz, CDCl ₃ ): δ 8.32 (s, 1H), 8.23 (s, 1H), 7.95 (m, 1H), 7.89 (m, 1H), 7.49 (M, 2H), 7.33 (m, 1H), 7.31 (m, 1H), 7.17 (m, 2H), 5.11 (d, J = 3.3 Hz, 1H), 5. 07 (d, J = 3.3 Hz, 1H), 3.43 (dd, J = 3.3 Hz, 8.4 Hz, 1H), 3.40 (dd, J = 3.3 Hz, 8.4 Hz, 1H) , 2.52 (s, 3H)
MS (70 eV, DI): 451.30 m / z

  All detected values of mass spectrometry (MS) are substantially in agreement with DNTT-1MMI (Mw = 451.56).

  The thermal desorption characteristics of DNTT-1MMI were evaluated using differential thermal balance analysis as in Example 10A. According to this, in the DNTT-1MMI (stereoisomer A), thermal desorption occurred in the temperature range of 220 ° C to 260 ° C. Since the sample amount of DNTT-1MMI (stereoisomer B) was very small, the thermal desorption characteristics could not be evaluated.

Regarding DNTT-1MMI (stereoisomer A), an organic semiconductor film was obtained as in Example 10A, and the semiconductor characteristics were evaluated. Here, the heating for obtaining the organic semiconductor film was performed at 225 ° C. for 2 hours under nitrogen. Evaluation of the characteristics of the obtained organic semiconductor film showed p-type semiconductor characteristics. The carrier mobility was 0.01 to 0.0001 cm ² / Vs, and the on / off ratio was 10 ³ to 10 ⁵ .

Example 13
Dinaphthothienothiophene (DNTT, MW = 340.46) 500 mg (1.47 mmol), N-cyclohexylmaleimide (CHMI, MW = 179.22) 2.63 g (14.7 mmol, 1000 mol% based on DNTT), radical supplement Hydroquinone (MW110.1) 16.2 mg (1 mol% based on N-phenylmaleimide) as an agent was mixed in a mesitylene solvent and stirred at 160 ° C. for 2 hours under nitrogen. Thereby, Diels-Alder addition reaction of DNTT and CHMI was performed.

  Then, the solid substance was obtained by filtration and washed with chloroform. This solid was confirmed to be DNTT (raw material) by NMR (yield 478.5 mg, yield 95.7 mol%).

  The filtrate was fractionated by HPLC to obtain 28.9 mg (DNTT-1CHMI, Mw = 519.13, yield 2.1 mol%) of an addition compound in which CHMI1 molecule was added to DNTT. The structural formula of this addition compound is shown below.

  The analysis results of the obtained DNTT-1CHMI are shown below. Note that a stereoisomer was not obtained for DNTT-1CHMI.

¹ H-NMR (600 MHz, CDCl ₃ ): δ 8.31 (s, 1H), 8.23 (s, 1H), 7.95 (m, 1H), 7.89 (m, 1H), 7.48 (M, 2H), 7.33 (m, 1H), 7.32 (m, 1H), 7.17 (m, 2H), 5.08 (d, J = 3.4 Hz, 1H), 5. 05 (d, J = 3.4 Hz, 1H), 3.51 (m, 1H), 3.33 (dd, J = 3.4 Hz, 8.3 Hz, 1H), 3.30 (dd, J = 3 .4 Hz, 8.3 Hz, 1 H), 1.68 (m, 4 H), 1.58 (m, 1 H), 1.09 (m, 3 H), 0.84 (m, 2 H)
MS (70 eV, DI): 519.20 m / z

  The detection value of mass spectrometry (MS) is substantially in agreement with DNTT-1CHMI (Mw = 519.13).

  The thermal desorption characteristics of DNTT-1CHMI were evaluated using differential thermal balance analysis as in Example 10A. According to this, in DNTT-1CHMI, thermal desorption occurred in a temperature range of 200 ° C. to 280 ° C.

Regarding DNTT-1CHMI, an organic semiconductor film was obtained as in Example 10A, and the semiconductor characteristics were evaluated. Here, the heating for obtaining the organic semiconductor film was performed at 210 ° C. for 2 hours under nitrogen. Evaluation of the characteristics of the obtained organic semiconductor film showed p-type semiconductor characteristics. The carrier mobility was 0.01 to 0.0001 cm ² / Vs, and the on / off ratio was 10 ³ to 10 ⁵ .

Example 14
Dinaphthothienothiophene (DNTT, MW = 340.46) 2000 mg (5.87 mmol), N-benzylmaleimide (BZMI, MW = 187.19) 10.99 g (58.7 mmol, 1000 mol% based on DNTT), radical supplementation Hydroquinone (MW110.1) 64.8 mg (1 mol% based on N-benzylmaleimide) was mixed in the mesitylene solvent as an agent and stirred at 160 ° C. for 4 hours under nitrogen. Thereby, Diels-Alder addition reaction of DNTT and BZMI was performed.

  Then, the solid substance was obtained by filtration and washed with chloroform. This solid was confirmed to be DNTT (raw material) by NMR (yield 980 mg, yield 49.0 mol%).

  The filtrate was fractionated by HPLC to obtain 659.2 mg (DNTT-1BZMI, Mw = 527.10, yield 21.3 mol%) of an addition compound in which BZMI1 molecule was added to DNTT. The structural formula of this addition compound is shown below.

  The analysis result about obtained DNTT-1BZMI is shown below. Note that a stereoisomer was not obtained for DNTT-1BZMI.

¹ H-NMR (600 MHz, CDCl ₃ ): δ 8.31 (s, 1H), 8.22 (s, 1H), 7.95 (m, 1H), 7.89 (m, 1H), 7.48 (M, 2H), 7.23 (m, 2H), 7.18 (t, J = 7.3 Hz, 1H), 7.14 (dd, J = 7.3 Hz, 7.3 Hz, 2H), 6 .99 (m, 2H), 6.75 (d, J = 7.3 Hz, 2H), 5.08 (d, J = 3.3 Hz, 1H), 5.05 (d, J = 3.3 Hz, 1H), 4.28 (s, 2H), 3.44 (dd, J = 3.3 Hz, 8.4 Hz, 1H), 3.41 (dd, J = 3.3 Hz, 8.4 Hz, 1H)
MS (70 eV, DI): 527.95 m / z

  The detection value of mass spectrometry (MS) is substantially in agreement with DNTT-1BZMI (Mw = 527.10).

  The thermal desorption characteristics of DNTT-1BZMI were evaluated using differential thermal balance analysis as in Example 10A. According to this, in DNTT-1BZMI, thermal desorption occurred in a temperature range of 190 ° C to 260 ° C.

Regarding DNTT-1BZMI, an organic semiconductor film was obtained as in Example 10A, and the semiconductor characteristics were evaluated. Here, the heating for obtaining the organic semiconductor film was performed at 200 ° C. for 2 hours under nitrogen. Evaluation of the characteristics of the obtained organic semiconductor film showed p-type semiconductor characteristics. Each carrier mobility, a 0.01~0.0001cm ² / Vs, the on / off ratio was ¹⁰ 3 to 10 ^5.

Example 15
Dinaphthothienothiophene (DNTT, MW = 340.46) 500 mg (1.47 mmol), Nt-butylmaleimide (TBMI, MW = 153.18) 2.25 g (14.7 mmol, 1000 mol% based on DNTT), Hydroquinone (MW110.1) 16.2 mg (1 mol% based on Nt-butylmaleimide) as a radical scavenger was mixed in a mesitylene solvent and stirred at 160 ° C. for 4 hours under nitrogen. Thereby, Diels-Alder addition reaction with TBMI was performed on DNTT.

  Then, the solid substance was obtained by filtration and washed with chloroform. This solid was confirmed to be DNTT (raw material) by NMR (yield: 486 mg, yield: 97.2 mol%).

  The filtrate was fractionated by HPLC to obtain 2.1 mg of an addition compound (DNTT-1TBMI, Mw = 493.64, yield 0.29 mol%) in which 1 molecule of TBMI was added to DNTT. The structural formula of this addition compound is shown below.

  The analysis results for DNTT-1TBMI are shown below. Note that a stereoisomer was not obtained for DNTT-1TBMI.

¹ H-NMR (600 MHz, CDCl ₃ ): δ 8.31 (s, 1H), 8.22 (s, 1H), 7.95 (m, 1H), 7.89 (m, 1H), 7.48 (M, 2H), 7.35 (m, 1H), 7.33 (m, 1H), 7.18 (m, 2H), 5.06 (d, J = 3.3 Hz, 1H), 5. 02 (d, J = 3.3 Hz, 1H), 3.23 (dd, J = 3.3 Hz, 8.8 Hz, 1H), 3.16 (dd, J = 3.3 Hz, 8.8 Hz, 1H) , 2.59 (s, 9H)

Example 16
Dinaphthothienothiophene (DNTT, MW = 340.46) 500 mg (1.47 mmol), maleic anhydride (MA, MW = 98.06) 1.44 g (14.7 mmol, 1000 mol% based on DNTT), radical scavenger As hydroquinone (MW110.1) as a mixture was mixed in a mesitylene solvent and stirred at 160 ° C. for 4 hours under nitrogen. Thereby, Diels-Alder addition reaction of DNTT and MA was performed.

  Then, the solid substance was obtained by filtration and washed with chloroform. This solid was confirmed to be DNTT (raw material) by NMR (yield 472.2 mg, yield 94.4 mol%).

  The filtrate was fractionated by HPLC to obtain 32.2 mg (DNTT-1MA, Mw = 438.52, yield 5.0 mol%) of an addition compound in which MA1 molecule was added to DNTT. The structural formula of this addition compound is shown below.

  The analysis results for the obtained DNTT-1MA are shown below.

¹ H-NMR (600 MHz, CDCl ₃ ): δ 8.31 (s, 1H), 8.22 (s, 1H), 7.95 (m, 1H), 7.89 (m, 1H), 7.48 (M, 2H), 7.23 (m, 2H), 7.00 (m, 2H), 5.09 (d, J = 3.3 Hz, 1H), 5.05 (d, J = 3.3 Hz) , 1H), 3.44 (dd, J = 3.3 Hz, 8.4 Hz, 1H), 3.41 (dd, J = 3.3 Hz, 8.4 Hz, 1H)
MS (70 eV, DI): 341.31 m / z

  The detection value of mass spectrometry (MS) is consistent with DNTT (molecular weight 340.46), and when DNTT-1MA is exposed to the conditions of mass spectrometry (70 eV, DI), MA is desorbed and DNTT is It is shown that it is playing.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to form the organic-semiconductor layer and organic-semiconductor device which consist of a condensed polycyclic aromatic compound using a solution method. Such a solution method is generally preferable in terms of manufacturing cost, manufacturing speed, etc. Therefore, according to the present invention, an organic semiconductor layer and an organic semiconductor device can be efficiently formed.

DESCRIPTION OF SYMBOLS 1 Organic semiconductor 2 Source electrode 3 Drain electrode 5 Dielectric layer (silicon oxide)
7 Silicon wafer substrate (gate electrode)
10 Organic semiconductor devices

Claims (31)

It has a structure in which a compound (II) having a double bond is detachably added to the substituted or unsubstituted condensed polycyclic aromatic compound of the following formula (I-4) via the double bond. And:
(Y is an element independently selected from chalcogen);
The compound (II) having a double bond has any of the following formulas (II-1) to (II-12):
(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); and the substitution of the condensed polycyclic aromatic compound of formula (I-4) is halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms And having 2 to 20 carbon atoms Lucinyl group, substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, ester group having 2 to 10 carbon atoms, ether group having 1 to 20 carbon atoms, ketone group having 1 to 20 carbon atoms, carbon Substitution independently selected from the group consisting of an amino group having 1 to 20 atoms, an amide group having 1 to 20 carbon atoms, an imide group having 1 to 20 carbon atoms, and a sulfide group having 1 to 20 carbon atoms Made by the group,
Addition compounds.   The addition compound according to claim 1, wherein the compound (II) having a double bond can be eliminated from the condensed polycyclic aromatic compound of the formula (I) by reduced pressure and / or heating. The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-6):
The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-1):
The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-2):
The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-3):
The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-4):
The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-5):
The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-7):
The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-8):
The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-9):
The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-10):
The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-11):
The addition compound according to claim 1 or 2, wherein the compound (II) having a double bond has the following formula (II-12):
The addition compound according to claim 1, which is a compound having the following formula (III-1) or a stereoisomer thereof:
(Y is an element independently selected from chalcogen,
R and R _r are each independently hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Alkoxy group, aromatic group having 4 to 10 carbon atoms, ester group having 1 to 10 carbon atoms, ether group having 1 to 10 carbon atoms, ketone group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms Selected from the group consisting of an amino group, 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, and the condensed benzene ring moiety is substituted or Unsubstituted). The addition compound according to claim 1, which is a compound having the following formula (III-6) or a stereoisomer thereof:
(Y is an element independently selected from chalcogen,
R is independently hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, Aromatic group having 4 to 10 carbon atoms, ester group having 1 to 10 carbon atoms, ether group having 1 to 10 carbon atoms, ketone group having 1 to 10 carbon atoms, amino group having 1 to 10 carbon atoms Selected from the group consisting of 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, and the fused benzene ring moiety may be substituted or unsubstituted. is there).   The adduct according to claim 16, which is an Exo adduct.   The addition compound containing solution formed by melt | dissolving the addition compound as described in any one of Claims 1-17 in a solvent.   The addition compound according to any one of claims 1 to 17 and at least one stereoisomer thereof are dissolved in a solvent, and the thermal desorption temperature relative to the sum of the addition compound and the stereoisomer is lowest. The ratio of stereoisomers {the stereoisomer with the lowest thermal desorption temperature of the addition compound and its stereoisomer / the addition compound and its stereoisomer} is more than 50 mol%. solution.   The Exo-form and Endo-form of the addition compound according to any one of claims 1 to 17 are contained in a solvent, and the thermal desorption temperature relative to the sum of the Exo-form and Endo-form of the addition compound is lower The solution according to claim 19, wherein the ratio of the stereoisomers of {the stereoisomer with the lower thermal desorption temperature of the Exo and Endo isomers / (Exo ++ Endo)} is more than 50 mol%.   The Exo isomer and Endo isomer of the addition compound according to claim 16 are contained in a solvent, and the ratio of the Exo isomer to the sum of the Exo isomer and the Endo isomer of the addition compound {Exo isomer / (Exo isomer + Endo isomer)] } Is a solution according to claim 18, wherein> is more than 50 mol%. A step of applying the additive compound-containing solution according to any one of claims 18 to 21 to a substrate to produce a film, and subjecting the film to reduced pressure and / or heating, Removing and removing the compound (II) having a double bond to obtain an organic semiconductor film comprising a substituted or unsubstituted condensed polycyclic aromatic compound of the formula (I-4);
A method for producing an organic semiconductor film, comprising:   The method according to claim 22, wherein the elimination and removal of the compound (II) having a double bond is carried out by heating at a heating rate exceeding 100 ° C / min.   The heating comprises bringing the substrate having the film into direct contact with a heated object, introducing the substrate having the film into a heated region, and / or on the film side or the substrate side. The method according to claim 22 or 23, which is carried out by radiating electromagnetic waves.   The method according to claim 23 or 24, wherein the organic semiconductor film has a crystal of the condensed polycyclic aromatic compound of the formula (I-4) having a major axis diameter of more than 5 µm.   The method according to any one of claims 22 to 25, wherein the desorption and removal are performed in the atmosphere.   The manufacturing method of an organic-semiconductor device including the step which produces | generates an organic-semiconductor film by the method as described in any one of Claims 22-26.   An organic semiconductor device having an organic semiconductor film, wherein the organic semiconductor film is made of a substituted or unsubstituted condensed polycyclic aromatic compound of the formula (I-4), and the organic semiconductor film is The organic-semiconductor device containing the addition compound as described in any one of Claims 1-17. A thin film transistor having a source electrode, a drain electrode, a gate electrode, a gate insulating film, and the organic semiconductor film, wherein the source electrode, the drain electrode, and the gate electrode are insulated by the gate insulating film, and the gate electrode 29. The organic semiconductor device of claim 28 , wherein the organic semiconductor device is a thin film transistor that controls a current flowing through the organic semiconductor from the source electrode to the drain electrode by a voltage applied to the source.   18. The method according to claim 1, comprising a step of mixing a substituted or unsubstituted condensed polycyclic aromatic compound of the formula (I-4) with the compound (II) having a double bond. A method for synthesizing organic compounds. (A) providing an addition compound comprising the steps of:
The addition compound has a structure in which a compound (II) having a double bond is added to the compound of the following formula (I ′) via the double bond:
Ar ₁ Q (I ′)
{Ar ₁ is a substituted or unsubstituted fused benzene ring moiety of (b4) below:
Q has the following formula and forms part of the fused aromatic ring of Ar ₁ :
(Y is an element selected from chalcogen)}; and the substitution of the condensed benzene ring part in (b4) is halogen, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms , An alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 4 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, an ether group having 1 to 20 carbon atoms, and the number of carbon atoms A group consisting of a 1-20 ketone group, an amino group having 1-20 carbon atoms, an amide group having 1-20 carbon atoms, an imide group having 1-20 carbon atoms, and a sulfide group having 1-20 carbon atoms. Made by substituents independently selected from each other,
Providing an adduct compound;
(B) reacting two molecules of the addition compound to obtain a compound of the following formula:
Formula Ar ₁ Q = QAr ₁
(Q = Q represents the following structure:
And (c) reacting the resulting compound of the formula Ar ₁ Q = QAr ₁ with iodine,
The manufacturing method of the addition compound as described in any one of Claims 1-17 containing this.