JP2017218381A - Thiophene ring-condensed aromatic compound and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of condensing a thiophene ring on various aromatic compounds only with simple one process.SOLUTION: There is provided a manufacturing method of a thiophene ring-condensed aromatic compound having one or more thiophene ring condensed to a polycyclic aromatic hydrocarbon ring or heterocyclic aromatic ring, including a process of reacting a polycyclic aromatic compound or a heterocyclic compound with sulfur and the polycyclic aromatic compound or the heterocyclic compound has one or more structure represented by the general formula (1), where Rrepresents an aryl group which may be substituted, n represents an integer of 1 to more and binds represented by dotted lines and broken lines represent single bonds or double bonds.SELECTED DRAWING: None

Description

  The present invention relates to a thiophene ring-fused aromatic compound and a method for producing the same.

  Π-conjugated aromatic compounds fused with thiophene are used as organic semiconductor materials in various fields such as organic EL, transistors, solar cells, conductive materials, photoconductors, and liquid crystal materials.

  So far, a large number of thiophene ring-condensation reactions have been reported, but for the synthesis of conventional thiophene ring-fused aromatic compounds, thiophene was added to polycyclic aromatic hydrocarbons (PAH) into which two substituents were introduced. Methods for condensing rings have been used, and methods for obtaining various thiophene ring-fused aromatic compounds have been reported (see, for example, Non-Patent Document 1). Recently, a method of obtaining a thiophene ring condensed aromatic compound in one step from PAH having an alkynyl group and a sulfur source such as thiourea and sodium sulfide is also known (see, for example, Non-Patent Document 2).

Eur. J. Org. Chem., 2013, 217-227. J. Am. Chem. Soc., 2013, 135, 11445-11448.

  However, since the method described in Non-Patent Document 1 requires a substrate in which two substituents are introduced into PAH, a complicated operation involving multi-step reaction and purification is required to synthesize a thiophene-ring condensed aromatic compound. Was necessary. In addition, there are problems in terms of versatility, such as limitations on the substrates that can be used. In the method described in Non-Patent Document 2, only a substrate having a carbonyl group at an appropriate position can be used, and there is a problem in versatility.

  In order to efficiently search for thiophene ring-fused aromatic compounds with the aim of developing excellent new organic semiconductor materials, a method that allows thiophene rings to be fused to various substrates with a simpler method The development of is urgent. Therefore, an object of the present invention is to provide a method capable of simply condensing a thiophene ring with a single step for various aromatic compounds.

  As a result of intensive studies in view of the above problems, the present inventors have achieved a very simple reaction of reacting sulfur with a polycyclic aromatic hydrocarbon or heterocyclic compound into which only one specific substituent has been introduced. By adopting such a technique, it has been found that a thiophene ring can be condensed to a polycyclic aromatic hydrocarbon or heterocyclic compound in only one step. The present invention has been completed as a result of further research based on such knowledge. That is, the present invention includes the following configurations.

Item 1. A method for producing a thiophene ring condensed aromatic compound in which one or more thiophene rings are condensed to a polycyclic aromatic hydrocarbon ring or a heteroaromatic ring,
Comprising a step of reacting a polycyclic aromatic compound or heterocyclic compound with sulfur;
The polycyclic aromatic compound or heterocyclic compound has the general formula (1):

[Wherein, R ¹ represents an optionally substituted aryl group. n represents an integer of 1 or more. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond. ]
A manufacturing method having one or more structures represented by:

  Item 2. The polycyclic aromatic compound or heterocyclic compound is represented by the general formula (3):

[Wherein, R ¹ and n are the same as defined above. Ar represents a polycyclic aromatic hydrocarbon ring which may be substituted or a heteroaromatic ring which may be substituted. R ³ represents a group represented by — (C≡C) _n —R ¹ . The group represented by-(C≡C) _n -R ¹ is not bonded to at least one carbon atom adjacent to the carbon atom on the Ar ring to which R ³ is bonded. Hydrogen atoms are bonded. m represents an integer of 0 or more. ]
Item 2. The production method according to Item 1, which is a compound represented by:

  Item 3. Ar represents an optionally substituted naphthalene ring, an optionally substituted anthracene ring, an optionally substituted phenanthrene ring, and an optionally substituted tetracene. A ring, an optionally substituted pyrene ring, an optionally substituted fluoranthene ring, an optionally substituted pentacene ring, an optionally substituted perylene ring, A corannulene ring optionally having a substituent, a chrysene ring optionally having a substituent, a thiophene ring optionally having a substituent, a benzothiophene ring optionally having a substituent, or Item 3. The production method according to Item 2, which is a dithienobenzene ring optionally having a substituent, or a ring obtained by condensing one or more benzene rings to these rings.

  Item 4. Item 4. The production method according to any one of Items 1 to 3, wherein the reaction step is performed in a polar solvent.

  Item 5. The polycyclic aromatic compound or heterocyclic compound has the general formula (1A)

[Wherein, R ¹ is the same as defined above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
Having one or more structures represented by
The produced thiophene ring-fused aromatic compound has the general formula (2A):

Wherein, R ² is either same group as R ^1, a group R ¹ is reduced, it represents an aryl group which may be substituted. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
Item 2. The production method according to Item 1, comprising one or more structures represented by:

  Item 6. The polycyclic aromatic compound or heterocyclic compound has the general formula (1B)

[Wherein, R ¹ is the same as defined above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
Having one or more structures represented by
The produced thiophene ring-fused aromatic compound has the general formula (2B):

Wherein, R ² is either same group as R ^1, a group R ¹ is reduced, it represents an aryl group which may be substituted. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
Item 2. The production method according to Item 1, comprising one or more structures represented by:

  Item 7. The polycyclic aromatic compound or the heterocyclic compound is represented by the general formula (3E):

[Wherein, R ¹ is the same or different and is the same as defined above. ]
Or a compound represented by the general formula (3F):

[Wherein, R ¹ is the same or different and is the same as defined above. ]
The manufacturing method in any one of claim | item 1 -6 which is a compound represented by these.

Item 8. A thiophene ring-fused aromatic compound in which a polycyclic aromatic hydrocarbon ring which may have a substituent is condensed with a thiophene ring which may have one or more substituents,
A reaction between a polycyclic aromatic compound and sulfur,
The polycyclic aromatic compound is
General formula (3):

[Wherein, R ¹ represents an optionally substituted aryl group. n represents an integer of 1 or more. Ar represents a polycyclic aromatic hydrocarbon ring which may be substituted or a heteroaromatic ring which may be substituted. R ³ represents a group represented by — (C≡C) _n —R ¹ . The group represented by-(C≡C) _n -R ¹ is not bonded to at least one carbon atom adjacent to the carbon atom on the Ar ring to which R ³ is bonded. Hydrogen atoms are bonded. m represents an integer of 0 or more. ]
A thiophene ring-condensed aromatic compound represented by (a compound in which two thiophene rings optionally having a substituent are condensed on the naphthalene ring, a thiophene ring optionally having a substituent on the anthracene ring is 1 or 4 condensed compounds, and compounds in which anthraquinone optionally having one substituent thiophene ring is condensed).

  According to the present invention, by adopting a very simple technique of reacting a polycyclic aromatic hydrocarbon or heterocyclic compound into which only one specific substituent is introduced, and sulfur, it is possible to perform the process only in one step. A thiophene ring can be fused to a polycyclic aromatic hydrocarbon or heterocyclic compound. For this reason, it is not necessary to prepare a substrate into which two substituents are introduced, which is a simpler method than in the past.

2 is an absorption spectrum and a fluorescence spectrum of Compound 2a obtained in Example 1-1. It is the absorption spectrum and fluorescence spectrum of the compound 2f obtained in Example 1-2. It is the absorption spectrum and fluorescence spectrum of the compound 2g obtained in Example 1-2. 2 is an absorption spectrum and a fluorescence spectrum of Compound 2h obtained in Example 1-2. 2 is an absorption spectrum and a fluorescence spectrum of Compound 2i obtained in Example 1-2. It is the absorption spectrum and fluorescence spectrum of the compound 2j obtained in Example 1-2. It is the absorption spectrum and fluorescence spectrum of the compound 2k obtained in Example 1-2. It is an absorption spectrum and a fluorescence spectrum of the compound 2l obtained in Example 1-2. 2 is an absorption spectrum and a fluorescence spectrum of the compound 2m obtained in Example 1-2. It is the absorption spectrum and fluorescence spectrum of the compound 2n obtained in Example 1-2. It is the absorption spectrum and fluorescence spectrum of the compound 2o obtained in Example 1-2. It is the absorption spectrum and fluorescence spectrum of the compound 2p obtained in Example 1-2. It is the absorption spectrum and fluorescence spectrum of the compound 2q obtained in Example 1-2. It is the absorption spectrum and fluorescence spectrum of the compound 2r obtained in Example 1-2. 2 is an absorption spectrum and a fluorescence spectrum of Compound 2u obtained in Example 3-1. It is the absorption spectrum and fluorescence spectrum of the compound 2v obtained in Example 3-2.

1. Production method of thiophene ring condensed aromatic compound The production method of the present invention is a method of producing a thiophene ring condensed aromatic compound in which one or more thiophene rings are condensed to a polycyclic aromatic hydrocarbon ring or a heteroaromatic ring. ,
Comprising a step of reacting a polycyclic aromatic compound or heterocyclic compound with sulfur;
The polycyclic aromatic compound or heterocyclic compound has the general formula (1):

[Wherein, R ¹ represents an optionally substituted aryl group. n represents an integer of 1 or more. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond. ]
It has one or more structures represented by

By adopting such a method, a thiophene ring condensation reaction involving cleavage of the C—H bond at the ortho position adjacent to the ethynylene group proceeds. In addition, when the polycyclic aromatic compound or heterocyclic compound has a plurality of groups represented by-(C≡C) _n -R ¹ , the thiophene ring is condensed by the number of the groups. Can be ringed. When a thiophene ring is condensed by a condensation reaction, an aromatic compound in which the R ¹ group is directly bonded to the condensed thiophene ring is obtained, but when R ¹ has a nitro group (—NO ₂ ) In this case, the nitro group is reduced to the amino group (—NH ₂ ) simultaneously with the ring condensation reaction. For this reason, when R ¹ is an aryl group substituted with a nitro group, the nitro group is reduced simultaneously with the ring condensation reaction to become an aryl group substituted with an amino group.

  More specifically, when the structure represented by the general formula (1) is n = 1, that is, the general formula (1A):

[Wherein, R ¹ is the same as defined above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
In the case of having one or more structures represented by general formula (2A), a thiophene ring condensation reaction involving cleavage of the C—H bond at the ortho position of the arylethynyl group proceeds.

Wherein, R ² is either same group as R ^1, a group R ¹ is reduced, it represents an aryl group which may be substituted. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
A thiophene ring-fused aromatic compound having one or more structures represented by

  On the other hand, when the structure represented by the general formula (1) is n = 2, that is, the general formula (1B):

[Wherein, R ¹ is the same as defined above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
In the case of having one or more structures represented by formula (2B), the thiophene ring condensation reaction involving cleavage of the C—H bond at the ortho position of the arylethynyl group proceeds twice.

Wherein, R ² is either same group as R ^1, a group R ¹ is reduced, it represents an aryl group which may be substituted. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
A thiophene ring-fused aromatic compound having one or more structures represented by

  That is, in the production method of the present invention, the thiophene ring condensation reaction involving the cleavage of the C—H bond at the ortho position of the arylethynyl group proceeds by the number of triple bonds, and the thiophene ring is condensed for the number of times. A compound is obtained.

  In the present invention, the polycyclic aromatic compound or heterocyclic compound used as a substrate is a structure represented by the general formula (1) as described above (for example, a structure represented by the general formula (1A), 1 or more (preferably an integer of 1 to 10), but the number is not limited. As described above, since the thiophene ring can be condensed by the number having the structure represented by the general formula (1), it can be appropriately set according to the number of the thiophene ring to be condensed. Specifically, the polycyclic aromatic compound or the heterocyclic compound may have one, two, three, four, or five structures represented by the general formula (1) as described above. .

The polycyclic aromatic compound or heterocyclic compound used as the substrate has a structure represented by the general formula (1) as described above, and — (C≡C ) Of the two carbon atoms adjacent to the carbon atom on the polycyclic aromatic hydrocarbon ring or heterocyclic ring to which the group represented by _n- R ¹ is bonded, at least one carbon atom includes the above- When the group represented by (C≡C) _n -R ¹ is not bonded and a hydrogen atom is bonded, the hydrogen atom is bonded to the two adjacent carbon atoms. The thiophene ring-fused aromatic compound includes structural isomers. For this reason, considering the efficiency of the reaction, etc., the polycyclic aromatic hydrocarbon to which the group represented by — (C≡C) _n —R ¹ constituting the structure represented by the general formula (1) is bonded The group represented by-(C≡C) _n -R ¹ is not bonded to only one of the two carbon atoms adjacent to the carbon atom on the ring or heterocyclic ring. It is preferable that a hydrogen atom is bonded.

In the general formulas (1), (1A) and (1B), the aryl group represented by R ¹ includes a monocyclic aryl group (phenyl group) and a polycyclic aryl group (fused ring aryl group, polycyclic non-fused ring aryl). Group) and the like, and examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group. Among these, from the viewpoints of ease of synthesis, yield, and the like, a monocyclic or condensed ring aryl group is preferable, and a phenyl group is more preferable.

The aryl group represented by R ¹ may be substituted. Examples of the substituent that the aryl group represented by R ¹ may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl group (methyl group, ethyl group, n-propyl group, isopropyl). Group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-hexyl group, n-octyl group and other C1-10 alkyl groups), haloalkyl group (trifluoromethyl group and other C1- 6 haloalkyl group), alkoxy group (C1-6 alkoxy group such as methoxy group, ethoxy group, etc.), acyl group (C2-7 acyl group such as acetyl group, propionyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxy group) (C1-6 alkoxy) carbonyl group such as carbonyl group), substituted or unsubstituted amino group (di (C1-6 alkyl) such as amino group, dimethylamino group, diethylamino group) Amino group etc.) and a nitro group. In the case of having these substituents, the number of substituents is preferably 1 to 6, more preferably 1 to 3. In the general formula (1), n is an integer of 1 or more. The number of n can be appropriately set according to the number of thiophene rings to be condensed, but from the viewpoint of ease of synthesis, yield, etc., an integer of 1 to 5 is preferable and an integer of 1 to 3 is more preferable.

In formula (2A) and (2B), R ² is either same group as R ^1, a group R ¹ is reduced, an aryl group which may be substituted. As described above, when R ¹ has a nitro group, it is reduced to an amino group during the condensation reaction of the thiophene ring. Therefore, when R ¹ is an aryl group substituted with a nitro group, R ² is an amino group. An aryl group substituted with a group. When R ¹ is an unsubstituted aryl group or an aryl group substituted with a substituent other than a nitro group, R ² is the same as R ¹ .

  As a structure represented by the general formula (1) that satisfies such conditions, for example,

[Wherein ⁿ Bu represents an n-butyl group. ^t Bu represents a tert-butyl group. ⁿ hexyl represents an n-hexyl group. ⁿ octyl represents an n-octyl group. The same applies hereinafter. ]
The structure represented by etc. is mentioned.

  Specifically, the polycyclic aromatic compound or heterocyclic compound having such a structure is represented by the general formula (3):

[Wherein, R ¹ and n are the same as defined above. Ar represents a polycyclic aromatic hydrocarbon ring which may be substituted or a heteroaromatic ring which may be substituted. R ³ represents a group represented by — (C≡C) _n —R ¹ . The group represented by-(C≡C) _n -R ¹ is not bonded to at least one carbon atom adjacent to the carbon atom on the Ar ring to which R ³ is bonded. Hydrogen atoms are bonded. m represents an integer of 0 or more. ]
The compound represented by these is preferable.

  In the general formula (3), the polycyclic aromatic hydrocarbon ring represented by Ar includes a naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, pyrene ring, fluoranthene ring, pentacene ring, perylene ring, corannulene ring, chrysene ring Benzo [c] naphtho [2,1-p] chrysene ring and the like, and those obtained by condensing a benzene ring (coronene ring, triphenylene ring, hexabenzocoronene ring, terylene ring, etc.). The polycyclic aromatic hydrocarbon ring represented by Ar may be substituted. Examples of the substituent that the polycyclic aromatic hydrocarbon ring represented by Ar may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl group (methyl group, ethyl group, n- C1-10 alkyl group such as propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-hexyl group and n-octyl group), haloalkyl group (trifluoromethyl group) C1-6 haloalkyl groups, etc.), alkoxy groups (C1-6 alkoxy groups, such as methoxy groups and ethoxy groups), acyl groups (C2-7 acyl groups, such as acetyl groups and propionyl groups), alkoxycarbonyl groups (methoxy) (C1-6 alkoxy) carbonyl group such as carbonyl group and ethoxycarbonyl group), substituted or unsubstituted amino group (amino group, dimethylamino group, diethylamino group and other di (C1-6) Alkyl) amino group, etc.), and a nitro group. In the case of having these substituents, the number of substituents is preferably 1 to 6, more preferably 1 to 3.

  In the general formula (3), examples of the heteroaromatic ring represented by Ar include a thiophene ring, a benzothiophene ring, a dithienobenzene ring, and the like, and a ring condensed with a benzene ring. The heteroaromatic ring represented by Ar may be substituted. Examples of the substituent that the polyheteroaromatic ring represented by Ar may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl group (methyl group, ethyl group, n-propyl group, C1-10 alkyl group such as isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-hexyl group and n-octyl group), haloalkyl group (C1 such as trifluoromethyl group) -6 haloalkyl group, etc.), alkoxy group (C1-6 alkoxy group such as methoxy group, ethoxy group, etc.), acyl group (C2-7 acyl group such as acetyl group, propionyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, (C1-6 alkoxy) carbonyl group such as ethoxycarbonyl group), substituted or unsubstituted amino group (di (C1-6 alkyl) such as amino group, dimethylamino group, diethylamino group) Amino group etc.) and a nitro group. In the case of having these substituents, the number of substituents is preferably 1 to 6, more preferably 1 to 3.

In the general formula (3), R ³ represents a group represented by — (C≡C) _n —R ¹ . As R ¹ and n in R ³ , those described above can be adopted. The group represented by-(C≡C) _n -R ¹ is bonded to at least one carbon atom adjacent to the carbon atom on the Ar ring to which R ³ is bonded. A hydrogen atom is bonded. That is, when m is 1 or more, it means that the polycyclic aromatic compound or the heterocyclic compound has a plurality of structures represented by the general formula (1).

In the general formula (3), m which is the number of R ³ is an integer of 0 or more, preferably an integer of 0 to 10. This m can be 0, 1, 2, 3, 4 or 5. That is, the polycyclic aromatic compound or the heterocyclic compound can have one, two, three, four, five, or six structures represented by the general formula (1).

  Examples of the polycyclic aromatic compound or heterocyclic compound satisfying such conditions include, for example, the general formula (3A):

[Wherein, R ¹ and Ar are the same as defined above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond. ]
The compound represented by these is mentioned.

  As this compound (3A), for example,

Etc.

  Examples of the polycyclic aromatic compound or heterocyclic compound satisfying the above conditions include, for example, the general formula (3B):

[Wherein, R ¹ and Ar are the same as defined above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond. ]
The compound represented by these is also mentioned.

  As this compound (3B), for example,

Etc.

  Examples of the polycyclic aromatic compound or heterocyclic compound satisfying the above conditions include, for example, the general formula (3C):

[Wherein, R ¹ is the same or different and is the same as defined above. Ar is the same as described above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond. ]
The compound represented by these is also mentioned.

  As this compound (3C), for example,

Etc.

  Examples of the polycyclic aromatic compound or heterocyclic compound satisfying the above conditions include, for example, the general formula (3D):

[Wherein, R ¹ is the same or different and is the same as defined above. Ar is the same as described above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond. ]
The compound represented by these is also mentioned.

  As this compound (3D), for example,

Etc.

  Examples of the polycyclic aromatic compound or heterocyclic compound satisfying the above conditions include, for example, the general formula (3E):

[Wherein, R ¹ is the same or different and is the same as defined above. ]
The compound represented by these is also mentioned.

  As this compound (3E), for example,

Etc.

  Examples of the polycyclic aromatic compound or heterocyclic compound satisfying the above conditions include, for example, the general formula (3F):

[Wherein, R ¹ is the same or different and is the same as defined above. ]
The compound represented by these is also mentioned.

  As this compound (3F), for example,

Etc.

  In the production method of the present invention, a thiophene condensed ring reaction involving the cleavage of the C—H bond at the ortho position adjacent to the ethynylene group proceeds. For this reason, the thiophene ring condensation reaction proceeds while breaking the bond between the ethynylene group and the adjacent ring (such as a benzene ring). For this reason, as a polycyclic aromatic compound and a heterocyclic compound, when the number of rings is larger, the aromaticity of the ring (benzene ring, etc.) adjacent to the ethynylene group in the above-mentioned condensed ring reaction is destroyed. Since the stability is excellent, the synthesis is easy and the yield tends to be high. For this reason, it is preferable to employ a polycyclic aromatic compound and a heterocyclic compound having a large number of rings.

  The polycyclic aromatic compound and the heterocyclic compound described above may be added after being prepared in advance, or synthesized in the system (for example, by Sonogashira coupling, Ueda / Kosugi / Still coupling, etc.). May be. That is, the thiophene ring-condensation reaction can be carried out in one pot from aryl triflate and alkyne via Sonogashira coupling reaction, Ueda, Kosugi, Stille coupling and the like.

In the present invention, sulfur (single sulfur) is used as a sulfur source for condensing a thiophene ring with respect to the above polycyclic aromatic hydrocarbon ring or heteroaromatic ring. The amount of sulfur used can be appropriately set depending on the number of groups represented by — (C≡C) _n —R ¹ (value of n) possessed by the polycyclic aromatic compound and the heterocyclic compound. For example, when n is 0, the amount of sulfur used is converted to 1 mol of the group represented by-(C≡C) _n -R ¹ in the polycyclic aromatic compound or heterocyclic compound, 0.2-5.0 mol is preferable and 0.3-4.0 mol is more preferable.

  In the present invention, the reaction conditions between the polycyclic aromatic hydrocarbon ring or heteroaromatic ring and sulfur are not particularly limited. Usually, a method of heating a polycyclic aromatic hydrocarbon ring or heteroaromatic ring and sulfur in a solvent with stirring as necessary is simple and obtains a thiophene ring condensed aromatic compound in a high yield. Can do.

  The solvent that can be used at this time is preferably a polar solvent. By employing such a polar solvent, a thiophene ring condensed aromatic compound can be obtained with higher yield. As such a solvent, both a protic polar solvent and an aprotic polar solvent can be adopted. Examples of the protic polar solvent include 1,4-dioxane, tetrahydrofuran, anisole, cyclopentyl methyl ether, ethyl acetate, and the like. Can be mentioned. Examples of the aprotic polar solvent include dimethyl sulfoxide, amide solvents (N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), nitrile solvents (acetonitrile, propionitrile, etc.). ) And the like. Among them, a solvent having a boiling point higher than the reaction temperature described later is preferable, and 1,4-dioxane, anisole, cyclopentylmethyl ether, dimethyl sulfoxide, amide solvents (N, N-dimethylformamide, N, N-dimethylacetamide, N -Methylpyrrolidone and the like) are preferred, and anisole, dimethyl sulfoxide, amide solvents (N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like) and the like are more preferred. In addition, when alcohol, such as methanol and ethanol, is used in combination with these solvents, the reaction rate can be further accelerated.

  The heating temperature is not particularly limited as long as the ring condensation reaction of the present invention proceeds. Specifically, from the viewpoint of yield and the like, 100 to 180 ° C is preferable, 120 to 160 ° C is more preferable, and 130 to 150 ° C is more preferable. The heating time may be a time during which the ring condensation reaction of the present invention proceeds sufficiently. For example, 10 minutes to 96 hours are preferable, and 30 minutes to 72 hours are more preferable. The reaction atmosphere is preferably an inert gas (nitrogen gas, argon gas, etc.) atmosphere.

  After completion of the reaction, the thiophene ring-condensed aromatic compound of the present invention, which is the target compound, can be obtained through ordinary isolation and purification steps as necessary.

2. Thiophene ring condensed aromatic compound The thiophene ring condensed aromatic compound of the present invention obtained as described above has one or more substituents on the polycyclic aromatic hydrocarbon ring which may have a substituent. It is a thiophene ring condensed aromatic compound in which a thiophene ring which may be condensed is condensed.

  Among these thiophene ring-fused aromatic compounds, the thiophene ring-fused aromatic compound obtained when the compound represented by the general formula (3) and Ar is a polycyclic aromatic hydrocarbon ring is used as a substrate. A compound in which two thiophene rings optionally having a substituent are condensed, a compound in which one or four thiophene rings optionally having a substituent in an anthracene ring are condensed, and anthraquinone are substituted. Except for a compound in which one thiophene ring which may have is condensed, it is a novel compound not described in any literature.

  Such a thiophene-ring-fused aromatic compound is represented by the general formula (4A) when the compound represented by the general formula (3A) is used as a substrate:

[Wherein, R ¹ and Ar are the same as defined above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond. ]
It is a compound represented by these.

Examples of R ¹ include those described above. Examples of Ar also include those described above, which may have a naphthalene ring which may have a substituent, a phenanthrene ring which may have a substituent, a tetracene ring which may have a substituent, and a substituent. A pyrene ring which may have a substituent, a fluoranthene ring which may have a substituent, a pentacene ring which may have a substituent, a perylene ring which may have a substituent, and a substituent. The compound is a novel compound when the ring is a corannulene ring, a chrysene ring which may have a substituent, or a benzo [c] naphtho [2,1-p] chrysene ring which may have a substituent. As the substituent, those described above can be adopted.

  For example,

Etc.

  Further, the thiophene ring condensed aromatic compound, when the compound represented by the general formula (3B) is used as a substrate, the general formula (4B):

[Wherein, R ¹ and Ar are the same as defined above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond. ]
It is a compound represented by these.

Examples of R ¹ include those described above. Examples of Ar also include those described above, which may have a naphthalene ring which may have a substituent, an anthracene ring which may have a substituent, a phenanthrene ring which may have a substituent, and a substituent. A tetracene ring which may have a substituent, a pyrene ring which may have a substituent, a fluoranthene ring which may have a substituent, a pentacene ring which may have a substituent, and a substituent. Perylene ring, optionally substituted coranulene ring, optionally substituted chrysene ring, or optionally substituted benzo [c] naphtho [2,1-p ] A new compound when it is a chrysene ring. As the substituent, those described above can be adopted.

  For example,

Etc.

  Moreover, the thiophene ring condensed aromatic compound, when the compound represented by the general formula (3C) is used as a substrate, the general formula (4C):

[Wherein, R ¹ is the same or different and is the same as defined above. Ar is the same as described above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond. ]
It is a compound represented by these.

Examples of R ¹ include those described above. Examples of Ar also include those described above. An anthracene ring which may have a substituent, a phenanthrene ring which may have a substituent, a tetracene ring which may have a substituent, and a substituent A pyrene ring which may have a substituent, a fluoranthene ring which may have a substituent, a pentacene ring which may have a substituent, a perylene ring which may have a substituent, and a substituent. The compound is a novel compound when the ring is a corannulene ring, a chrysene ring which may have a substituent, or a benzo [c] naphtho [2,1-p] chrysene ring which may have a substituent. As the substituent, those described above can be adopted.

  For example,

Etc.

  Moreover, the thiophene ring condensed aromatic compound, when the compound represented by the general formula (3D) is used as a substrate, the general formula (4D):

[Wherein, R ¹ is the same or different and is the same as defined above. Ar is the same as described above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond. ]
It is a compound represented by these.

Examples of R ¹ include those described above. Examples of Ar also include those described above. An anthracene ring which may have a substituent, a phenanthrene ring which may have a substituent, a tetracene ring which may have a substituent, and a substituent A pyrene ring which may have a substituent, a fluoranthene ring which may have a substituent, a pentacene ring which may have a substituent, a perylene ring which may have a substituent, and a substituent. The compound is a novel compound when the ring is a corannulene ring, a chrysene ring which may have a substituent, or a benzo [c] naphtho [2,1-p] chrysene ring which may have a substituent. As the substituent, those described above can be adopted.

  For example,

Etc.

  In addition, the thiophene ring-fused aromatic compound, when the compound represented by the general formula (3E) is used as a substrate, the general formula (4E):

[Wherein, R ¹ is the same or different and is the same as defined above. ]
It is a compound represented by these.

Examples of R ¹ are those described above and are novel compounds.

  For example,

Etc.

  Moreover, the thiophene ring condensed aromatic compound, when the compound represented by the general formula (3F) is used as a substrate, the general formula (4F):

It is a compound represented by these.

Examples of R ¹ are those described above and are novel compounds.

  For example,

Etc.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited at all by these Examples.

  Unless otherwise restricted, all materials including dry solvents were used without purification of commercial products. Moreover, the dry solvent was used for all the solvents. Compounds 1a-1w were synthesized according to previous reports. All reactions were performed using standard vacuum line and Schlenk techniques. All work-up and purification procedures were performed in air with reagent grade solvents.

Analytical thin layer chromatography (TLC) was performed using E. Merck silica gel 60 F254 precoated plates (0.25 mm). The obtained chromatogram was analyzed with a UV lamp (254 nm). Flash column chromatography was performed using E. Merck silica gel 60 (230-400 mesh). Preparative recycle gel permeation chromatography (GPC) was performed using a JAI LC-9260 II NEXT equipped with a JAIGEL-1H / JAIGEL-2H column with chloroform as the eluent. High resolution mass spectra (HRMS) were performed on a Bruker Daltonics Ultraflex III TOF / TOF (MALDI-TOF-MS). Nuclear magnetic resonance (NMR) spectra were recorded on a JEOL ECA 500II spectrometer equipped with an UltraCool probe ( ¹ H 500 MHz, ¹³ C 125 MHz). ¹ H NMR chemical shifts were expressed as relative parts per million (ppm) of CHCl ₃ (δ 7.26 ppm). The chemical shift of ¹³ C NMR was expressed in relative parts per million (ppm) of CDCl ₃ (δ77.0 ppm). Data is reported in the order of chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet), couplinh constant (Hz), and integration.

[Example 1: Thiophene ring condensation reaction]
Example 1-1: Synthesis of compound 2a

In the open air, compound 1a (17.8 g, 53.2 mmol, 1.0 equivalent) and sulfur (S ₈ ; 13.6 g, 53.2 mmol, 1.0 equivalent) were added to a Schlenk tube. The tube was filled with argon using the usual Schlenk technique (evacuate-refill cycle). The tube was charged with dimethylformamide (DMF; 200 mL) and the mixture was heated at 140 ° C. for 36 hours. The mixture was then cooled to room temperature. The resulting solution was concentrated under vacuum. Further purification by recrystallization from CH ₂ Cl ₂ / methanol solution gave the target compound 2a (18.0 g, 93% yield). This embodiment corresponds to entry 1 in Table 1 described later.
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.72-8.68 (m, 2H), 8.36 (dd, J = 7, 2 Hz, 1H), 8.15-8.13 (m, 2H), 7.77 (d, J = 9 Hz, 2H), 7.68-7.61 (m, 4H) 7.50 (d, J = 9 Hz, 2H), 1.39 (s, 9H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 151.3, 143.4, 135.9, 135.8 , 131.5, 129.1, 128.7, 128.5, 128.2, 127.2, 127.0, 126.1, 126.0, 124.2, 124.1, 123.6, 123.5, 118.3, 34.7, 31.3; HRMS (ESI-MS) m / zcalcd for C ₂₆ H ₂₂ S (M + H] ⁺ : 367.1515, found: 367.1507.

In this reaction, the palladium concentration of compound 1a, sulfur (S ₈ ), and DMF was measured and found to be less than 1 ppm (less than the measurement limit). From this, it can be understood that the thiophene ring condensation reaction of the present invention is not a catalytic reaction, and no catalyst is required.

Example 1-2: Synthesis of Compound 2b The target compound 2b was obtained in the same manner as in Example 1-1 except that the conditions shown in Table 1 below were used. In addition, it is purified by recrystallization from a CH ₂ Cl ₂ / methanol solution for entry 1, purified by GPC for entries 2 to 3, 6 to 7, 12 to 13, and 16 to 20, and TLC (n-hexane for entry 4 / Ethyl acetate / CH ₂ Cl ₂ = 20: 1: 2), and for entry 5, 8-9 and 15, purified by TLC (n-hexane / CH ₃ Cl = 10: 1), entry 10-11 And purified by TLC (n-hexane / CH ₃ Cl = 5: 1), and entry 14 was purified by TLC (n-hexane / CH ₃ Cl = 5: 2).

In addition, the spectrum data of each obtained compound are as follows.
Compound 2b:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.36 (d, J = 9 Hz, 1H), 8.16 (s, 1H), 7.94 (d, J = 8 Hz, 1H), 7.84 (d, J = 8 Hz , 1H), 7.73-7.69 (m, 3H), 7.62 (t, J = 8 Hz, 1H), 7.53 (t, J = 8 Hz, 1H), 7.27 (d, J = 8 Hz, 2H), 2.42 (s, 3H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 144.2, 138.1, 136.9, 136.8, 131.7, 131.1, 129.7, 129.2, 128.6, 126.4, 126.2, 125.2, 124.8, 123.5, 120.5, 117.1, 21.2 HRMS (DART-MS) m / zcalcd for C ₁₅ H ₁₅ S [M + H] ⁺ : 275.0889, found: 275.0911.
Compound 2c:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.12 (d, J = 8 Hz, 1H), 7.91 (d, J = 8 Hz, 1H), 7.78 (d, J = 9 Hz, 1H), 7.72 (d , J = 9 Hz, 1H), 7.67 (d, J = 8 Hz, 2H), 7.62 (s, 1H), 7.57 (t, J = 8 Hz, 1H), 7.50 (t, J = 8 Hz, 1H ), 2.41 (s, 3H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 137.6, 135.0, 134.6, 133.7, 132.9, 129.4, 129.0, 128.2, 127.9, 127.8, 127.7, 126.5, 126.4, 126.3, 125.8, 123.5, 21.3; HRMS (ESI-MS) m / z calcd for C ₁₅ H ₁₅ S [M + H] ⁺ : 275.0889, found: 275.0882.
Compound 2d:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.01 (s, 1H), 7.73 (t, J = 9 Hz, 2H), 7.51 (d, J = 8 Hz, 2H), 7.44 (t, J = 7 Hz , 1H), 7.35 (t, J = 7 Hz, 1H), 7.17 (d, J = 8 Hz, 2 H), 7.13 (s, 1H), 4.02 (s, 3H), 2.63 (t, J = 8 Hz, 2H), 1.62 (quint, J = 7 Hz, 2H), 1.37 (sext, J = 7 Hz, 2H), 0.94 (t, J = 7 Hz, 3H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 153.2, 143.1, 143.0, 138.0, 132.4, 132.2, 131.8, 129.0, 127.6, 126.2, 125.8, 124.8, 124.2, 123.3, 116.8, 55.4, 35.4, 33.5, 22.4, 14.0; HRMS (ESI-MS) m / z calcd for C ₂₃ H ₂₂ OS [M + H] ⁺ : 347.1464, found: 347.1458.
Compound 2e:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.03 (d, J = 8 Hz, 1H), 7.90 (s, 1H), 7.79 (d, J = 8 Hz, 1H), 7.75 (s, 1H), 7.68 (d, J = 9 Hz, 2H), 7.55 (t, J = 8 Hz, 1H), 7.48 (t, J = 8 Hz, 1H), 7.25 (d, J = 9 Hz, 2H), 2.66 (t , J = 8 Hz, 2H), 1.64 (quint, J = 7 Hz, 2H), 1.39 (sext, J = 7 Hz, 2H), 0.95 (t, J = 7 Hz, 3H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 144.0, 143.6, 138.0, 137.0, 131.5, 131.3, 129.1, 128.0, 127.9, 127.8, 126.9, 126.3, 126.2, 123.5, 120.5, 115.6, 35.4, 33.5, 22.4, 14.0; HRMS (ESI- MS) m / z calcd for C ₂₂ H ₁₉ BrS [M + H] ⁺ : 395.0464, found: 395.0457.
Compound 2f:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.45 (s, 1H), 8.34 (d, J = 9 Hz, 1H), 8.23 (d, J = 1 Hz, 1H), 8.20 (d, J = 9 Hz , 1H), 8.19 (s, 1H), 8.04 (d, J = 9 Hz, 1H), 7.96 (d, J = 9 Hz, 1H), 7.89 (s, 1H), 7.77 (d, J = 8 Hz , 2H), 7.30 (d, J = 8 Hz, 2H), 2.44 (s, 3H), 1.60 (s, 9H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 148.8, 144.3, 138.8, 138.4, 134.9 , 131.6, 131.0, 130.8, 129.7, 129.1, 128.2, 127.8, 126.9, 126.6, 125.3, 123.4, 122.5, 122.4, 122.1, 119.7, 119.3, 35.2, 31.9, 21.3; HRMS (ESI-MS) m / z calcd for C ₂₉ H ₂₄ S [M + H] ⁺ : 405.1671, found: 405.1666.
Compound 2g:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.30 (s, 1H), 8.22 (d, J = 8 Hz, 1H), 8.18 (s, 1H), 7.97 (d, J = 7.0 Hz, 1H), 7.95 -7.92 (m, 2H), 7.75-7.72 (m, 3H), 7.40-7.38 (m, 2H), 7.29 (d, J = 8 Hz, 2H), 2.68 (t, J = 8 Hz, 2H), 1.67 (quint, J = 7 Hz, 2H), 1.41 (sext, J = 7 Hz, 2H), 0.97 (t, J = 7 Hz, 3H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 145.6, 143.4 , 140.1, 139.2, 138.9, 137.02, 136.98, 133.7, 131.7, 131.0, 129.1, 128.0, 127.5, 127.4, 126.2, 126.0, 122.6, 121.5, 121.3, 119.0, 117.2, 115.3, 35.4, 33.5, 22.4, 14.0; HRMS (ESI-MS) m / z calcd for C ₂₈ H ₂₂ S [M + H] ⁺ : 391.1515, found: 391.1507.
Compound 2h:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.61 (d, J = 8 Hz, 1H), 8.40 (d, J = 7 Hz, 1H), 8.30 (s, 1H), 8.18 (d, J = 7 Hz , 1H), 8.15 (d, J = 8 Hz, 1H), 8.10-8.00 (m, 4H), 7.80 (d, J = 8 Hz, 2H), 7.32 (d, J = 8 Hz, 2H), 2.70 (t, J = 8 Hz, 2H), 1.68 (quint, J = 7 Hz, 2H), 1.43 (sext, J = 7 Hz, 2H), 0.98 (t, J = 7 Hz, 3H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 143.9, 143.1, 136.3, 135.9, 131.7, 131.7, 129.1, 127.7, 127.3, 126.14, 126.08, 125.9, 125.0, 124.8, 123.4, 122.9, 121.0, 120.5, 118.4, 35.4, 33.5, 22.4, 14.0; HRMS (ESI-MS) m / z calcd for C ₂₈ H ₂₂ S [M + H] ⁺ : 391.1515, found: 391.1508.
Compound 2i:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.20 (s, 1H), 8.07 (d, J = 9 Hz, 1H), 7.95 (d, J = 9 Hz, 1H), 7.88 (d, J = 9 Hz , 1H), 7.86 (d, J = 9 Hz, 1H), 7,82-7.76 (m, 6H), 7.52 (d, J = 9 Hz, 1H), 1.40 (s, 9H); ¹³ C NMR ( 125 MHz, CDCl ₃ ) δ 151.5,144.6, 138.6, 136.5, 136.0, 135.55, 135.48, 134.4, 133.6, 131.5, 130.8, 129.9, 129.6, 127.8, 127.7, 127.5, 127.1, 127.0, 126.71, 126.68, 126.03, 125.98 , 124.8, 124.5, 118.2, 34.7, 31.3; HRMS (ESI-MS) m / zcalcd for C ₃₂ H ₂₂ S [M + H] ⁺ : 439.1515, found: 439.1508.
Compound 2j:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.01 (d, J = 9 Hz, 2H), 7.87 (d, J = 9 Hz, 2H), 7.70 (d, J = 8 Hz, 4H), 7.65 (s , 2H), 7.27 (d, J = 8 Hz, 4H), 2.67 (t, J = 8 Hz, 2H), 1.66 (quint, J = 7 Hz, 2H), 1.41 (sext, J = 7 Hz, 2H ), 0.97 (t, J = 7 Hz, 3H); ¹³ C NMR (125 MHz, C ₂ D ₂ Cl ₄ ) δ 143.5, 143.3, 138.1, 137.5, 131.3, 129.0, 126.1, 125.5, 122.6, 121.2, 120.1 , 35.3, 33.4, 22.6, 14.0; HRMS (ESI-MS) m / zcalcd for C ₃₄ H ₃₂ S ₂ [M + H] ⁺ : 505.2018, found: 505.2010.
Compound 2k:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.38 (dd, J = 6, 3 Hz, 2H), 8.14 (s, 2H), 7.72 (d, J = 8 Hz, 4H), 7.63 (dd, J = 6, 3 Hz, 2H), 7.28 (d, J = 8 Hz, 4H), 2.68 (t, J = 8 Hz, 4H), 1.67 (quint, J = 7 Hz, 4H), 1.42 (sext, J = 7 Hz, 4H), 0.97 (t, J = 7 Hz, 6H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 143.0, 142.2, 135.0, 131.6, 131.0, 129.0, 127.5, 126.0, 125.6, 124.3, 117.6 , 35.4, 33.5, 22.4, 14.0; HRMS (ESI-MS) m / zcalcd for C ₃₄ H ₃₂ S ₂ [M + H] ⁺ : 505.2018, found: 505.2008.
Compound 2l:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.33 (d, J = 8 Hz, 1H), 8.12 (d, J = 8 Hz, 1H), 8.11 (s, 1H), 7.72 (s, 1H), 7.71 (d, J = 7 Hz, 4H), 7.58-7.40 (m, 2H), 7.26 (d, J = 7 Hz, 4H), 2.67 (t, J = 8 Hz, 4H), 1.66 (quint, J = 7 Hz, 4H), 1.41 (sext, J = 7 Hz, 4H), 0.97 (t, J = 7 Hz, 6H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 144.8, 143.4, 143.0, 142.5, 135.4 , 133.9, 132.9, 132.2, 131.8, 131.5, 129.1, 127.3, 127.1, 126.2, 126.1, 125.94, 125.89, 124.58, 124.2, 117.7, 117.5, 35.4, 33.5, 22.4, 14.0; HRMS (ESI-MS) m / z calcd for C ₃₄ H ₃₂ S ₂ [M + H] ⁺ : 505.2018, found: 505.2010.
Compound 2m:
¹ H NMR (500 MHz, CDCl ₃ , 25 ° C) δ 7.9 (s, 4H), 7.81 (d, J = 8.0 Hz, 4H), 7.78 (s, 2H), 7.30 (d, J = 8.0 Hz, 4H ), 2.68 (t, J = 7.8 Hz, 2H), 1.70-1.64 (m, 4H), 1.40-1.31 (m, 12H), 0.92-0.89 (m, 6H); ¹³ C NMR (125 MHz, CDCl ₃ , 25 ° C) δ 145.2, 143.4, 140.8, 139.0, 133.5, 131.7, 129.1, 129.0, 126.5, 126.1, 124.3, 121.4, 119.8, 35.8, 31.7, 31.4, 29.0, 22.6, 14.1; HRMS (ESI-MS) m / z calcd for C ₃₈ H ₄₀ S ₂ [M + H] ⁺ : 561.2644, found: 561.2632.
Compound 2n:
¹ H NMR (500 MHz, CDCl ₃ ) δ 9.36 (dd, J = 8, 2 Hz, 2H), 8.50 (dd, J = 8, 2 Hz, 2H), 8.22 (s, 2H), 7.79 (d, J = 8 Hz, 4H), 7.79-7.75 (m, 4H), 7.29 (d, J = 8 Hz, 4H), 2.68 (t, J = 7 Hz, 4H), 1.69 (quint, J = 7 Hz, 4H), 1.43-1.31 (m, 12H), 0.92 (t, J = 7 Hz, 6H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 144.0, 143.2, 136.4, 133.9, 131.4, 129.0, 128.8, 128.6 , 126.8, 126.1, 126.0, 124.6, 124.1, 117.2, 35.8, 31.8, 31.4, 29.0, 22.6, 14.1; HRMS (ESI-MS) m / z calcd for C ₄₆ H ₄₄ S ₂ [M + H] ⁺ : 661.2957 , found: 661.2937.
Compound 2o:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.71-8.67 (m, 2H), 8.35-8.34 (m, 1H), 8.13-8.10 (m, 1H), 8.00 (s, 1H), 7.71 (d, J = 9 Hz, 2H), 7.68-7.58 (m, 4H), 6.82 (d, J = 8 Hz, 2H), 3.04 (s, 6H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 150.3, 144.4, 136.1, 134.6, 129.1, 128.7, 128.3, 128.2, 127.14, 127.10, 125.8, 125.7, 124.2, 124.0, 123.5, 123.4, 122.5, 116.1, 112.4, 115.6, 40.4; HRMS (MALDI-TOF-MS) m / z calcd for C ₂₄ H ₁₉ NS [M] ⁺ : 353.1233, found: 353.1208.
Compound 2p:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.69 (t, J = 9 Hz, 2H), 8.34 (d, J = 7 Hz, 1H), 8.10 (d, J = 7 Hz, 1H), 8.00 (s , 1H), 7.67-7.58 (m, 6H), 6.77 (d, J = 9 Hz, 2 H), 3.83 (s, 2H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 146.6, 144.1, 136.1, 134.9, 129.1, 128.7, 128.3, 128.3, 127.47, 127.46, 127.19, 127.0, 125.9, 124.9, 124.2, 124.0, 123.6, 123.5, 116.7, 115.3; HRMS (MALDI-TOF-MS) m / zcalcd for C ₂₂ H ₁₅ NS [M] ⁺ : 325.0920, found: 325.09051.
Compound 2q:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.72 (d, J = 8 Hz, 3H), 8.41 (d, J = 8 Hz ,, 3H), 8.03 (s, 3H), 7.71 (t, J = 7 Hz, 3H), 7.56 (d, J = 8 Hz, 6H), 7.40 (t, J = 8 Hz, 3H), 7.19 (d, J = 8 Hz, 6H), 2.62 (t, J = 8 Hz, 6H), 1.62 (quint, J = 8 Hz, 6H), 1.38 (sext, J = 7 Hz, 6H), 0.94 (t, J = 7 Hz, 9H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 143.6, 143.0, 137.0, 136.3, 132.0, 131.4, 128.9, 128.7, 128.0, 127.6, 126.6, 126.2, 125.2, 123.9, 123.1, 116.5, 35.3, 33.5, 22.3, 14.0; HRMS (ESI-MS) m / z calcd for C ₆₆ H ₅₄ S ₃ [M + H] ⁺ : 943.3460, found: 943.3445.
Compound 2r:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.73 (s, 5H), 7.85 (d, J = 2 Hz, 10H), 7.55 (d, J = 2 Hz, 5H), 1.49 (s, 90H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 151.8, 146.2, 136.7, 135.5, 133.6, 131.8, 122.9, 122.6, 121.3, 120.2, 35.1, 31.4.HRMS (MALDI-TOF-MS) m / zcalcd for C ₁₀₀ H ₁₁₀ S ₅ [M] ⁺ : 1470.721, found: 1470.720.
Compound 2s:
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.19 (d, J = 9 Hz, 1H), 8.11-8.02 (m, 5H), 7.95-7.93 (m, 2H), 7.71-7.57 (m, 10H), 7.44 (s, 1H), 7.33-7.31 (m, 2H), 7.22-7.21 (m, 2H), 7.04 (d, J = 8 Hz, 2H), 2.35 (t, J = 8 Hz, 2H), 1.57 -1.52 (m, 2H), 1.31 (quint, J = 7 Hz, 2H), 0.89 (t, J = 7 Hz, 2H).
Compound 2t:
¹ H NMR (500 MHz, CDCl ₃ ) δ 9.38 (m, 1H), 8.55 (s, 1H), 8.47 (s, 2H), 7.90-7.84 (m, 4H), 7.69 (9) -7.69 (6) (m, 4H), 7.48 (s, 2H), 1.45 (s, 36H).

  [Example 2: One-pot synthesis of thiophene ring condensed aromatic compound (Sonogashira coupling-thiophene ring condensed ring)]

[Wherein, Tf represents a trifluoromethanesulfonyl group. dppf represents 1,1′-bis (diphenylphosphino) ferrocene. Et represents an ethyl group. The same applies hereinafter. ]
In the open air, phenanthrene-9-yltrifluoromethanesulfonate (163 mg, 0.5 mmol, 1.0 equivalent), palladium acetate (Pd (OAc) ₂ ; 2.2 mg, 0.01 mmol, 2 mol%), 1,1′-bis ( Diphenylphosphino) ferrocene (dppf; 5.5 mg, 0.01 mmol, 2 mol%) and CuI (1.9 mg, 0.01 mmol, 2 mol%) were put into a Schlenk tube. The tube was filled with argon using the usual Schlenk technique (evacuate-refill cycle). A tube was charged with dimethylformamide (DMF; 5.0 mL), triethylamine (Et ₃ N; 2 eq), and 1- (tert-butyl) -4-ethynylbenzene (79 mg, 0.5 mmol, 1.0 eq). Heated at 12 ° C. for 12 hours, then 3 equivalents of sulfur (S ₈ ) was added to the reaction mixture under an argon atmosphere and further heated at 140 ° C. for 48 hours with stirring with a magnetic stir bar. The mixture was then cooled to room temperature. The resulting solution was concentrated under vacuum. Furthermore, the mixture was purified by TLC to obtain the target compound 2a (128 mg, 70% yield).

[Example 3: Thiophene ring condensation reaction of diaryldiyne]
Example 3-1: Synthesis of compound 2u

In the open air, compound 1u (35.6 mg, 0.1 mmol, 1.0 equivalent) and sulfur (S ₈ ; 102 mg, 0.4 mmol, 4.0 equivalent) were added to a Schlenk tube. The tube was filled with argon using the usual Schlenk technique (evacuate-refill cycle). The tube was charged with dry dimethylformamide (DMF; 1.0 mL) and the mixture was heated at 140 ° C. for 48 hours. The mixture was then cooled to room temperature. The resulting solution was concentrated under vacuum. Further, purification by GPC gave the target compound 2u (15.3 mg, 36% yield).
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.78 (d, J = 8 Hz, 1H), 8.73-8.71 (m, 1H), 8.46 (d, J = 8 Hz, 1H), 8.14-8.12 (m, 1H), 7.81 (t, J = 7 Hz, 1H), 7.72 (t, J = 7 Hz, 1H), 7,68 (d, J = 8 Hz, 2H), 7.67-7.63 (m, 1H), 7.26 (d, J = 8 Hz, 1H), 2.68 (t, J = 8 Hz, 2H), 1.67 (quint, J = 7 Hz, 2H), 1.42 (sext, J = 7 Hz, 2H), 0.97 ( t, J = 7 Hz, 3H); ¹³ C NMR (125 MHz, C ₂ D ₂ Cl ₄ ) δ 150.5, 146.4, 141.8, 141.1, 136.9, 134.7, 132.3, 132.2, 131.8, 131.5, 131.0, 130.7, 130.6 , 130.2, 129.7, 129.4, 128.9, 127.7, 127.0, 126.8, 126.7, 118.4, 38.5, 36.6, 25.7, 17.2.HRMS (MALDI-TOF-MS) m / z calcd for C ₂₈ H ₂₂ S ₂ [M] ⁺ : 422.1157, found: 422.1148.

Example 3-2: Synthesis of compound 2v

In the open air, Compound 1v (149 mg, 0.24 mmol, 1.0 equivalent) and sulfur (S ₈ ; 122.9 mg, 0.48 mmol, 2 equivalent) were added to a Schlenk tube. The tube was filled with argon using the usual Schlenk technique (evacuate-refill cycle). The tube was charged with dry dimethylformamide (DMF; 3.0 mL) and dry ethanol (EtOH; 1.2 mL) and the mixture was heated at 140 ° C. for 48 hours. The mixture was then cooled to room temperature. The resulting solution was concentrated under vacuum. Further, purification by GPC gave the target compound 2v (46.3 mg, 28% yield).
¹ H NMR (500 MHz, CDCl ₃ ) δ 8.27 (s, 2H), 7.55 (s, 2H), 7.53 (d, J = 2 Hz, 4H), 7.44 (t, J = 2 Hz, 2H), 1.40 (s, 36H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 151.7, 148.8, 140.1, 140.0, 133.8, 132.7, 130.4, 122.7, 120.6, 116.3, 115.4, 35.1, 31.5; HRMS (MALDI-TOF-MS ) m / z calcd for C ₄₂ H ₄₆ S ₄ [M] ⁺ : 614.3035, found: 614.3024.HRMS (MALDI-TOF-MS) m / z calcd for C ₄₂ H ₄₆ S ₄ [M] ⁺ : 678.2477, found : 678.2479.

Example 3-3: Synthesis of compound 2w

In the open air, Compound 1w (157.2 mg, 0.3 mmol, 1.0 equivalent) and sulfur (S ₈ ; 153.6 mg, 0.6 mmol, 2 equivalent) were added to a Schlenk tube. The tube was filled with argon using the usual Schlenk technique (evacuate-refill cycle). The tube was charged with dry dimethylformamide (DMF; 3.0 mL) and dry ethanol (EtOH; 1.2 mL) and the mixture was heated at 140 ° C. for 24 hours. The mixture was then cooled to room temperature. The resulting solution was concentrated under vacuum. Further, purification by GPC gave the target compound 2w (38.4 mg, 22% yield).
¹ H NMR (500 MHz, CDCl ₃ ) δ 7.56 (d, J = 8 Hz, 4H), 7.46 (s, 2H), 7.23 (d, J = 8 Hz, 4H), 2.63 (t, J = 7 Hz , 4H), 1.64 (quint, J = 7 Hz, 4H), 1.37-1.26 (m, 20H), 0.88 (t, J = 7 Hz, 6H); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 145.3, 143.1, 141.6, 132.1, 130.1, 129.2, 125.7, 116.1, 35.8, 32.0, 31.5, 29.6, 29.4 (2), 29.3 (6), 22.8, 14.2.

In addition, since the compound having the same skeleton as the obtained compound 2w is reported as μ = 10.2 cm ² V ⁻¹ s ⁻¹ , according to the production method of the present invention, the world-class conductivity is obtained. It can be understood that the organic semiconductors can be easily synthesized.

[Test Example 1: Photophysical properties]
Compound 2a obtained in Example 1-1, Compound 2f obtained in Example 1-2, Compound 2g obtained in Example 1-2, Compound 2h obtained in Example 1-2, Example 1-2 Compound 2i obtained, Compound 2j obtained in Example 1-2, Compound 2k obtained in Example 1-2, Compound 2l obtained in Example 1-2, Compound 2m obtained in Example 1-2, Implementation Compound 2n obtained in Example 1-2, Compound 2o obtained in Example 1-2, Compound 2p obtained in Example 1-2, Compound 2q obtained in Example 1-2, Obtained in Example 1-2 With respect to Compound 2r, Compound 2u obtained in Example 3-1, and Compound 2v obtained in Example 3-2, an absorption spectrum and a fluorescence spectrum were measured. The results are shown in FIGS. In addition, in FIGS. 1-16, a continuous line shows an absorption spectrum and a broken line shows a fluorescence spectrum. Φ _F indicates the absolute fluorescence quantum yield.

Claims (8)

A method for producing a thiophene ring condensed aromatic compound in which one or more thiophene rings are condensed to a polycyclic aromatic hydrocarbon ring or a heteroaromatic ring,
Comprising a step of reacting a polycyclic aromatic compound or heterocyclic compound with sulfur;
The polycyclic aromatic compound or heterocyclic compound has the general formula (1):

[Wherein, R ¹ represents an optionally substituted aryl group. n represents an integer of 1 or more. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond. ]
A manufacturing method having one or more structures represented by: The polycyclic aromatic compound or heterocyclic compound is represented by the general formula (3):

[Wherein, R ¹ and n are the same as defined above. Ar represents a polycyclic aromatic hydrocarbon ring which may be substituted or a heteroaromatic ring which may be substituted. R ³ represents a group represented by — (C≡C) _n —R ¹ . The group represented by-(C≡C) _n -R ¹ is not bonded to at least one carbon atom adjacent to the carbon atom on the Ar ring to which R ³ is bonded. Hydrogen atoms are bonded. m represents an integer of 0 or more. ]
The manufacturing method of Claim 1 which is a compound represented by these. Ar represents an optionally substituted naphthalene ring, an optionally substituted anthracene ring, an optionally substituted phenanthrene ring, and an optionally substituted tetracene. A ring, an optionally substituted pyrene ring, an optionally substituted fluoranthene ring, an optionally substituted pentacene ring, an optionally substituted perylene ring, Optionally substituted corannulene ring, optionally substituted chrysene ring, optionally substituted benzo [c] naphtho [2,1-p] chrysene ring, substituent A thiophene ring optionally having a substituent, a benzothiophene ring optionally having a substituent, a dithienobenzene ring optionally having a substituent, or one or more of these rings condensed with a benzene ring The production method according to claim 2, wherein the ring is a ring. The manufacturing method in any one of Claims 1-3 with which the said reaction process is performed in a polar solvent. The polycyclic aromatic compound or heterocyclic compound has the general formula (1A)

[Wherein, R ¹ is the same as defined above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
Having one or more structures represented by
The produced thiophene ring-fused aromatic compound has the general formula (2A):

Wherein, R ² is either same group as R ^1, a group R ¹ is reduced, it represents an aryl group which may be substituted. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
The manufacturing method of Claim 1 which has one or more structures represented by these. The polycyclic aromatic compound or heterocyclic compound has the general formula (1B)

[Wherein, R ¹ is the same as defined above. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
Having one or more structures represented by
The produced thiophene ring-fused aromatic compound has the general formula (2B):

Wherein, R ² is either same group as R ^1, a group R ¹ is reduced, it represents an aryl group which may be substituted. A bond indicated by a dotted line and a broken line indicates a single bond or a double bond constituting a part of a polycyclic aromatic hydrocarbon ring or a heterocyclic ring. ]
The manufacturing method of Claim 1 which has one or more structures represented by these. The polycyclic aromatic compound or the heterocyclic compound is represented by the general formula (3E):

[Wherein, R ¹ is the same or different and is the same as defined above. ]
Or a compound represented by the general formula (3F):

[Wherein, R ¹ is the same or different and is the same as defined above. ]
The manufacturing method in any one of Claims 1-6 which is a compound represented by these. A thiophene ring-fused aromatic compound in which a polycyclic aromatic hydrocarbon ring which may have a substituent is condensed with a thiophene ring which may have one or more substituents,
A reaction between a polycyclic aromatic compound and sulfur,
The polycyclic aromatic compound is
General formula (3):

[Wherein, R ¹ represents an optionally substituted aryl group. n represents an integer of 1 or more. Ar represents a polycyclic aromatic hydrocarbon ring which may be substituted or a heteroaromatic ring which may be substituted. R ³ represents a group represented by — (C≡C) _n —R ¹ . The group represented by-(C≡C) _n -R ¹ is not bonded to at least one carbon atom adjacent to the carbon atom on the Ar ring to which R ³ is bonded. Hydrogen atoms are bonded. m represents an integer of 0 or more. ]
A thiophene ring-condensed aromatic compound represented by (a compound in which two thiophene rings optionally having a substituent are condensed on the naphthalene ring, a thiophene ring optionally having a substituent on the anthracene ring is 1 or 4 condensed compounds, and compounds in which anthraquinone optionally having one substituent thiophene ring is condensed).

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