JP6386754B2 - Organic semiconductors containing polycyclic aromatic compounds - Google Patents

Description

  The present invention relates to a polycyclic aromatic compound containing an azulene ring and a method for producing the same. Moreover, it is related with the use of the said polycyclic aromatic compound.

  To date, pentacene (a) and picene (b) shown below are known as 22π hydrocarbons in which five benzene rings are condensed in a linear form. These exhibit strong intermolecular interactions derived from a π-conjugated system spreading on a plane, and are reported to be useful as field effect transistors (Patent Document 1, Non-Patent Document 1, and Non-Patent Document 2).

  Azulene is a 10π-type aromatic hydrocarbon having a structure in which a 5-membered ring and a 7-membered ring are condensed, but it can also be said that a cycloheptatrienium cation and a cyclopentadienyl anion are condensed. . Therefore, by adopting an electron arrangement in which the 5-membered ring is negative and the 7-membered ring is positively polarized, it has a characteristic of having a large dipole moment despite being a hydrocarbon. It has been pointed out that this feature may be useful as an electronic material such as an organic semiconductor.

  Patent Document 2 and Patent Document 3 describe organic semiconductor materials or charge transfer materials made of a compound containing a plurality of azulene rings. However, these were obtained by bonding two azulene rings directly or via an aromatic ring with a single bond, and had a structure represented by the following formula (c).

  Non-Patent Document 3 and Non-Patent Document 4 describe polycyclic aromatic compounds containing an azulene ring and further condensed with another aromatic ring. The polycyclic aromatic compound described therein has a structure represented by the following formulas (d) to (f) and is a tetracyclic compound having a structure in which an azulene ring and a naphthalene ring are condensed. It was. In addition, these documents do not describe any semiconductor characteristics of these polycyclic aromatic compounds.

JP 2009-218333 A JP 2013-58674 A Japanese Patent Laid-Open No. 2003-261481

Lin, Y.-Y .; Gundlach, D.J .; Nelson, S.F .; Jackson, T.N., IEEE Electron Device Lett. 1997, 18, 606-608 Okamoto, H .; Kawasaki, N .; Kaji, Y .; Kubozono, Y .; Fujiwara, A .; Yamaji, M., J. Am. Chem. Soc., 2008, 130, 10470-10471 Yasunami, M .; Yang, P.W .; Kondo, Y .; Noro, Y .; Takase, K., Chemistry Letters, 1980, 167-170 Yamamura, K .; Kawabata, S .; Kimura, T .; Eda, K .; Hashimoto, M., J. Org. Chem., 2005, 70, 8902-8906

  Until now, as the polycyclic aromatic compound containing an azulene ring, as described above, only a compound having a structure in which an azulene ring and a naphthalene ring are condensed is known, and there is a method for synthesizing a compound having another structure. It was sought after. In particular, polycyclic aromatic compounds containing five or more rings containing an azulene ring and polycyclic aromatic compounds containing an azulene ring and a heteroaromatic ring have not been reported as examples of their synthesis. There has been a need to provide aromatic compounds. A new organic semiconductor containing a polycyclic aromatic compound has also been demanded.

  The above-described problem is characterized in that a compound represented by the following formula (1), formula (3), formula (5) or formula (7) is cyclized to the following formula (2), formula (4), This is solved by providing a method for producing a polycyclic aromatic compound represented by formula (6) or formula (8).

[In Formula (1), R is an alkyl group which may have a substituent. X ^{1 to} X ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, Aryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocyclic group which may have a substituent, hydroxyl group which may be protected, alkoxy group, aryloxy group, formyl Group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an optionally protected amino group , Alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, protected A thiol group, an alkylthio group, an arylthio group, an optionally protected sulfinic acid group or a salt thereof, an alkylsulfinyl group, an arylsulfinyl group, an optionally protected sulfonic acid group or a salt thereof, an alkylsulfonyl group, An arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group. X ^{2 to} X ⁷ may be connected to each other. X ² and X ³ , X ³ and X ⁴ , X ⁴ and X ⁵ , and X ⁵ and X ⁶ may be connected to each other to form an aromatic ring. Ar ¹ represents an aromatic ring. ]

[In the formula (2), X ^{1 to} X ⁷ and Ar ¹ are the same as those in the formula (1). ]

[In the formula (3), R, X ¹ and Ar ¹ are the same as in the formula (1). X ^{8 to} X ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, Aryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocyclic group which may have a substituent, hydroxyl group which may be protected, alkoxy group, aryloxy group, formyl Group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an optionally protected amino group , Alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, protected Thiol group, alkylthio group, arylthio group, sulfinic acid group or salt thereof which may be protected, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group or salt thereof which may be protected, alkylsulfonyl group An arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group. X ^{8 to} X ¹³ may be connected to each other. X ⁹ and X ¹⁰ , X ¹⁰ and X ¹¹ , X ¹² and X ¹³ may each form an aromatic ring. ]

Wherein ^{(4), X 1, X} 8 ~X 13 and Ar ¹ are as defined in the formula (3). ]

[In formula (5), R and X ¹ are the same as those in formula (1). X ^{14 to} X ¹⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, Aryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocyclic group which may have a substituent, hydroxyl group which may be protected, alkoxy group, aryloxy group, formyl Group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an optionally protected amino group , Alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, protection Thiol group, alkylthio group, arylthio group, optionally protected sulfinic acid group or salt thereof, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group or salt thereof optionally protected, alkylsulfonyl A group, an arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group. X ^{14 to} X ¹⁹ may be connected to each other. X ¹⁴ and X ¹⁵ , X ¹⁵ and X ¹⁶ , X ¹⁶ and X ¹⁷ , and X ¹⁷ and X ¹⁸ may each form an aromatic ring. Ar ² represents an aromatic ring. ]

[In the formula (6), X ¹ , X ^{14 to} X ¹⁹ and Ar ² are the same as in the formula (5). ]

[In the formula (7), R and X ¹ are the same as those in the formula (1). X ^{20 to} X ²⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, Aryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocyclic group which may have a substituent, hydroxyl group which may be protected, alkoxy group, aryloxy group, formyl Group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an optionally protected amino group , Alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, protection Thiol group, alkylthio group, arylthio group, optionally protected sulfinic acid group or salt thereof, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group or salt thereof optionally protected, alkylsulfonyl A group, an arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group. X ^{20 to} X ²⁵ may be connected to each other. X ²¹ and X ²² , X ²² and X ²³ , and X ²⁴ and X ²⁵ may each form an aromatic ring. Ar ² is the same as in formula (5). ]

[In the formula (8), X ¹ , X ^{20 to} X ²⁵ and Ar ² are the same as in the formula (7). ]

At this time, Ar ¹ and Ar ² are preferably condensed aromatic rings. It is also preferred that Ar ¹ and Ar ² are heteroaromatic rings. Moreover, it is also preferable to carry out the cyclization reaction in the presence of an acid catalyst, and the acid catalyst is more preferably a Lewis acid catalyst comprising a transition metal salt.

  The said subject is also solved by providing the polycyclic aromatic compound represented by following formula (2), Formula (4), Formula (6), or Formula (8).

[In Formula (2), X ^{1 to} X ⁷ each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An alkynyl group that may have a substituent, an aryl group that may have a substituent, a cycloalkyl group that may have a substituent, a heterocyclic group that may have a substituent, a hydroxyl group that may be protected, Alkoxy group, aryloxy group, formyl group, optionally protected carboxyl group or salt thereof, alkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyl group, aryloxycarbonyl group, protection May be amino group, alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium Group, thiol group which may be protected, alkylthio group, arylthio group, sulfinic acid group which may be protected or salt thereof, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group which may be protected or salt thereof , Alkylsulfonyl group, arylsulfonyl group, alkylazo group, arylazo group, optionally protected phosphate group or salt thereof, optionally protected phosphorous acid group or salt thereof, cyano group, nitro group or azide group It is. X ^{2 to} X ⁷ may be connected to each other. X ² and X ³ , X ³ and X ⁴ , X ⁴ and X ⁵ , and X ⁵ and X ⁶ may be connected to each other to form an aromatic ring. Ar ¹ represents a condensed aromatic ring or a heteroaromatic ring. ]

[In Formula (4), X ¹ and Ar ¹ are the same as those in Formula (2). X ^{8 to} X ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, Aryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocyclic group which may have a substituent, hydroxyl group which may be protected, alkoxy group, aryloxy group, formyl Group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an optionally protected amino group , Alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, protected Thiol group, alkylthio group, arylthio group, sulfinic acid group or salt thereof which may be protected, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group or salt thereof which may be protected, alkylsulfonyl group An arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group. X ^{8 to} X ¹³ may be connected to each other. X ⁹ and X ¹⁰ , X ¹⁰ and X ¹¹ X ¹² and X ¹³ may each form an aromatic ring. ]

Wherein (6), ^{X 1} is the same as equation (2). X ^{14 to} X ¹⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, Aryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocyclic group which may have a substituent, hydroxyl group which may be protected, alkoxy group, aryloxy group, formyl Group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an optionally protected amino group , Alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, protection Thiol group, alkylthio group, arylthio group, optionally protected sulfinic acid group or salt thereof, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group or salt thereof optionally protected, alkylsulfonyl A group, an arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group. X ^{14 to} X ¹⁹ may be connected to each other. X ¹⁴ and X ¹⁵ , X ¹⁵ and X ¹⁶ , X ¹⁶ and X ¹⁷ , and X ¹⁷ and X ¹⁸ may each form an aromatic ring. Ar ² represents a condensed aromatic ring or a heteroaromatic ring. ]

Wherein (8), ^{X 1} is the same as equation (2). X ^{20 to} X ²⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, Aryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocyclic group which may have a substituent, hydroxyl group which may be protected, alkoxy group, aryloxy group, formyl Group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an optionally protected amino group , Alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, protection Thiol group, alkylthio group, arylthio group, optionally protected sulfinic acid group or salt thereof, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group or salt thereof optionally protected, alkylsulfonyl A group, an arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group. X ^{20 to} X ²⁵ may be connected to each other. X ²¹ and X ²² , X ²² and X ²³ , and X ²⁴ and X ²⁵ may each form an aromatic ring. Ar ² is the same as in formula (6). ]

  Moreover, the suitable embodiment of this invention is an organic semiconductor containing the said polycyclic aromatic compound.

  According to the production method of the present invention, various polycyclic aromatic compounds containing an azulene ring can be easily produced. In particular, novel compounds such as a polycyclic aromatic compound having 5 or more rings containing an azulene ring and a polycyclic aromatic compound containing an azulene ring and a heteroaromatic ring can be provided. And the organic semiconductor containing such a polycyclic aromatic compound can also be provided.

10 is a cross-sectional view illustrating a structure of a transistor in Example 8. FIG.

  In the production method of the present invention, the compound represented by the formula (1), formula (3), formula (5) or formula (7) is cyclized to obtain the formula (2), formula (4), The polycyclic aromatic compound represented by the formula (6) or the formula (8) is produced. The compound represented by the formula (1) is cyclized to produce the polycyclic aromatic compound represented by the formula (2). The compound represented by formula (3) is cyclized to produce a polycyclic aromatic compound represented by formula (4). The compound represented by the formula (5) is cyclized to produce the polycyclic aromatic compound represented by the formula (6). Moreover, the compound represented by Formula (7) is cyclized to produce the polycyclic aromatic compound represented by Formula (8).

  The compound represented by the formula (1) has the structure shown below.

  In formula (1), R is an alkyl group which may have a substituent. The alkyl group may be a linear alkyl group or a branched alkyl group. The substituent that the alkyl group has is not particularly limited as long as it does not inhibit the cyclization reaction, and is a halogen atom, alkenyl group, alkynyl group, aryl group, cycloalkyl group, heterocyclic group, hydroxyl group that may be protected. , An alkoxy group, an aryloxy group, a formyl group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Amino group that may be protected, alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, thiol group that may be protected, alkylthio group, arylthio group, sulfine that may be protected Acid group or its Alkylsulfinyl group, arylsulfinyl group, sulfonic acid group which may be protected or a salt thereof, alkylsulfonyl group, arylsulfonyl group, alkylazo group, arylazo group, a phosphoric acid group which may be protected or a salt thereof, protection Examples thereof may include a phosphite group or a salt thereof, a cyano group, a nitro group or an azide group. The carbon number of R as a whole is not particularly limited, but is preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less. Particularly preferred as R is an alkyl group having 5 or less carbon atoms that has no substituent.

In formula (1), X ^{1 to} X ⁷ each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An alkynyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, a hydroxyl group which may be protected, an alkoxy Group, aryloxy group, formyl group, optionally protected carboxyl group or a salt thereof, alkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyl group, aryloxycarbonyl group, protected Amino group, alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium An optionally protected thiol group, an alkylthio group, an arylthio group, an optionally protected sulfinic acid group or a salt thereof, an alkylsulfinyl group, an arylsulfinyl group, an optionally protected sulfonic acid group or a salt thereof, An alkylsulfonyl group, an arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group; is there. The alkyl group, alkenyl group, and alkynyl group may be linear or branched.

Substituents X ¹ to X ⁷ has is not particularly limited as long as it does not inhibit the cyclization reaction, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a cycloalkyl group, a heterocyclic group, protected Hydroxyl group, alkoxy group, aryloxy group, formyl group, optionally protected carboxyl group or salt thereof, alkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyl group , Aryloxycarbonyl group, amino group which may be protected, alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, thiol group which may be protected, alkylthio group, arylthio group, protection Sulfi that may have been Acid group or salt thereof, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group which may be protected or salt thereof, alkylsulfonyl group, arylsulfonyl group, alkylazo group, arylazo group, phosphoric acid group which may be protected Or the salt, the phosphorous acid group which may be protected, or its salt, a cyano group, a nitro group, or an azide group is illustrated.

X ^{2 to} X ⁷ may be linked to each other to form a ring structure. At this time, X ² and X ³ , X ³ and X ⁴ , X ⁴ and X ⁵ , X ⁵ and X ⁶ may be linked to form an aromatic ring. In this case, the aromatic ring and azulene The rings are condensed and conjugated. The aromatic ring is not particularly limited as long as it can be conjugated with an azulene ring, and examples thereof include a benzene ring and a naphthalene ring. The aromatic ring may have a substituent, the substituent in this case, same as the substituents which the X ¹ to X ⁷ has is exemplified.

The number of carbon atoms of X ^{1 to} X ⁷ is not particularly limited, but is preferably 20 or less. When X ^{2 to} X ⁷ are connected to each other, the number of carbon atoms as a whole unit contributing to the connection is preferably 20 or less.

In formula (1), Ar ¹ represents an aromatic ring. The aromatic ring is not particularly limited as long as it does not inhibit the cyclization reaction, and examples thereof include a benzene ring, a condensed aromatic ring, and a heteroaromatic ring. These aromatic rings may have a substituent, and examples of the substituent in that case include the same substituents as those in X ^{1 to} X ⁷ .

Among these, when Ar ¹ is a condensed aromatic ring, a polycyclic aromatic compound having five or more rings including an azulene ring can be obtained. A polycyclic aromatic compound that has never been synthesized can be obtained, and its significance is extremely large. Examples of the condensed aromatic ring include those listed in the following formulas (9a) to (9n). The fused aromatic rings shown in formulas (9a) to (9n) are bonded to other parts of formula (1) at adjacent carbon atoms that are not bridgehead positions. Thus, for example, in the case of the naphthalene ring of the formula (9a), when bonded at the 1-position and 2-position (5-position and 6-position), and when bonded at the 2-position and 3-position (6-position and 7-position) There are three ways of bonding at the 3rd and 4th positions (7th and 8th positions), and each becomes a compound of the different formula (1).

From the viewpoint of solubility of the compound represented by the formula (1) and its raw material compound in a solvent, it is preferable that Ar ¹ is not too large. From this viewpoint, the condensed aromatic rings represented by (9a) to (9l) are preferable, and the condensed aromatic rings represented by (9a) to (9e) are more preferable. On the other hand, from the viewpoint of stability of the compound represented by the formula (1) and the compound represented by the formula (2) obtained by cyclization thereof, (9a), (9b), (9d), (9h) , (9i) and (9n) are preferred.

When Ar ¹ is a heteroaromatic ring, a polycyclic aromatic compound containing an azulene ring and a heteroaromatic ring can be obtained. Also in this case, a polycyclic aromatic compound that has never been synthesized can be obtained, and its significance is extremely large. Examples of the heteroaromatic ring include those listed in the following formulas (10a) to (10d). The heteroaromatic rings shown in formulas (10a) to (10d) are bonded to other parts of formula (1) at adjacent carbon atoms that are not bridgehead positions. Here, the heteroaromatic rings represented by the formulas (10b) and (10c) are also condensed aromatic rings.

X in the formulas (10a) to (10c) is O (furan ring), S (thiophene ring), Se (selenophene ring), Te (tellurophen ring), Si (R ¹ ) ₂ (silole ring), or P (R ² ) (phosphole ring). R ¹ in the silole ring is an alkyl group which may have a substituent, and the same thing as the “alkyl group which may have a substituent” described in X ^{1 to} X ⁷ should be used. Can do. Two R ^{1 s} may be the same or different, or may be connected to each other. R ² in the phosphole ring is an aryl group which may have a substituent, and the same “aryl group which may have a substituent” described in X ^{1 to} X ⁷ is used. be able to.

  A method for synthesizing the compound represented by the formula (1) is not particularly limited. A 2-borylazulene represented by the following formula (11) and an aromatic halide represented by the following formula (12) are subjected to a coupling reaction to obtain a compound represented by the following formula (13), and then the following formula (14). A preferred method is to obtain a compound represented by the formula (1) by Wittig reaction with a phosphonium salt represented by the formula (1).

In formula (11), X ^{2 to} X ⁷ are the same as in formula (1). R ³ is a hydrogen atom or an alkyl group which may have a substituent. As the “alkyl group optionally having substituent (s)”, the same groups as those described for X ^{1 to} X ⁷ can be used. Two R ^{3 s} may be the same or different, or may be connected to each other.

In formula (12), X ¹ and Ar ¹ are the same as in formula (1). Hal represents a halogen atom.

In formula (13), X ^{1 to} X ⁷ and Ar ¹ are the same as in formula (1).

In Formula (14), R is the same as Formula (1). R ⁴ is an aryl group which may have a substituent. As the “aryl group optionally having substituent (s)”, the same groups as those described in X ^{1 to} X ⁷ can be used. The three R ^{4 s} may be the same or different, or may be connected to each other. An represents an anionic species, and halide ions and the like are used.

In the synthesis method of the compound represented by the formula (1), an azulene ring having various substituents (X ^{2 to} X ⁷ ) can be used as a raw material by introducing a boryl group into the azulene ring. Moreover, it is easy to introduce various aromatic rings (Ar ¹ ) and substituents (X ¹ ) into the halide represented by the formula (12). Therefore, since compounds having various skeletons into which various substituents are introduced as the compound represented by the formula (1) can be easily prepared, a wide variety of polycyclic aromatic compounds including an azulene ring can be easily synthesized. it can.

  A polycyclic aromatic compound represented by the following formula (2) is obtained by cyclization of the compound represented by the formula (1).

  In the cyclization reaction, the cyclization reaction is preferably performed in the presence of an acid catalyst. At this time, the acid catalyst is more preferably a Lewis acid catalyst made of a transition metal salt. The transition metal salt may be any transition metal salt having Lewis acidity, and the metal species is not particularly limited. For example, a salt of bismuth, gold, iron, copper, rhenium, indium, scandium, or the like can be used. Of these, bismuth, gold, and iron salts are preferred. In the examples of the present application, the reaction proceeded almost quantitatively using bismuth, gold and iron salts, and a polycyclic aromatic compound represented by the formula (2) could be obtained. In addition to the bismuth, gold, and iron salts, the present inventors have used copper, rhenium, indium, and scandium, in a compound in which the azulene ring is replaced with a benzene ring instead of the compound represented by the formula (1). It has been confirmed that the cyclization reaction proceeds in good yield even when a salt is used. From this, it is presumed that the cyclization reaction of the present invention proceeds even if a salt of copper, rhenium, indium, or scandium is used as a catalyst. The anion species of the transition metal salt is not particularly limited, and halide anions such as chloride anions and bromide anions, and sulfonate anions such as triflate can be used. The usage-amount of a catalyst is about 0.01-20 mol% with respect to the compound represented by Formula (1). The reaction can be carried out under mild conditions of 100 ° C. or lower, more preferably 60 ° C. or lower, in an organic solvent capable of dissolving the compound represented by formula (1).

When the compound represented by the formula (3) is cyclized to produce the polycyclic aromatic compound represented by the formula (4), in the compound represented by the formula (11), 2 of the azulene ring. Instead of introducing a boryl group at the position, a boryl group may be introduced at the 6-position of the azulene ring. Except for this point, the compound represented by the formula (1) is cyclized to give a formula (2) is the same as the case of producing the polycyclic aromatic compound ^represented, it can be replaced by X 2 to X ⁷ to ^X 8 ^{to X 13.}

When the compound represented by formula (5) is cyclized to produce the polycyclic aromatic compound represented by formula (6), the compound represented by formula (11) is replaced with an azulene ring. to introduce a boryl group in the aromatic ring represented by Ar ^2, in the compounds represented by formula (12), by introducing the (attachment at the 1-position and 2-position) azulene ring in place of an aromatic ring represented by Ar ¹ That's fine. Except for these points, the compound represented by the formula (1) is cyclized to produce the polycyclic aromatic compound represented by the formula (2), and X ^{2 to} X ⁷ are Ar ² can be replaced with Ar ¹ in X ^{14 to} X ¹⁹ , respectively.

When the compound represented by formula (7) is cyclized to produce the polycyclic aromatic compound represented by formula (8), the compound represented by formula (11) is replaced by an azulene ring. to introduce a boryl group in the aromatic ring represented by Ar ^2, in the compounds represented by formula (12), by introducing (binding at the 5-position and 6-position) azulene ring in place of an aromatic ring represented by Ar ¹ That's fine. Except for these points, the compound represented by the formula (1) is cyclized to produce the polycyclic aromatic compound represented by the formula (2), and X ^{2 to} X ⁷ are Ar ² can be replaced with Ar ¹ in X ^{20 to} X ²⁵ , respectively.

The polycyclic aromatic compounds obtained in this way are various, and it is possible to synthesize polycyclic aromatic compounds containing an azulene ring, which could not be synthesized so far. The structure is not particularly limited, but representative examples include compounds having the following condensed aromatic rings. In the following compounds, X ^{1 to} X ²⁵ described in formula (2), formula (4), formula (6), or formula (8) can be applied. Further, Equation (2), Equation (4) may have a substituent described for the aromatic rings Ar ¹ and Ar ² in the formula (6) or Formula (8).

Moreover, the compound which has the following hetero aromatic rings can be illustrated as a typical thing. In the following compounds, X ^{1 to} X ²⁵ and X described in Formula (2), Formula (4), Formula (6), or Formula (8) can be applied. Further, Equation (2), Equation (4) may have X and substituents described formula (6) or Formula (8) aromatic ring Ar ¹ and Ar ² in.

  The polycyclic aromatic compounds of the present invention represented by the formulas (2), (4), (6) and (8) thus obtained have absorption in the visible region and have a narrow HOMO-LUMO band gap. . Moreover, it can have a large dipole moment derived from the azulene ring. Therefore, it can be used for applications utilizing this characteristic.

  Among these, a preferred embodiment is an organic semiconductor containing the polycyclic aromatic compound of the present invention. As an organic semiconductor, it is useful as an organic field effect transistor, an organic thin film solar cell, or the like.

Example 1
In a 50 mL Schlenk flask under an argon atmosphere, 2-borylazulene (pinacol ester: 127 mg, 0.50 mmol), 2-bromo-1-formylnaphthalene (129 mg, 0.55 mmol), Pd (PPh ₃ ) ₄ (57.7 mg, 0.50 mmol), Sodium carbonate (106 mg, 1.0 mmol), degassed THF (3.0 mL), and H ₂ O (1.0 mL) were added, and the mixture was heated to reflux for 2 hours. After cooling to room temperature, water was added to stop the reaction. The reaction mixture was extracted with ethyl acetate, and the organic layer was dried using sodium sulfate. After the solvent was distilled off with a rotary evaporator, recrystallization was performed using a mixed solvent of methylene chloride and hexane to obtain 127 mg (0.45 mmol, yield 89%) of Compound 1 as a blue-green solid. The measurement results of NMR are shown below.

¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 6.79 (t, J = 9.6 Hz, 2H), 7.16 (t, J = 9.6 Hz, 1H), 7.28 (t, J = 8.0 Hz, 1H) , 7.30 (s, 2H), 7.47 (t, J = 8.0Hz, 1H), 7.56 (d, J = 8.8Hz, 1H), 7.60 (d, J = 8.8Hz, 1H), 7.67 (d, J = 8.0Hz, 1H), 7.89 (d, J = 9.6Hz, 2H), 9.71 (d, J = 8.8Hz, 1H), 10.54 (s, 1H). ¹³ C-NMR (100 MHz, C ₆ D ₆ ): δ 120.6, 124.2, 126.6, 127.0, 128.4, 129.0, 129.4, 129.9, 131.0, 133.3, 133.5, 137.6, 137.7, 140.8, 143.5, 148.1, 194.7.

  Under an argon atmosphere, (methoxymethyl) triphenylphosphonium chloride (175 mg, 0.51 mmol) and THF (1.4 mL) were added to a 50 mL two-necked flask and cooled to 0 ° C. When a solution of tert-butoxy potassium (57.1 mg, 0.51 mmol) and THF (1.4 mL) was added thereto, the reaction mixture gradually changed from a white suspension to a red-orange homogeneous solution. After stirring at 0 ° C. for 20 minutes, the temperature was raised to 25 ° C. and stirred for 1 hour. Under an argon atmosphere, Compound 1 (95.9 mg, 0.34 mmol) and THF (1.4 mL) were added to another 50 mL two-necked flask and cooled to 0 ° C. When the Wittig reactant prepared earlier was slowly dropped here, the solution changed from blue to green to black purple. After stirring at 0 ° C for 15 minutes, the temperature was raised to 25 ° C and stirring was continued for 30 minutes. The reaction was stopped by adding water, followed by extraction with ethyl acetate. The organic layer was dried with magnesium sulfate, and the solvent was distilled off with a rotary evaporator. Purification by silica gel column chromatography (hexane / ethyl acetate / triethylamine = 20/1 / 0.15) and 92.5 mg (E / Z = 94/6, 0.30 mmol, yield 89%) of the desired vinyl ether 2 as a green solid )Obtained. The NMR measurement results of the E isomers are shown below.

¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 3.17 (s, 3H), 6.15 (d, J = 13.6 Hz, 1H), 6.33 (t, J = 13.6 Hz, 1H), 6.81 (t, J = 9.6Hz, 2H), 7.16 (t, J = 9.6Hz, 1H), 7.31 (d, J = 8.0Hz, 1H), 7.32-7.39 (m, 2H), 7.67 (s, 2H), 7.71 ( d, J = 9.6Hz, 1H), 7.83 (d, J = 8.0Hz, 1H), 7.99 (d, J = 10.0Hz, 2H), 8.44 (d, J = 8.0Hz, 1H). ¹³ C-NMR (100 MHz, C ₆ D ₆ ): δ 55.8, 101.5, 119.8, 123.5, 126.2, 126.3, 126.8, 127.2, 128.6, 129.5, 132.4, 133.8, 134.1, 134.6, 136.1 (two peaks overlapped), 136.2, 140.9, 152.9, 153.1.

In an argon atmosphere, add vinyl ether 2 (93.0 mg, 0.30 mmol), Bi (OTf) ₃ (9.8 mg, 0.015 mmol), 1,2-dichloroethane (3.0 mL) to a 50 mL Schlenk flask, and stir at 25 ° C. for 3 hours. did. After the solvent was distilled off with an evaporator, the residue was purified by silica gel column chromatography (THF) to obtain 82.7 mg (0.30 mmol, yield 99%) of azuleno [2,1-a] phenanthrene 3 as a green solid. The measurement result of ¹ H-NMR is shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.10 (t, J = 8.4 Hz, 1H), 7.28 (t, J = 10.4 Hz, 1H), 7.48 (t, J = 8.4 Hz, 1H), 7.64 (t, J = 7.2Hz, 1H), 7.72 (t, 8.4Hz, 1H), 7.99 (d, J = 8.8Hz, 1H), 8.01 (d, J = 8.8Hz, 1H), 8.09 (s, 1H ), 8.34 (d, J = 8.8Hz, 1H), 8.56 (d, J = 8.8Hz, 1H), 8.63 (d, J = 8.8Hz, 1H), 8.70 (d, J = 8.8Hz, 1H), 8.60 (d, J = 8.8Hz, 1H), 8.80 (d, J = 8.8Hz, 1H).

Example 2
In Example 1, azureno [2,1-a] phenanthrene 3 was converted into green in the same manner as in Example 1 except that AuCl ₃ (4.5 mg, 0.015 mmol) was used instead of Bi (OTf) ₃ as a catalyst. As a solid, 81.8 mg (0.29 mmol, yield 98%) was obtained.

Example 3
In Example 1, azureno [2,1-a] phenanthrene 3 was converted to green as in Example 1 except that FeCl ₃ (2.4 mg, 0.015 mmol) was used instead of Bi (OTf) ₃ as a catalyst. As a solid, 82.0 mg (0.29 mmol, yield 98%) was obtained.

Example 4
Under an argon atmosphere, vinyl ether 4 (123 mg, 0.30 mmol), Bi (OTf) ₃ (9.8 mg, 0.015 mmol) and 1,2-dichloroethane (3.0 mL) were added to a 50 mL Schlenk flask and stirred at 25 ° C. for 3 hours. . After the solvent was distilled off with an evaporator, the residue was purified by silica gel column chromatography (THF) to obtain 110 mg (0.30 mmol, yield 97%) of 9-heptylazuleno [2,1-a] phenanthrene 5 as a green solid. . The measurement results of NMR are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.89 (t, J = 6.8 Hz, 3H), 1.30-1.38 (m, 8H), 1.75 (quint, J = 8.0 Hz, 2H), 2.80 (t, J = 8.0Hz, 2H), 7.04 (d, J = 10.4Hz, 1H), 7.18 (d, J = 9.6Hz, 1H), 7.37 (s, 1H), 7.64 (t, J = 8.0Hz, 1H) , 7.72 (t, J = 8.0Hz, 1H), 7.98 (d, J = 8.8Hz, 1H), 8.00 (d, J = 8.0Hz, 1H), 8.27 (d, J = 10.8Hz, 1H), 8.55 (d, J = 8.8Hz, 1H), 8.59 (d, J = 6.0Hz, 1H), 8.61 (d, J = 6.0Hz, 1H), 8.73 (d, J = 8.8Hz, 1H), 8.87 (d , J = 8.0 Hz, 1 H). ¹³ C-NMR (100 MHz, CDCl ₃ ): δ 14.1, 22.7, 29.2, 29.3, 31.8, 32.1, 42.3, 108.2, 112.5, 116.9, 117.6, 119.6, 123.4, 123.7, 124.3, 125.2, 126.2, 126.3, 126.4, 128.3, 128.5, 128.8, 129.8, 129.9, 131.0, 132.4, 135.8, 137.3, 152.2.

Example 5
In an argon atmosphere, add vinyl ether 6 (79.8 mg, 0.30 mmol), Bi (OTf) ₃ (9.8 mg, 0.015 mmol), 1,2-dichloroethane (3.0 mL) to a 50 mL Schlenk flask, and stir at 80 ° C. for 3 hours. did. After the solvent was distilled off with an evaporator, the residue was purified by silica gel column chromatography (THF) to obtain 63.2 mg (0.27 mmol, yield 90%) of 7 as a green solid. The measurement result of ¹ H-NMR is shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.08 (t, J = 9.6 Hz, 1H), 7.25 (t, J = 10.4 Hz, 1H), 7.44 (t, J = 9.6 Hz, 1H), 7.60 (d, J = 6.0, 1H), 7.78 (s, 1H), 7.93 (d, J = 6.0Hz, 1H), 7.95 (d, J = 9.6Hz, 1H), 8.26 (d, J = 10.4Hz, 1H), 8.37 (d, J = 8.8Hz, 1H), 8.62 (d, J = 8.8Hz, 1H).

Example 6
Under an argon atmosphere, vinyl ether 8 (30.3 mg, 0.10 mmol), AuCl ₃ (1.5 mg, 0.0050 mmol) and 1,2-dichloroethane (1.0 mL) were added to a 50 mL Schlenk flask, and the mixture was stirred at 80 ° C. for 12 hours. After the solvent was distilled off with an evaporator, the residue was purified by silica gel column chromatography (hexane / EtOAc = 10/1) to obtain 17.4 mg (0.064 mmol, yield 64%) of 9 as a yellowish green solid. The measurement result of ¹ H-NMR is shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 3.15 (s, 6H), 7.22 (t, J = 9.6 Hz, 1H), 7.20-7.30 (m, 3H), 7.47 (t, J = 9.6 Hz, 1H), 7.65 (d, J = 8.8Hz, 1H), 7.97 (s, 1H), 8.30 (d, J = 8.8Hz, 1H), 8.32 (d, J = 8.8Hz, 1H), 8.45 (d, J = 9.6Hz, 1H), 8.62 (d, J = 8.8Hz, 1H).

Example 7
Under an argon atmosphere, add vinyl ether 10 (93.0 mg, 0.30 mmol), Bi (OTf) ₃ (9.8 mg, 0.015 mmol), 1,2-dichloroethane (3.0 mL) to a 50 mL Schlenk flask, and stir at 25 ° C. for 4 hours. did. After the solvent was distilled off with an evaporator, the residue was washed successively with diethyl ether and hexane to obtain 80.1 mg (0.29 mmol, yield 96%) of 11 as a green solid. The measurement result of ¹ H-NMR is shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.26 (t, J = 9.6 Hz, 1H), 7.38 (t, J = 9.6 Hz, 1H), 7.57 (d, J = 6.8 Hz, 1H), 7.58 (d, J = 6.8Hz, 1H), 7.66 (t, J = 9.6Hz, 1H), 7.84 (d, J = 8.8Hz, 1H), 8.10 (dd, J = 4.0, 7.2Hz, 1H), 8.19 (dd, J = 4.0, 7.2Hz, 1H), 8.30 (s, 1H), 8.30 (d, J = 7.2Hz, 1H), 8.52 (s, 1H), 8.53 (d, J = 9.6Hz, 1H) , 8.81 (d, J = 8.8Hz, 1H), 9.16 (s, 1H).

Example 8
Using azureno [2,1-a] phenanthrene as a p-type semiconductor, a thin film was formed on a Si / SiO ₂ substrate by vacuum deposition to produce a top contact type organic transistor device. The device structure is as shown in FIG. 1, and Si / SiO ₂ / azuleno [2,1-a] phenanthrene / 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodi. Methane (F ₄ TCNQ) / Au. Here, Si is a gate electrode, SiO ₂ is a gate insulating film, and azuleno [2,1-a] phenanthrene constitutes an active layer. F ₄ TCNQ was used to reduce the contact resistance between the electrode and the active layer interface. One of Au was a source electrode and the other was a drain electrode. When the transistor characteristics of these devices were measured, the charge mobility was 5.3 × 10 ⁻² cm ² / Vs. The ON / OFF ratio was 1.6 × 10 ⁵ , and good charge mobility and a high ON / OFF ratio were obtained.

Claims (1)

An organic semiconductor containing a polycyclic aromatic compound represented by the following formula (2), formula (4), formula (6) or formula (8).

[In Formula (2), X ^{1 to} X ⁷ each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An alkynyl group that may have a substituent, an aryl group that may have a substituent, a cycloalkyl group that may have a substituent, a heterocyclic group that may have a substituent, a hydroxyl group that may be protected, Alkoxy group, aryloxy group, formyl group, optionally protected carboxyl group or salt thereof, alkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyl group, aryloxycarbonyl group, protection May be amino group, alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium Group, thiol group which may be protected, alkylthio group, arylthio group, sulfinic acid group which may be protected or salt thereof, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group which may be protected or salt thereof , Alkylsulfonyl group, arylsulfonyl group, alkylazo group, arylazo group, optionally protected phosphate group or salt thereof, optionally protected phosphorous acid group or salt thereof, cyano group, nitro group or azide group It is. X ^{2 to} X ⁷ may be connected to each other. X ² and X ³ , X ³ and X ⁴ , X ⁴ and X ⁵ , and X ⁵ and X ⁶ may be connected to each other to form an aromatic ring. Ar ¹ represents a condensed aromatic ring or a heteroaromatic ring. ]

[In Formula (4), X ¹ and Ar ¹ are the same as those in Formula (2). X ^{8 to} X ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, Aryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocyclic group which may have a substituent, hydroxyl group which may be protected, alkoxy group, aryloxy group, formyl Group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an optionally protected amino group , Alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, protected Thiol group, alkylthio group, arylthio group, sulfinic acid group or salt thereof which may be protected, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group or salt thereof which may be protected, alkylsulfonyl group An arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group. X ^{8 to} X ¹³ may be connected to each other. X ⁹ and X ¹⁰ , X ¹⁰ and X ¹¹ , X ¹² and X ¹³ may each form an aromatic ring. ]

Wherein (6), ^{X 1} is the same as equation (2). X ^{14 to} X ¹⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, Aryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocyclic group which may have a substituent, hydroxyl group which may be protected, alkoxy group, aryloxy group, formyl Group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an optionally protected amino group , Alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, protection Thiol group, alkylthio group, arylthio group, optionally protected sulfinic acid group or salt thereof, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group or salt thereof optionally protected, alkylsulfonyl A group, an arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group. X ^{14 to} X ¹⁹ may be connected to each other. X ¹⁴ and X ¹⁵ , X ¹⁵ and X ¹⁶ , X ¹⁶ and X ¹⁷ , and X ¹⁷ and X ¹⁸ may each form an aromatic ring. Ar ² represents a condensed aromatic ring or a heteroaromatic ring. ]

Wherein (8), ^{X 1} is the same as equation (2). X ^{20 to} X ²⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, Aryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocyclic group which may have a substituent, hydroxyl group which may be protected, alkoxy group, aryloxy group, formyl Group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an optionally protected amino group , Alkylamino group, arylamino group, ammonium group, alkylammonium group, arylammonium group, protection Thiol group, alkylthio group, arylthio group, optionally protected sulfinic acid group or salt thereof, alkylsulfinyl group, arylsulfinyl group, sulfonic acid group or salt thereof optionally protected, alkylsulfonyl A group, an arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group. X ^{20 to} X ²⁵ may be connected to each other. X ²¹ and X ²² , X ²² and X ²³ , and X ²⁴ and X ²⁵ may each form an aromatic ring. Ar ² is the same as in formula (6). ]

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