JP7097573B2 - Compounds and organic semiconductor materials containing them - Google Patents

Description

The present invention relates to tetrazolopyridine compounds. More specifically, the present invention relates to a novel tetrazolopyridine compound that can be used as an organic semiconductor material.

Tetrazolopyridine compounds are known as pharmaceutical intermediates. For example, in Patent Document 1, a tetrazolopyridine compound having a glycidyl group is synthesized using 6-chloronicotinic acid chloride as a raw material. Further, Non-Patent Document 1 proposes a tetrazolopyridine compound having various substituents.

Special Table 2001-526282 Gazette

John M. Keith, "One-Step Conversion of Pyridine N-Oxides to Tetrazole [1,5-a] Pyridines", Journal of Organic Chemistry, 2006, 71, p. 9540-9543

However, the effect of using the above tetrazolopyridine compound as an organic semiconductor material has not been known.

As a result of diligent research to solve the above problems, the present inventors have fused a tetrazolopyridine compound with a 5-membered heterocycle containing at least one -SO _2- as a ring component. The present invention was completed by finding that the compound can lower the LUMO level and is useful as an organic semiconductor material.

That is, the compound of the present invention is characterized by being represented by any of the following formulas (1) to (3). In the following formulas (1) to (3), Y ¹ and Y ² each independently represent a 5-membered heterocycle containing at least one -SO _2- as a ring component.

It is preferable that Y ¹ and Y ² are heterocycles independently represented by the following formulas (Y1) or (Y2). In the following formula (Y1) or (Y2), R ¹ represents a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, or an alkyl halide group. p1 represents an integer of 0 to 2, p2 represents an integer of 0 to 1, and p3 represents an integer of 0 to 3. One of * a and * b is * 1 in the equations (1) to (3), and the other is * 2.

Compounds having structural units represented by any of the following formulas (I), (IIA), (IIB), (IIC) and (IID) are also included in the scope of the present invention. In the following formulas (I), (IIA), (IIB), (IIC) and (IID), Y ¹ , Y ² , Y ¹¹ and Y ¹² each independently have -SO _2- as a ring component. Represents a 5-membered heterocycle containing at least one. D represents a bond.

The compounds having a structural unit represented by any of the compounds (I), (IIA), (IIB), (IIC) and (IID) are the following formulas (I-1) and (II-1A) to (II-1A). It is preferably a compound represented by any of II-1J). In the following formulas (I-1) and (II-1A) to (II-1J), Y ¹ , Y ² , Y ¹¹ and Y ¹² each independently contain at least 1 -SO _2- as a ring component. Represents a 5-membered heterocycle including. A ¹ represents an aromatic ring which may have a substituent. n1 and n2 each independently represent an integer of 1 or more. R ³ independently represents a hydrogen atom or an alkyl group.

The present invention also includes a polymer compound having a structural unit represented by the formula (I) and one or more donor units. In formula (I), Y ¹¹ and Y ¹² each independently represent a 5-membered heterocycle containing at least one —SO _2- as a ring component.

The donor unit is preferably a structural unit represented by any of the formulas (Dn-1) to (Dn-15). In the following formulas (Dn-1) to (Dn-15), R ³⁰ independently represents an aliphatic hydrocarbon group. R ³¹ represents a hydrogen atom or an aliphatic hydrocarbon group. * Represents a bond.

An organic semiconductor material containing the compound or a polymer compound and an organic electronic device containing the organic semiconductor material are also included in the technical scope of the present invention.

Since the compound of the present invention is a tetrazolopyridine compound fused with a 5-membered heterocycle containing at least one -SO _2- as a ring component, the LUMO level can be lowered and it is useful as an organic semiconductor material. be.

Hereinafter, the present invention will be described. In addition, the "compound represented by the formula (x)" may be simply referred to as "compound (x)" below. The compound of the present invention also includes tautomers thereof and salts thereof, and each component and functional group exemplified below can be used alone or in combination.

1. 1. Compound The compound of the present invention is represented by the following formula (1), (2) or (3). In the following formulas (1) to (3), Y ¹ and Y ² each independently represent a 5-membered heterocycle containing at least one -SO _2- as a ring component.

Examples of the heterocycle represented by Y ¹ or Y ² include a heterocycle represented by the following formula.

Of these, a dioxothiophene ring and a dioxothiazole ring are preferable.

The heterocycle represented by Y ¹ or Y ² does not have to have a substituent and is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an aliphatic hydrocarbon group; an alkoxy group; and a halogen. It is also preferable that it is substituted with one or more selected from the alkylated groups.

(Halogen atom)
As the halogen atom, a bromine atom and an iodine atom are preferable, and a bromine atom is particularly preferable.

(Adipose hydrocarbon group)
The aliphatic hydrocarbon group may be chain-like or cyclic. In the case of a chain, it may be either a linear chain or a branched chain.

The chain aliphatic hydrocarbon group may be any of an alkyl group; or a chain unsaturated aliphatic hydrocarbon group such as an alkenyl group and an alkynyl group, and is more preferably an alkyl group.

The chain aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms, and further preferably 1 to 20 carbon atoms.

The alkyl group may be either a linear or branched alkyl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, or n. -Hexyl group, n-heptyl group, n-octyl group, 1-n-butylbutyl group, 1-n-propylpentyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1 -Methylheptyl group, 2-methylheptyl group, 6-methylheptyl group, 2,4,4-trimethylpentyl group, 2,5-dimethylhexyl group, n-nonyl group, 1-n-propylhexyl group, 2- n-Propylhexyl group, 1-ethylheptyl group, 2-ethylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 6-methyloctyl group, 2,3,3,4-tetramethylpentyl group, 3 , 5,5-trimethylhexyl group, n-decyl group, 1-n-pentylpentyl group, 1-n-butylhexyl group, 2-n-butylhexyl group, 1-n-propylheptyl group, 1-ethyloctyl Group, 2-ethyloctyl group, 1-methylnonyl group, 2-methylnonyl group, 3,7-dimethyloctyl group, n-undecyl group, 1-n-butylheptyl group, 2-n-butylheptyl group, 1-n -Propyloctyl group, 2-n-propyloctyl group, 1-ethylnonyl group, 2-ethylnonyl group, n-dodecyl group, 1-n-pentylheptyl group, 2-n-pentylheptyl group, 1-n-butyloctyl group Group, 2-n-butyl octyl group, 1-n-propylnonyl group, 2-n-propylnonyl group, n-tridecyl group, 1-n-pentyloctyl group, 2-n-pentyloctyl group, 1-n -Butylnonyl group, 2-n-butylnonyl group, 1-methyldecyl group, 2-methyldecyl group, n-tetradecyl group, 1-n-heptylheptyl group, 1-n-hexyloctyl group, 2-n-hexyloctyl group, 1-n-pentylnonyl group, 2-n-pentylnonyl group, n-pentadecyl group, 1-n-heptyloctyl group, 1-n-hexylnonyl group, 2-n-hexylnonyl group, n-hexadecyl group, 2-Hexyldecyl group, 1-n-octyloctyl group, 1-n-heptylnonyl group, 2-n-heptylnonyl group, n-heptadecyl group, 1-n-octylnonyl group, n-octadecyl group, 1-n- Nonyl Nonyl group, n-nonadecyl group, n-eicosyl group, 2-octyldodecyl group, Examples thereof include an n-heneicosyl group, an n-docosyl group, an n-tricosyl group, an n-tetracosyl group and a 2-decyltetradecyl group.

The cyclic aliphatic hydrocarbon group (alicyclic hydrocarbon group) may be either monocyclic or polycyclic.

The alicyclic hydrocarbon group may be either a cycloalkyl group or an unsaturated alicyclic hydrocarbon group such as a cycloalkenyl group or a cycloalkynyl group, and is preferably a cycloalkyl group.

The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 14 carbon atoms.

Specific examples of the alicyclic hydrocarbon group include a monocyclic cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group; bicyclohexyl. Examples thereof include a polycyclic cycloalkyl group such as a group, a bicycloheptyl group and a bicyclooctyl group.

(Alkoxy group)
Examples of the alkoxy group include a group in which —O— is bonded to the alkyl group.

The alkoxy group preferably has 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms.

(Halogenated alkyl group)
Examples of the halogenated alkyl group include groups in which the hydrogen atom of the alkyl group is replaced with a halogen atom (particularly preferably a fluorine atom) such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl halide group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms.

Specific examples of the alkyl halide group include a perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group and a nonafluorobutyl group, and a trifluoromethyl group is particularly preferable.

The number of substitutions of the substituent is preferably 0, 1 or 2 for each heterocycle represented by Y ¹ or Y ² , and particularly preferably 0 or 1.

As the heterocycle represented by Y ¹ or Y ² , specifically, a ring represented by the following formula is preferable. In the following formula (Y1) or (Y2), R ¹ represents a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, or an alkyl halide group. p1 represents an integer of 0 to 2, and p2 represents an integer of 0 to 1. One of * a and * b is * 1 in the equations (1) to (3), and the other is * 2.

(Halogen atom)
Examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a bromine atom and an iodine atom are preferable.

(Adipose hydrocarbon group)
The aliphatic hydrocarbon group represented by R ¹ preferably has 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms, and even more preferably 1 to 20 carbon atoms.

Examples of the aliphatic hydrocarbon group represented by R ¹ include groups similar to the aliphatic hydrocarbon group in which the heterocycle represented by Y ¹ or Y ² may be substituted.

(Alkoxy group)
The alkoxy group represented by R ¹ preferably has 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms, and even more preferably 1 to 20 carbon atoms.

Examples of the alkoxy group represented by R ¹ include groups similar to the alkoxy group in which the heterocycle represented by Y ¹ or Y ² may be substituted.

(Halogenated alkyl group)
The alkyl halide group represented by R ¹ preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms.

Specific examples of the alkyl halide group represented by R ¹ include a perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group and a nonafluorobutyl group, and trifluoro. Methyl groups are particularly preferred.

Compound (1) will be described in detail.

In the formula (1), Y ¹ and Y ² are preferably heterocycles represented by the following formulas (Y1-1), (Y1-2), (Y2-1), or (Y2-2). In the following formula, R ¹ , p1 and p2 have the same meaning as above, and * 1 and * 2 correspond to * 1 or * 2 in the above formula (1).

Of these, the heterocycle represented by the formula (Y1-1) or (Y2-1) is preferable.

Further, Y ¹ and Y ² may or may not be the same, and it is more preferable that they are the same heterocycle.

Among them, the compounds shown in the following table are preferable, and the compounds (1-1), (1-3), (1-11), (1-13), (1-21), (1-23), (1-2) are preferable. 31) and (1-33) are more preferable.

Compound (2) will be described in detail.

In the formula (2), Y ¹ is preferably a heterocycle represented by the above formula (Y1-1), (Y1-2), (Y2-1), or (Y2-2). Of these, the heterocycle represented by the formula (Y1-1) or (Y2-1) is more preferable. That is, the compounds shown in the table below are preferable, and compounds (2-1) and (2-3) are more preferable.

Compound (3) will be described in detail.

In the formula (3), Y ² is preferably a heterocycle represented by the above formula (Y1-1), (Y1-2), (Y2-1), or (Y2-2). Of these, the heterocycle represented by the formula (Y1-1) or (Y2-1) is more preferable. That is, the compounds shown in the table below are preferable, and compounds (3-1) and (3-3) are more preferable.

2. 2. Manufacturing Method The outline of the manufacturing method of the present invention is represented by the following scheme. In the following scheme, Y ¹ and Y ² are synonymous with the above. Further, in the following scheme, Z ¹ and Z ² each independently represent a 5-membered heterocycle containing at least one S as a component of the ring.

That is, in the compound (1) of the present invention, after the compound (1-X2) is oxidized (oxidation step: step 1), the azido compound is reacted with the obtained compound (1-X1) in the presence of a base. Thereby, the compound (Z1) can be produced (cyclization step (1): step 2) and oxidized (oxidation step: step 21).

Similarly, in the compound (2) of the present invention, after the compound (2-X2) is oxidized (oxidation step: step 1), the azido compound is reacted with the obtained compound (2-X1) in the presence of a base. The compound (Z2) can be produced by allowing the compound (Z2) to be produced (cyclization step (1): step 2), and can be produced by oxidizing the compound (Z2) (oxidation step: step 21).

Further, in the compound (3) of the present invention, after the compound (3-X2) is oxidized (oxidation step: step 1), the azido compound is reacted with the obtained compound (3-X1) in the presence of a base. Thereby, the compound (Z3) can be produced (cyclization step (1): step 2) and oxidized (oxidation step: step 21).

Examples of the heterocycle represented by Z ¹ or Z ² include a heterocycle represented by the following formula.

Of these, the thiophene ring and the thiazole ring are preferable.

The heterocycle represented by Z ¹ or Z ² does not have to have a substituent and is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an aliphatic hydrocarbon group; an alkoxy group; and a halogen. It is also preferable that it is substituted with one or more selected from the alkylated groups.

The halogen atom, the aliphatic hydrocarbon group, the alkoxy group, and the alkyl halide group that replace the heterocycle represented by Z ¹ or Z ² are halogens that replace the heterocycle represented by Y ¹ or Y ² . The same atoms, aliphatic hydrocarbon groups, alkoxy groups, and alkyl halides can be used.

As the heterocycle represented by Z ¹ or Z ² , specifically, an aromatic ring represented by the following formula is preferable.

In the formula (ZY1) or (ZY2), ^R1 , p1 and p2 are synonymous with the above, one of * a and * b is * 1 in the formulas (Z1) to (Z3), and the other is * 2. be.

2-1. Oxidation step: Step 1
In step 1, the compound (1-X1), (2-X1) or (3-X1) or (3-X1) or (3-X1) is reacted by reacting the compound (1-X2), (2-X2) or (3-X2) with an oxidizing agent. X1) can be obtained.

The specific structures and preferred structures of the compounds (1-X2), (2-X2), and (3-X2) correspond to the specific structures and preferred structures of the compounds (1), (2) and (3). do.

As the oxidizing agent, for example, a percarboxylic acid such as metachloroperbenzoic acid (mCPBA) or hydrogen peroxide can be used, and it is preferable to use the percarboxylic acid.

The amount of the oxidizing agent is preferably 0.1 mol or more and 10 mol or less, more preferably 0.5 mol, with respect to 1 mol of the compound (1-X2), (2-X2) or (3-X2). It is 5 mol or less.

The oxidation step: Examples of the reaction solvent in step 1 include halogen-based solvents such as dichloromethane, chloroform, dichloroethane and dichloropropane; alcohol-based solvents such as methanol, ethanol, n-propanol, 2-propanol and n-butanol; acetic acid. , A carboxylic acid solvent such as trifluoroacetic acid; water; or a mixed solvent thereof; and a halogen solvent is preferable.

The reaction temperature is preferably −80 ° C. or higher and 60 ° C. or lower, more preferably 0 ° C. or higher and 40 ° C. or lower.

2-2. Cyclization step: Step 2
In step 2, the compound (Z1), (Z2) or (Z3) is reacted with the above compound (1-X1), (2-X1) or (3-X1) in the presence of a base by reacting the azide compound with the compound (Z1), (Z2) or (Z3). Can be obtained.

The specific structures and preferred structures of the compounds (1-X1), (2-X1), and (3-X1) correspond to the specific structures and preferred structures of the compounds (1), (2) and (3). do.

Examples of the azide compound include organic azide compounds such as diphenylphosphoryl azide (DPPA), diarylphosphoryl azide such as bis (4-nitrophenyl) phosphoryl azide; trialkylsilyl azide such as trimethylsilyl azide (TMSA); and sodium azide. Inorganic azide compounds such as are preferred.

The amount of the azide compound is preferably 0.5 mol or more and 10 mol or less, more preferably 1 mol or more, with respect to 1 mol of the compound (1-X1), (2-X1) or (3-X1). , 8 mol or less, more preferably 1 mol or more and 5 mol or less. When the amount of the azide compound is in this range, the yield and the reaction efficiency are good.

The organic azide compound may be supported on a polymer, for example. Of these, trialkylsilyl azide compounds such as diphenylphosphoryl azide (DPPA) and trimethylsilyl azide are preferred.

When a trialkylsilyl azide is used as the azide compound, a sulfonyl halide compound or a phosphoric acid halide compound may be further coexisted.

(Sulfonyl halide compound)
Examples of the sulfonyl halide compound include alkylsulfonyl chloride compounds such as methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, isopropanesulfonyl chloride, butanesulfonyl chloride, pentanesulfonyl chloride, and hexanesulfonyl chloride; benzenesulfonyl chloride, 2-. Methylbenzenesulfonyl chloride, 3-methylbenzenesulfonyl chloride, 4-methylbenzenesulfonyl chloride, 2-chlorobenzenesulfonyl chloride, 3-chlorobenzenesulfonyl chloride, 4-chlorobenzenesulfonyl chloride, 2-bromobenzenesulfonyl chloride, 3-bromobenzenesulfonyl chloride , 4-bromobenzenesulfonyl chloride, 2-iodobenzenesulfonyl chloride, 3-iodobenzenesulfonyl chloride, 4-iodobenzenesulfonyl chloride, 2-fluorobenzenesulfonyl chloride, 3-fluorobenzenesulfonyl chloride, 4-fluorobenzenesulfonyl chloride, Arylsulfonyl chloride compounds such as 2-trifluoromethylbenzenesulfonyl chloride, 3-trifluoromethylbenzenesulfonyl chloride, 4-trifluoromethylbenzenesulfonyl chloride; sulfonyl chloride compounds such as sulfryl chloride; Sulfonyl fluoride compounds such as sulfonic acid fluoride; and the like. Among them, a sulfonyl chloride compound is preferable, an arylsulfonyl chloride compound is more preferable, and 4-methylbenzenesulfonyl chloride is further preferable.

The amount of the sulfonyl halide compound is preferably 0.5 mol or more and 20 mol or less, more preferably 1 mol, with respect to 1 mol of the compound (1-X1), (2-X1) or (3-X1). The above is 15 mol or less, more preferably 1 mol or more, 13 mol or less, and particularly preferably 1 mol or more and 10 mol or less. When the amount of the sulfonyl halide compound is in this range, the yield and the reaction efficiency are good.

(Phosphate halide compound)
Examples of the phosphoric acid halide compound include dialkylphosphoryl chloride compounds such as dimethylphosphoryl chloride, diethylphosphoryl chloride, dipropylphosphoryl chloride, diisopropylphosphoryl chloride, and dibutylphosphoryl chloride; bis (2,2,2-trichloroethyl) phosphoryl chloride. Dihalogenated alkyl phosphoryl chloride compounds such as 2-chloro-2-oxo-1,3,2-dioxaphosphorane; diphenylphosphoryl chloride, bis (2-methylphenyl) phosphoryl chloride, bis (3-methylphenyl) phosphoryl Chloride, bis (4-methylphenyl) phosphoryl chloride, bis (3,5-dimethylphenyl) phosphoryl chloride, bis (2-chlorophenyl) phosphoryl chloride, bis (3-chlorophenyl) phosphoryl chloride, bis (4-chlorophenyl) phosphoryl chloride , Diarylphosphoryl chloride compounds such as bis (3,5-dichlorophenyl) phosphoryl chloride; 1,2-phenylene phosphorochloridate; and the like. Of these, dihalogenated alkylphosphoryl chloride compounds and diarylphosphoryl chloride compounds are preferable, and bis (2,2,2-trichloroethyl) phosphoryl chloride and diphenylphosphoryl chloride are more preferable.

The amount of the phosphate halide compound is preferably 0.5 mol or more and 20 mol or less, more preferably 1 mol, with respect to 1 mol of the compound (1-X1), (2-X1) or (3-X1). It is 1 mol or more and 15 mol or less, more preferably 1 mol or more and 13 mol or less, and particularly preferably 1 mol or more and 10 mol or less. When the amount of the phosphoric acid halide compound is in this range, the yield and the reaction efficiency are good.

Examples of the base coexisting in the reaction of the azido compound include pyridine; imidazole compounds such as N-methylimidazole and imidazole; lithium hydroxide, sodium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate and potassium carbonate. Alkali metal salt compounds such as cesium carbonate; alkaline earth metal salt compounds such as magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, barium carbonate; lithium methoxyd, sodium methoxyd, potassium methoxyd, Lithium ethoxide, sodium ethoxydo, potassium ethoxydo, lithium isopropoxide, sodium isopropoxide, potassium isopropoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-amylalkoxide, sodium tert -Amethylalkalkoxide, potassium tert-alkoxy alkali metal compounds such as amylalkoxide; hydride metal compounds such as lithium hydride, sodium hydride, potassium hydride; trimethylamine, triethylamine, tripropylamine, diisopropylethylamine, tributylamine, tripentyl Amine, trihexylamine, trioctylamine, triallylamine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, N-methylmorpholine, N, N-dimethylcyclohexylamine, N, N-dimethylaniline, Examples include N-methylimidazole, 1,4-diazabicyclo [2.2.2] octane, tertiary amines such as 1,8-diazabicyclo [5.4.0] undeceth-7-ene; and the like. Among them, pyridine, imidazole compound, alkali metal salt compound, tertiary amine are preferable, pyridine, N-methylimidazole, potassium carbonate and triethylamine are more preferable, and pyridine, potassium carbonate and triethylamine are more preferable.

The amount of the base is preferably 0.5 mol or more and 10 mol or less, more preferably 1 mol or more, with respect to 1 mol of the compound (1-X1), (2-X1) or (3-X1). It is 8 mol or less, more preferably 1 mol or more, 7 mol or less, and particularly preferably 1 mol or more and 5 mol or less.

It is preferable that no reaction solvent is used during the above reaction in step 2.

When a reaction solvent is used, it can be used as long as it does not affect the reaction. For example, an ether solvent, an aromatic solvent, an ester solvent, a hydrocarbon solvent, a halogen solvent, a ketone solvent, or an amide solvent can be used. Etc. can be used.

Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyl tetrahydrofuran, dimethoxyethane, cyclopentylmethyl ether, t-butyl methyl ether, dioxane and the like.

Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene and the like.

Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and the like.

Examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, heptane and the like.

Examples of the halogen-based solvent include dichloromethane, chloroform, dichloroethane, dichloropropane and the like.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone and the like.

Examples of the amide-based solvent include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro. -(1H) -pyrimidine and the like can be mentioned.

Further, a nitrile solvent such as acetonitrile, a sulfoxide solvent such as dimethyl sulfoxide, and a sulfone solvent such as sulfolane can be used.

The reaction temperature is preferably 0 ° C. or higher and 200 ° C. or lower, more preferably 30 ° C. or higher and 180 ° C. or lower, and even more preferably 40 ° C. or higher and 150 ° C. or lower from the viewpoint of increasing the reaction yield. The reaction temperature may be adjusted using microwaves.

2-3. Oxidation step: Step 21
In step 21, the compound (1), (2) or (3) can be obtained by reacting the compound (Z1), (Z2) or (Z3) with an oxidizing agent.

The specific structures and preferred structures of the compounds (Z1), (Z2), and (Z3) correspond to the specific and preferred structures of the compounds (1), (2) and (3).

As the oxidizing agent, a percarboxylic acid such as metachloroperbenzoic acid (mCPBA) or hydrogen peroxide can be used, and hydrogen peroxide is preferably used.

The amount of the oxidizing agent is preferably 0.1 mol or more and 10 mol or less, more preferably 0.5 mol or more and 5 mol or less, with respect to 1 mol of the compound (Z1), (Z2) or (Z3). be.

The oxidation step: Examples of the reaction solvent in step 21 include halogen-based solvents such as dichloromethane, chloroform, dichloroethane and dichloropropane; alcohol-based solvents such as methanol, ethanol, n-propanol, 2-propanol and n-butanol; acetic acid. , A carboxylic acid solvent such as trifluoroacetic acid; water; or a mixed solvent thereof; and a carboxylic acid solvent is preferable.

The reaction temperature is preferably 0 ° C. or higher and 120 ° C. or lower, more preferably 40 ° C. or higher and 100 ° C. or lower.

2-4. Production of Compounds (1-X2), (2-X2) and (3-X2) As the above-mentioned compounds (1-X2), (2-X2) or (3-X2), commercially available products may be used. , Those manufactured by the method represented by the following scheme may be used. In the following scheme, Z ¹ and Z ² are synonymous with the above, respectively. Further, R ^x1 to R ^x12 represent a ring-forming functional group.

That is, the compound (1-X2) can be produced by reacting the compound (1-X3) with the compound (1-X4) and further reacting with an acid (cyclization step (2): step 3). The compound (2-X2) or (3-X2) can be produced by reacting the compound (2-X3) or the compound (3-X3) with an acid (cyclization step (3): step 4). The compound (2-X2) or (3-X2) can also be produced by reacting the compound (2-X4) or the compound (3-X4) with a ketone, a carboxylic acid derivative, or the like (cyclization step (4). ): Step 5).

The ring-forming functional groups represented by R ^x1 to R ^x12 are hydrogen atoms; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups having 5 to 7 carbon atoms; -OH; -SH. -NHP ^x1 ; or -M ^x1 (L ^x1 ) _kx is preferable, and the methylene group contained in the alkyl group may be replaced with -S-, -O- or -N (P ^x1 )-. The hydrogen atom contained in the alkyl group may be substituted with -OP ^x2 or -SP ^x2 .

P ^x1 represents an amino-protecting group, specifically, tert-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, allyl. Carbamate-based protecting groups such as oxycarbonyl groups; amide-based protecting groups such as trifluoroacetyl groups; imide-based protecting groups such as phthaloyl groups; sulfonamide-based protecting groups such as p-toluenesulfonyl groups and 2-nitrobenzenesulfonyl groups; Can be mentioned. Among them, as the amino-protecting group, a carbamate-based protecting group or a sulfonamide-based protecting group is preferable, and a tert-butoxycarbonyl group or a p-toluenesulfonyl group is particularly preferable.

P ^x2 represents an alkyl group having 2 to 3 carbon atoms, and when a plurality of (preferably two) -OP ^x2 or -SP ^x2 are bonded to one carbon atom, a plurality of (preferably two) -OP x2 or -SP x2 are bonded to one carbon atom. P ^{x 2} may be combined to form a ring.

M ^x1 represents a boron atom or a tin atom.

L ^x1 represents an alkyl group having 1 to 6 carbon atoms, -OH, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms or an aralkyloxy group having 7 to 10 carbon atoms, and a plurality of L's. ^x1 may form a ring with M ^x1 .

Examples of the alkyl group represented by L ^x 1 include groups similar to the alkyl group exemplified as the aliphatic hydrocarbon group represented by R ¹ , and the alkyl group preferably has 1 to 4 carbon atoms. .. Examples of the alkoxy group represented by L ^x 1 include a group in which —O— is bonded to the alkyl group exemplified as the aliphatic hydrocarbon group represented by R ¹ , and the alkoxy group has 1 to 4 carbon atoms. Is preferable. Examples of the aryloxy group represented by L ^x 1 include a phenyloxy group, and the aryloxy group preferably has 6 to 8 carbon atoms. Further, examples of the aralkyloxy group represented by L ^x 1 include a benzyloxy group, and the carbon number is preferably 7 to 8.

kx represents an integer of 2 or 3 depending on the type of M ^x1 . kx is 2 when M ^x1 is a boron atom and 3 when M ^x1 is a tin atom.

When M ^x1 is a boron atom, examples of * -M ^x1 (L ^x1 ) _kx include groups represented by the following formulas (Om-1) to (Om-4). In the following formula, R ^x14 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (preferably a hydrogen atom). * Represents a bond.

When M ^x1 is a tin atom, examples of * -M ^x1 (L ^x1 ) _kx include a group represented by the following formula (Om-5) or (Om-6). In the following formula, * represents a bond.

Of these, the groups represented by the above formulas (Om-1), (Om-2), (Om-5), and (Om-6) are preferable.

Cyclization step (2): Step 3
In step 3, the catalyst may coexist.

Examples of the catalyst include metal catalysts, and transition metal catalysts such as palladium-based catalysts, nickel-based catalysts, iron-based catalysts, copper-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts. Of these, a palladium-based catalyst is preferable.

Examples of the palladium-based catalyst include palladium (II) chloride, palladium (II) bromide, palladium (II) iodide, palladium (II) oxide, palladium (II) sulfide, palladium (II) telluride, and hydroxylation. Palladium (II), Palladium selenium (II), Palladium cyanide (II), Palladium acetate (II), Palladium trifluoroacetate (II), Palladium acetylacetonate (II), Diacetate bis (triphenylphosphine) palladium (II), Tetraquis (Triphenylphosphine) Palladium (0), Dichlorobis (Triphenylphosphine) Palladium (II), Dichlorobis (acetaceant) Palladium (II), Dichlorobis (benzonitrile) Palladium (II), Dichloro [1, 2 -Bis (diphenylphosphino) ethane] palladium (II), dichloro [1,3-bis (diphenylphosphino) propane] palladium (II), dichloro [1,4-bis (diphenylphosphino) butane] palladium (II) ), Dichloro [1,1-bis (diphenylphosphinoferrocene)] palladium (II), dichloro [1,1-bis (diphenylphosphino) ferrocene] palladium (II) dichloromethane adduct, bis (dibenzideneacetone) palladium (0), Tris (dibenzilidenacetone) dipalladium (0), Tris (dibenzidyleneacetone) dipalladium (0) chloroform adduct, dichloro [1,3-bis (2,6-diisopropylphenyl) imidazole-2- Iliden] (3-chloropyridyl) palladium (II), bis (tri-tert-butylphosphine) palladium (0), dichloro [2,5-norbornadiene] palladium (II), dichlorobis (ethylenediamine) palladium (II), dichloro Examples thereof include (1,5-cyclooctadiene) palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II), dichlorobis (triphenylalcin) palladium (II) and the like. As these catalysts, only one kind may be used, or two or more kinds may be used.

The molar ratio of the compound (1-X3) to the catalyst (compound (1-X3): catalyst) is generally about 1: 0.0001 to 1: 0.5 and is not particularly limited, but the yield and reaction efficiency are not particularly limited. From the viewpoint of the above, 1: 0.001 to 1: 0.4 is preferable, 1: 0.005 to 1: 0.3 is more preferable, and 1: 0.01 to 1: 0.2 is even more preferable.

A specific ligand may be coordinated to the catalyst.

Examples of the ligand include trimethylphosphin, triethylphosphin, tri (n-butyl) phosphin, tri (isopropyl) phosphin, tri (tert-butyl) phosphin, tri-tert-butylphosphonium tetrafluoroborate, and bis ( tert-butyl) Methylphosphine, Tricyclohexylphosphine, Diphenyl (Methyl) phosphine, Triphenis phosphine, Tris (o-tolyl) phosphine, Tris (m-tolyl) phosphine, Tris (p-tolyl) phosphine, Tris (2-frill) ) Phosphin, Tris (2-methoxyphenyl) phosphin, Tris (3-methoxyphenyl) phosphin, Tris (4-methoxyphenyl) phosphin, 2-dicyclohexylphosphinobiphenyl, 2-dicyclohexylphosphino-2'-methylbiphenyl, 2 -Dicyclohexylphosphino-2', 4', 6'-triisopropyl-1,1'-biphenyl, 2-dicyclohexylphosphino-2', 6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino -2'-(N, N'-dimethylamino) biphenyl, 2-diphenylphosphino-2'-(N, N'-dimethylamino) biphenyl, 2- (di-tert-butyl) phosphino-2'-( N, N'-dimethylamino) biphenyl, 2- (di-tert-butyl) phosphinobiphenyl, 2- (di-tert-butyl) phosphino-2'-methylbiphenyl, 1,2-bis (diphenylphosphino) Etan, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,2-bis (dicyclohexylphosphino) ethane, 1,3-bis (dicyclohexylphosphino) propane, 1,4-Bis (dicyclohexylphosphino) butane, 1,2-bisdiphenylphosphinoethylene, 1,1'-bis (diphenylphosphino) ferrocene, 1,2-ethylenediamine, N, N, N', N' -Tetramethylethylenediamine, 2,2'-bipyridyl, 1,3-diphenyldihydroimidazolidene, 1,3-dimethyldihydroimidazolidene, diethyldihydroimidazolidene, 1,3-bis (2,4,6- Trimethylphenyl) dihydroimidazolidene, 1,3-bis (2,6-diisopropylphenyl) dihydroimidazolidene, 1,10-phenanthroline, 5,6 -Dimethyl-1,10-phenanthroline, butophenanthroline and the like can be mentioned. As these ligands, only one kind may be used, or two or more kinds may be used.

When coordinating a ligand, the molar ratio (catalyst: ligand) between the catalyst and the ligand is generally about 1: 0.5 to 1:10 and is not particularly limited, but the yield and reaction efficiency are not particularly limited. From the above viewpoint, 1: 1 to 1: 8 is preferable, 1: 1 to 1: 7 is more preferable, and 1: 1 to 1: 5 is even more preferable.

The molar ratio of the compound (1-X3) to the base (compound (1-X3): base) is generally about 1: 1 to 1:10 and is not particularly limited, but 1: from the viewpoint of yield and reaction efficiency. It is preferably 1.5 to 1: 8, more preferably 1: 1.8 to 1: 6, and even more preferably 1: 2 to 1: 5.

In step 3, the acid to be reacted after the compound (1-X3) and the compound (1-X4) are reacted is preferably an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid, and hydrochloric acid is particularly preferable.

The reaction solvent in step 3 is not particularly limited as long as it does not affect the reaction, and is, for example, an ether solvent, an aromatic solvent, an ester solvent, a hydrocarbon solvent, a halogen solvent, or a ketone solvent. , Amid solvent and the like can be used.

Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyl tetrahydrofuran, dimethoxyethane, cyclopentylmethyl ether, t-butyl methyl ether, 1,4-dioxane and the like.

Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene and the like.

Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and the like.

Examples of the hydrocarbon solvent include pentane, hexane, heptane and the like.

Examples of the halogen-based solvent include dichloromethane, chloroform, dichloroethane, dichloropropane and the like.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone and the like.

Examples of the amide-based solvent include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl3,4,5,6-tetrahydro-. (1H) -Pyrimidine and the like can be mentioned.

Further, a nitrile solvent such as acetonitrile, a sulfoxide solvent such as dimethyl sulfoxide, and a sulfone solvent such as sulfolane can be used.

Among these, toluene, xylene, tetrahydrofuran, 1,4-dioxane, N, N-dimethylformamide are particularly preferable.

The reaction temperature is not particularly limited, but is preferably 0 ° C. or higher and 200 ° C. or lower from the viewpoint of increasing the reaction yield. The reaction temperature may be adjusted using microwaves.

As step 3, for example, a step represented by the following scheme can be preferably adopted.

In the above scheme, P ^x1 , P ^x2 , M ^x1 , L ^x1 , kx, Z ¹ , Z ² are synonymous with the above. X ¹ represents a halogen atom.

Cyclization step (3): Step 4
In step 4, as the acid to react with the compound (2-X3) or the compound (3-X3), the same acid as the acid exemplified as the acid used in the cyclization step (2): step 3 can be used. , Inorganic acids are preferred, and hydrochloric acid is particularly preferred.

As the reaction solvent in the step 4, the same solvent as the reaction solvent used in the cyclization step (2): step 3 can be used, and for example, toluene, xylene, tetrahydrofuran, 1,4-dioxane, N, N- Dimethylformamide is particularly preferred.

The reaction temperature is preferably 0 ° C. or higher and 200 ° C. or lower from the viewpoint of increasing the reaction yield. The reaction temperature may be adjusted using microwaves.

As the step 4, for example, a step represented by the following scheme can be preferably adopted. In the following scheme, P ^x1 , P ^x2 , Z ¹ are synonymous with the above.

Cyclization step (4): Step 5
As the oxidizing agent used in the step 5, the same oxidizing agent as the oxidizing agent used in the above-mentioned oxidizing step: step 1: can be used, and a percarboxylic acid such as metachloroperbenzoic acid is preferable.

As the reaction solvent in step 5, the same solvent as the reaction solvent in the above oxidation step: step 1 can be used, and a halogen-based solvent is preferable.

As the step 5, for example, a step represented by the following scheme can be preferably adopted. In the scheme below, P ^x1 is synonymous with the above.

3. 3. Tetrazolopyridine multimer The structural unit derived from the compounds (1), (2) or (3) of the present invention is represented by the formulas (I), (IIA), (IIB), (IIC) or (IID). Structural unit (hereinafter, may be simply referred to as "structural unit (I)", "structural unit (IIA)", "structural unit (IIB)", "structural unit (IIC)" or "structural unit (IID)". The tetrazolopyridine multimer containing.) Is also included in the technical scope of the present invention.

Having a structural unit derived from the formulas (1), (2) or (3) tends to lower the LUMO of the compound, which is useful as a semiconductor material (n-type or bipolar).

In formulas (I), (IIA), (IIB), (IIC) and (IID), Y ¹ , Y ² , Y ¹¹ and Y ¹² each independently have at least -SO _2- as a ring component. Represents a 5-membered heterocycle containing one. D represents a bond.

Specific examples and preferred ranges of Y ¹ and Y ² in structural units (I), (IIA), (IIB), (IIC), and structural units (IID) are Y ¹ and in equations (1)-(3). It is the same as the specific example of Y ² and the preferable range.

Examples of the heterocycle represented by Y ¹¹ or Y ¹² include a heterocycle represented by the following formula.

Of these, a dioxothiophene ring and a dioxothiazole ring are preferable.

The heterocycle represented by Y ¹¹ or Y ¹² may not have a substituent and is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an aliphatic hydrocarbon group; an alkoxy group; and It is also preferable that the substituent is substituted with one or more selected from the alkyl halide groups.

The halogen atom, the aliphatic hydrocarbon group, the alkoxy group, and the alkyl halide group that replace the heterocycle represented by Y ¹¹ or Y ¹² are halogens that replace the heterocycle represented by Y ¹ or Y ² . The same atoms, aliphatic hydrocarbon groups, alkoxy groups, and alkyl halides can be used.

As the heterocycle represented by Y ¹¹ or Y ¹² , specifically, a ring represented by the following formula is preferable.

In the above formula (Y11) or (Y12), R ¹ is the same as R ¹ in the formula (Y1) or (Y2). D is the same as D in formula (I), (IIA), (IIB), (IIC) or (IID). q represents an integer from 0 to 1. One of * a and * b is * 1 in the formula (I), (IIA), (IIB), (IIC) or (IID), and the other is * 2.

Specific examples of the compound containing the structural unit (I) include a compound represented by the following formula (I-1). In the following formula (I-1), Y ¹¹ and Y ¹² are the same as described above. A ¹ represents an aromatic ring that may be substituted. n1 represents an integer of 1 or more. R ³ independently represents a hydrogen atom or an alkyl group.

Examples of the compound containing any of the structural units (IIA), (IIB), (IIC) and (IID) include compounds (II-1A) to (II-1J) represented by the following formulas. Of these, compound (II-1A) or compound (II-1C) is preferable.

In formulas (II-1A) to (II-1J), Y ¹ , Y ² , Y ¹¹ and Y ¹² are the same as described above. A ¹ represents an aromatic ring that may be substituted independently of each other. n2 represents an integer of 1 or more.

Examples of the aromatic ring represented by A ¹ include an aromatic hydrocarbon ring and an aromatic heterocycle.

Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and a benzene ring is preferable.

Examples of the aromatic heterocycle include an aromatic heterocycle represented by the following formula. In the following formula, R ³ represents a hydrogen atom or an alkyl group, and R ⁴ represents a halogen atom, an alkyl group, an alkoxy group or an alkyl halide group.

Among them, a thiophene ring, a thiazole ring, a pyridine ring, a pyrrole ring, an imidazole ring, a furan ring, an oxazole ring and the like are preferable.

Further, it is preferable that the aromatic ring represented by A ¹ is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the halogen atom, a bromine atom and an iodine atom are preferable, and a bromine atom is particularly preferable. The number of substitutions of the halogen atom is preferably 1 to 2, and particularly preferably 1.

The aromatic ring represented by A ¹ may have a substituent other than the halogen atom. Examples of the substituent other than the halogen atom include an alkyl group, an alkoxy group, an alkyl halide group and the like.

Examples of the alkyl group include groups similar to the alkyl group exemplified as the aliphatic hydrocarbon group of R ¹ , and the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms.

Examples of the alkoxy group include a group in which —O— is bonded to the alkyl group, and the alkoxy group preferably has 1 to 30 carbon atoms, and more preferably 1 to 24 carbon atoms.

Examples of the alkyl halide group include a group in which the hydrogen atom of the alkyl group is replaced with a halogen atom (particularly preferably a fluorine atom) such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and the halogenated alkyl group is used. The number of carbon atoms in the group is preferably 1 to 30, more preferably 1 to 10, and even more preferably 1 to 4.

Specific examples of the alkyl halide group include a perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group and a nonafluorobutyl group, and a trifluoromethyl group is particularly preferable.

Of the aromatic rings represented by A ¹ , the aromatic hydrocarbon ring is preferably bonded to the pyridine ring of tetrazolopyridine at the 2-position or 5-position, and the aromatic heterocycle is at the 2-position. It is preferable that it is bonded to the pyridine ring of tetrazolopyridine.

As the aromatic ring represented by A ¹ , the aromatic ring represented by the following formula is preferable.

In the formulas (Ar1) to (Ar16), R ³ independently represents a hydrogen atom or an alkyl group. R ⁴ independently represents a halogen atom, an alkyl group, an alkoxy group, or an alkyl halide group. n2 is an integer of 0 to 2, n3 is an integer of 0 to 1, n4 is an integer of 0 to 4, and n5 is an integer of 0 to 3.

Examples of the halogen atom represented by R ⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a bromine atom and an iodine atom are preferable.

As the alkyl group represented by R ³ and the alkyl group represented by R ⁴ , the alkoxy group and the halogenated alkyl group, the aliphatic oxidation may be possessed by the heterocyclic ring represented by Y ¹ above. Examples of the hydrogen group include an alkyl group, an alkoxy group, and a group similar to the alkyl halide group.

Specifically, as the above A ¹ , a structural unit represented by the following formula is more preferable.

In the following formulas (Ar1-1), (Ar2-1), and (Ar4-1), X ² is preferably bonded to the 2-position, and in the following formula (Ar3-1), X ² is in the 4-position. It is preferable that they are bonded.

In the above formulas (Ar1-1) to (Ar16-1), R ³ has the same meaning as above. R ⁵ represents an alkyl group, an alkoxy group, or an alkyl halide group. X ² represents a halogen atom. n6 is an integer of 0 to 1, n7 is an integer of 0 to 3, n8 is an integer of 0 to 2, and n9 is an integer of 0 to 4. * Represents a bond.

In the formulas (Ar1-1), (Ar2-1), (Ar3-1), and (Ar4-1), the halogen atom represented by X ² is the same as the halogen atom represented by R ⁴ above. A bromine atom or an iodine atom is preferable, and a bromine atom is more preferable. R ⁵ is the same as the alkyl group, alkoxy group, and alkyl halide group represented by R ⁴ , respectively, and an alkoxy group and an alkyl halide group are preferable. n6, n7, n8, and n9 are preferably integers of 0 to 1.

Examples of the compound (I-1) include compounds represented by the following formula (I-I).
HA ¹⁰ -Y ⁴⁰ -A ¹¹ -H (I-I)

In the above formula, Y ⁴⁰ represents the structure represented by the formula (I).

A ¹⁰ and A ¹¹ represent a structure represented by any of the formulas (Ar1-1) to (Ar8-1), and A ¹⁰ or A ¹¹ is the formula (Ar1-1) or (Ar1-2). The group represented by the formula (Ar1-2) is preferable, and the group represented by the formula (Ar1-2) is more preferable.

It is preferable that A ¹⁰ and A ¹¹ are the same.

Specifically, as the compound represented by the above formula (I), the compound shown in the following table is preferable. Of these, compounds (I-I-1) to (I-I-12) are preferable.

In the table below, (Y-I-1) to (Y-I-4) represent units represented by the following formulas, respectively.

Examples of the compound (II-1) include compounds represented by the following formula (II-I).
Y ⁵⁰ -A ²⁰ -Y ⁵¹ (II-I)

In the above formula, Y ⁵⁰ and Y ⁵¹ represent a structure represented by any of the formulas (IIA) to (IID).

A ²⁰ represents a structure represented by any of the formulas (Ar1-1) to (Ar16-1), and the formulas (Ar1-3), (Ar3-2), and (Ar13-1) are used as the A ²⁰ . The structure represented by is preferable.

As the compound represented by the above formula (II-I), specifically, the compound shown in the following table is preferable. Of these, compounds (II-I-97) to (II-I-120) are more preferred, and compounds (II-I-98), (II-I-99), (II-I-105), (II- I-108), (II-I-110), (II-I-111), (II-I-117), and (II-I-120) are even more preferred.

In the table below, (Y-II-1) to (Y-II-12) represent units represented by the following formulas.

3-1. Method for Producing Tetrazolopyridine Multimer The outline of the method for producing the above compound (I-1) is represented by the following scheme. In the following formula, X ³ represents a halogen atom. M ¹ is synonymous with M ^x 1, L ¹ is synonymous with L ^x 1, k 1 is synonymous with kx, and A ¹ is synonymous with the above. R ³ , Y ¹¹ , Y ¹² , Z ¹¹ , and Z ¹² are synonymous with the above.

That is, compound (I-1) can be produced by three routes.

(Route 1)
After the compound (I-X6) and the compound (I-X4) are reacted to add an aromatic ring (aromatic ring addition step (1): step 6), the obtained compound (I-X5) is oxidized. A compound (ZI-1) is produced by reacting with an agent (oxidation step: step 7) and reacting the obtained compound (I-X2) with an azido compound in the presence of a base (cyclization step (cyclization step (cyclization step)). 1): Can be produced by oxidation in step 8) (oxidation step: step 31).

(Route 2)
After the compound (I-X3) and the compound (I-X4) were reacted to add an aromatic ring (aromatic ring addition step (1): step 9), the obtained compound (I-X2) was added. The compound (ZI-1) can be produced by reacting the azide compound in the presence of a base (cyclization step (1): step 8), and can be produced by oxidation (oxidation step: step 31).

(Route 3)
The compound (ZI-1) is produced by reacting the compound (I-X1) with the compound (I-X4) to add an aromatic ring (aromatic ring addition step (1): step 10), and oxidation is performed. (Oxidation step: step 31).

The outline of the production method of the above compounds (II-1A) to (II-1J) is represented by the following scheme. In the following scheme, the above compounds (II-1A) to (II-IJ) are collectively represented by the compound (II-1).

However, in the above scheme, the structure represented by the following formula (II) means the structure represented by any of the following formulas (IIA), (IIB), (IIC) and (IID).

In the above scheme, the structure represented by the following formula (ZII) shall mean the structure represented by any of the following formulas (ZIIA), (ZIIB), (ZIIC) and (ZIID).

The structure represented by the following formula (II-X3) is a structure represented by any of the following formulas (IIA-X3), (IIB-X3), (IIC-X3) and (IID-X3). It shall mean.

Further, the structure represented by the following formula (II-X6) is a structure represented by any of the following formulas (IIA-X6), (IIB-X6), (IIC-X6) and (IID-X6). It shall mean.

Compounds (II-1A) to (II-1J) can be produced by three routes.

(Route 1)
After the compound (II-X6) and the compound (II-X4) are reacted to add an aromatic ring (aromatic ring addition step (2): step 11), the obtained compound (II-X5) is oxidized. The compound (ZII-1) is produced by reacting with an agent (oxidation step: step 12) and reacting the obtained compound (II-X2) with an azido compound in the presence of a base (cyclization step (1). ): Can be produced by oxidation in step 13) (oxidation step: step 32).

(Route 2)
After the compound (II-X3) and the compound (II-X4) were reacted to add an aromatic ring (aromatic ring addition step (2): step 14), the obtained compound (II-X2) was added. The compound (ZII-1) can be produced by reacting the azide compound in the presence of a base (cyclization step (1): step 13), and can be produced by oxidation (oxidation step: step 32).

(Route 3)
The compound (ZII-1) is produced by reacting the compound (II-X1) with the compound (II-X4) to add an aromatic ring (aromatic ring addition step (2): step 15), and oxidation is performed. (Oxidation step: step 32).

Aromatic ring addition step (1): Steps 6, 9, 10

(Step 6)
In step 6, the compound (IX5) can be produced by reacting the compound (IX6) with the compound (IX4).
M ¹ (L ¹ ) _k1- (A ¹ ) _n1 -R ³ (I-X4)

In the formula, A ¹ , M ¹ , L ¹ , R ³ , k 1, and n 1 have the same meanings as above.

Examples of the compound (I-X6) used in this step include compounds in which R ¹ is a halogen atom among the above-mentioned compounds (1-X2).

(Step 9)
In step 9, the compound (IX2) can be produced by reacting the compound (IX3) with the compound (IX4).

Examples of the compound (I-X3) used in this step include compounds in which R ¹ is a halogen atom among the above-mentioned compounds (1-X1).

(Step 10)
In step 10, the compound (ZI-1) can be produced by reacting the compound (I-X1) with the compound (I-X4).

Examples of the compound (IX1) used in this step include compounds in which R ¹ is a halogen atom among the compounds (1) exemplified above.

M ¹ , L ¹ , k1 in the formula (I-X4) are the same as M ^x 1, L ^x 1, kx in the formula (1-X4-1), and the compound (I-X4) is represented by the following formula. The compound to be used is mentioned.
M ¹⁰ (L ¹⁰ ) _k10 -A ²⁰ -R ³ (I-X4-I)

However, in the formula, R ³ has the same meaning as above. A ²⁰ represents a structure represented by any of the following formulas (Ar1-1) to (Ar16-1), and as A ²⁰ , a structure represented by the formula (Ar1-2) is preferable. * -M ¹⁰ (L ¹⁰ ) _k10 represents a group represented by any of the above formulas (Om-1) to (Om-6).

Among them, the compounds shown in the following table are preferable, more preferably compounds (I-X4-I-45) to (I-X4-I-66), and still more preferably compounds (I-X4-I-45) or. (I-X4-I-56).

The amount of the compound (I-X4) is preferably 0.6 to 10 mol, more preferably 0.8, with respect to 1 mol of the compound (I-X6), the compound (I-X3) or (I-X1). ~ 6 mol.

Further, when the compound (I-X6), the compound (I-X3) or the compound (I-X1) is reacted with the compound (I-X4), the cyclization step (2): the catalyst exemplified in the step 3 is performed. The same catalyst as above can be used under the same conditions.

The catalyst may be coordinated with a specific ligand similar to the ligand exemplified in the cyclization step (2): step 3 under the same conditions.

Further, when the compound (I-X6), the compound (I-X3) or the compound (I-X1) is reacted with the compound (I-X4), the cyclization step (2): a base similar to the base exemplified in the step 3. May coexist under the same conditions.

The reaction solvent used in steps 6, 9 and 10 is the same as the reaction solvent used in the cyclization step (2): step 3, and can be used under the same conditions.

The reaction temperatures of steps 6, 9 and 10 are the same as those of the cyclization step (2): step 3.

3-2. Aromatic ring addition step (2): Steps 11, 14, 15

(Step 11)
In step 11, the compound (II-X5) can be produced by reacting the compound (II-X6) with the compound represented by the following formula (II-X4).
X ^4- (A ² ) _n1 -X ⁴ (II-X 4)

In the formula, A ² and n 1 have the same meanings as above. X ⁴ represents a halogen atom.

(Step 14)
In step 14, compound (II-X2) can be produced by reacting compound (II-X3) with compound (II-X4).

(Step 15)
In step 15, compound (ZII-1) can be produced by reacting compound (II-X1) with compound (II-X4).

In formulas (II-X6), (II-X3) and (II-X1), M10, L10 and ^k10 are the same as M ^x1 , L ^x1 and kx in formula ( ¹ -X4-1), respectively. be.

The compound (II-X6) includes a group represented by any of the formulas (Om-1) to (Om-6) in the compound (1-X2), (2-X2) or (3-X2). Examples include bound compounds.

The compound (II-X3) includes a group represented by any of the formulas (Om-1) to (Om-6) in the compound (1-X1), (2-X1) or (3-X1). Examples include bound compounds.

Examples of the compound (II-X1) include compounds in which a group represented by any of the formulas (Om-1) to (Om-6) is bonded to the compound (Z1), (Z2) or (Z3). ..

Examples of the halogen atom in the formula (II-X4) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom, a bromine atom or an iodine atom is preferable.

Examples of the compound (II-X4) include compounds represented by the following formulas.
X ⁴⁰ -A ¹⁰ -X ⁴⁰ (II-X4-I)

However, in the formula, A ¹⁰ represents a unit represented by any of the following formulas, and X ⁴⁰ represents a bromine atom or an iodine atom.

Among them, the compounds shown in the table below are preferable, and the compounds (II-X4-I-2), (II-X4-I-3), (II-X4-I-9), (II-X4-I-12) are preferable. (II-X4-I-14), (II-X4-I-15), (II-X4-I-21), and (II-X4-I-24) are more preferable.

The amount of the compound (II-X4) is preferably 0.6 to 5 mol, more preferably 0., With respect to 1 mol of the compound (II-X6), the compound (II-X3) or the compound (II-X1). It is 8 to 3 mol.

The catalyst coexisting when the compound (II-X6), the compound (II-X3) or the compound (II-X1) is reacted with the compound (II-X4) is exemplified in the cyclization step (2): step 3. Similar to the catalyst. The molar ratio of the compound (II-X4) to the catalyst (compound (II-X4): catalyst) is generally about 1: 0.0001 to 1: 1.0 and is not particularly limited, but the yield and reaction efficiency are high. From the viewpoint, 1: 0.001 to 1: 0.8 is preferable, 1: 0.005 to 1: 0.6 is more preferable, and 1: 0.01 to 1: 0.4 is even more preferable.

The ligand exemplified in the cyclization step (2): step 3 may be coordinated to the catalyst under the same conditions.

In steps 11, 14 and 15, the bases exemplified in the cyclization step (2): step 3 may coexist under the same conditions.

Further, in this step, the same solvent as in the cyclization step (2): step 3 can be used as the reaction solvent under the same conditions.

Further, the reaction temperature can also be adjusted in the same manner as in the cyclization step (2): step 3.

3-3. Oxidation process: Steps 7 and 12
In step 7 or step 12, compound (I-X2) or compound (II-X2) can be obtained by reacting compound (I-X5) or compound (II-X5) with an oxidizing agent.

As the oxidizing agent, the same compound as the oxidizing agent exemplified in the oxidation step: Step 1 can be used under the same conditions.

Further, the same conditions as those in the oxidation step: step 1 can be adopted for the reaction solvent and the reaction temperature.

3-4. Cyclization step (1): Steps 8 and 13
In step 8 or step 13, compound (ZI-1) or compound (ZII-1) is obtained by reacting compound (I-X2) or compound (II-X2) with an azide compound in the presence of a base. be able to.

As the azide compound, a compound similar to the azide compound exemplified in the cyclization step (1): step 2 can be used under the same conditions.

Further, the base coexisting when reacting the azide compound is the same as the base exemplified in the cyclization step (1): step 2, and can be used under the same conditions.

Further, the same conditions as those in the cyclization step (1): step 2 can be adopted for the reaction solvent and the reaction temperature.

3-5. Oxidation step: Steps 31, 32
In step 31 or step 32, the compound (I-1) or the compound (II-1) of the present invention is obtained by reacting the compound (ZI-1) or the compound (ZII-1) with an oxidizing agent. Can be done.

As the oxidizing agent, the same compound as the oxidizing agent exemplified in the oxidation step: Step 21 can be used under the same conditions.

Further, the same conditions as those in the oxidation step: step 21 can be adopted for the reaction solvent and the reaction temperature.

4. Organic semiconductor materials The compounds (1), (2) and (3) of the present invention can lower the LUMO level, have excellent thermal stability, and can easily add various functional groups. It is excellent as an organic semiconductor material, and an organic semiconductor material obtained by using the compound (1), (2) or (3) of the present invention is also included in the technical scope of the present invention. Having structural units (I), (IIA), (IIB), (IIC) and (IID) derived from formulas (1), (2) or (3) tends to lower LUMO and is n-type. Alternatively, it is useful as a bipolar semiconductor material.

As the organic semiconductor material, a polymer compound having a structural unit represented by the formula (I) and one or more donor units is preferable.

In formula (I), Y ¹ , Y ² , Y ¹¹ and Y ¹² are synonymous with the above.

The structural units (I), (IIA), (IIB), (IIC) and (IID) derived from the above compounds (1) to (3) are electron acceptors and can be used as acceptor units in an extended π-conjugated system. It is preferable to combine one or more donor units into a donor-acceptor type semiconductor polymer compound, and structural units (I) and donor units are arranged alternately. Is preferable.

The structural unit (I) and the donor unit may be bonded via an aromatic ring.

As the structural unit (I), a unit (structural unit) represented by the above formulas (Y-I-1) to (Y-I-4) is preferable, and it is represented by the formula (Y-I-1). Structural units are particularly preferred.

Further, the polymer compound may contain one or more of the structural units represented by the formulas (I), (IIA), (IIB), (IIC) and (IID).

Such polymer compounds are particularly useful for organic electrodevices such as organic electroluminescence devices and organic thin film devices, organic semiconductor materials, photoelectric conversion devices, organic electronic devices, solar cells, and solar cell module applications.

Examples of the donor unit include structural units (groups) represented by the following formulas (Dn-1) to (Dn-15).

In the formulas (Dn-1) to (Dn-15), R ³⁰ independently represents an aliphatic hydrocarbon group. R ³¹ represents a hydrogen atom or an aliphatic hydrocarbon group. * Represents a bond.

The aliphatic hydrocarbon group represented by R ³⁰ or R ³¹ is the same as the group exemplified as the aliphatic hydrocarbon group in which the heterocycle represented by Y ¹ may be substituted, and has 1 to 1 to carbon atoms. 30 is preferable, 1 to 24 is more preferable, and 1 to 20 is more preferable.

The polymer compound of the present invention can be produced, for example, by reacting the compound represented by the above formula (I-1) with the compound represented by the formula (5) (hereinafter referred to as compound (1)). The step of reacting the compound (5) may be referred to as a "coupling step").

In the formula, A ¹ , M ¹ , L ¹ , k1, Y ¹¹ , Y ¹² , and X ³ have the same meanings as above, and X ³ represents a halogen atom. A ⁶ represents a donor unit. n10 represents an integer of 0 or 1. nx represents an integer of 1 or more.

A ⁶ is preferably a group represented by any of the above formulas (Dn-1) to (Dn-12), and is preferably any of the formulas (Dn-4), (Dn-6) and (Dn-7). The group represented is more preferred.

Examples of the halogen atom of X ³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a bromine atom is preferable.

n10 is preferably 0.

The molar ratio of compound (I-1) to compound (5) is preferably in the range of 1:99 to 99: 1, more preferably in the range of 20:80 to 80:20, and in the range of 40:60 to 60:40. The range is more preferred.

As the catalyst in the coupling step, a catalyst similar to the catalyst exemplified in the cyclization step (2): step 3 can be used under the same conditions.

The catalyst may be coordinated with a specific ligand similar to the ligand exemplified in the cyclization step (2): step 3 under the same conditions.

Further, the cyclization step (2): a base similar to the base exemplified in step 3 may coexist under the same conditions.

The reaction solvent used in the coupling step is the same as the reaction solvent used in the cyclization step (2): step 3, and can be used under the same conditions.

Further, the reaction temperature of the coupling step is the same as that of the cyclization step (2): step 3.

Since the compound of the present invention has high electron acceptability and can lower the LUMO level, it is possible to use organic electronic devices such as organic electroluminescence devices, organic thin film devices and other organic electrodevices, organic semiconductor materials, photoelectric conversion devices, and organic substances. It is useful for electronic devices, solar cells, solar cell modules, etc.

This application claims the benefit of priority under Japanese Patent Application No. 2017-176221 filed on September 13, 2017. The entire contents of the specification of Japanese Patent Application No. 2017-176221 are incorporated herein by reference.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can meet the purposes of the preceding and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention. In the following, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

Synthesis example 1:
Synthesis of 2- (2,2-dimethoxyethylamino) methylthiophene

2-thiophenecarboxyaldehyde (2.24 g, 20 mmol), aminoacetaldehydedimethylacetal (2.2 g, 20 mmol), p-toluenesulfonsulfonic acid (10 mg), and absolute ethanol (20 mL) were placed in a three-necked flask and stirred at 90 ° C. for 4 hours. After completion of the reaction, sodium borohydride (760 mg, 20 mmol) was added, and the mixture was further heated and stirred for 2 hours. After stopping the reaction by adding water, extraction was performed with ethyl acetate (AcOEt). The solvent was concentrated and purified using silica gel column chromatography (Hexane / AcOEt = 1: 1) to obtain 4.05 g of the target compound.

Synthesis example 2:
Synthesis of 2- (2,2-dimethoxyethyl-p-toluenesulfonylamino) methylthiophene

Toluene sulfonic acid chloride (4.6 g, 24 mmol) at 0 ° C. in a two-necked flask in the thiophene derivative (4.05 g, 20 mmol), pyridine (4.7 g, 60 mmol), and anhydrous dichloromethane (20 mL) shown in the above scheme. ) Was added and the mixture was stirred for 6 hours. After completion of the reaction, water was added to stop the reaction, and then extraction was performed with dichloromethane. The solvent was concentrated and purified using silica gel column chromatography (Hexane / AcOEt = 1: 1) to obtain 5.45 g (yield 77%) of the target compound.

Synthesis example 3:
Synthesis of Thieno [3,2-c] Pyridine (Step 4)

Thiophene (5.45 g, 15 mmol), hydrochloric acid (5 mL), and 1,4-dioxane (20 mL) shown in the above scheme were placed in a 100 mL flask and refluxed overnight. After completion of the reaction, the mixture was neutralized with an aqueous sodium hydroxide solution and extracted with dichloromethane. The solvent was concentrated and purified by silica gel column chromatography (Hexane / AcOEt = 1: 1) to obtain 1.37 g (yield 66%) of the target compound.

Synthesis example 4:
Synthesis of Thieno [3,2-c] Pyridine-N-Oxide (Step 1)

Thienopyridine (1.37 g, 10.1 mmol), metachloroperbenzoic acid (mCPBA) (2.6 g, 15 mmol), and anhydrous dichloromethane (50 mL) were placed in an eggplant flask and stirred at −5 ° C. for 2 days. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was added, and the organic layer was extracted with dichloromethane and dried over anhydrous sodium sulfate. After concentration, purification was performed using silica gel column chromatography (CHCl ₃ / MeOH = 20: 1) to obtain 520 mg (yield 34%) of thienopyridine-N-oxide. rice field.
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.29 (d, J = 5.5 Hz, 1H), 7.66 (d, J = 5.5 Hz, 1H), 7.72 (d, J = 7.0 Hz, 1H), 8.17 (dd) , J = 1.6, 7.0 Hz, 1H), 8.76 (d, J = 1.6 Hz, 1H).

Example 1:
Synthesis of Thienotetrazolopyridine (Compound (Tz-1)) (Step 2)

Thienopyridine-N-oxide (520 mg, 3.45 mmol), diphenylphosphoryl azide (DPPA) (4.7 g, 17 mmol), and anhydrous pyridine in a screw cap test tube. (75 mL, 6.9 mmol) was added, and the mixture was stirred at 120 ° C. for 24 hours under a nitrogen atmosphere. By directly purifying the reaction solution by silica gel column chromatography (CH ₂ Cl ₂ / MeOH = 50: 1), 288 mg (yield 47%) of Thienotetrazolopyridine (compound (Tz-1)) was obtained. rice field.
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.61 (d, J = 7.3 Hz, 1H), 7.83 (d, J = 5.4 Hz, 1H), 8.10 (d, J = 5.4 Hz, 1H), 8.66 (d) , J = 7.3 Hz, 1H).

Synthesis example 5:
Synthesis of 2-Tributylstannyl Thieno [3,2-c] Pyridine

Diisopropylamine (0.21 mL, 5.4 mmol), butyllithium (2.6 M, 1.7 mL) at −78 ° C. in thienopyridine (408 mg, 3.0 mmol) and anhydrous tetrahydrofuran (30 mL) in a two-necked flask. ), Lithium diisopropylamide (LDA) was added, and the mixture was stirred for 1 hour. Then, tributyltin chloride (1.3 mL, 4.8 mmol) was added, and the mixture was further stirred at room temperature for 2 hours. After stopping the reaction by adding water, extraction was performed with diethyl ether. The solvent was concentrated and purified using alumina column chromatography (Hexane / AcOEt = 1: 1) to quantitatively obtain 1.83 g of the target compound.
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.76-0.95 (m, 9H), 1.20-1.41 (m, 12H), 1.49-1.69 (m, 6H), 7.47 (s, 1H), 7.79 (d, J) = 5.5 Hz, 1H), 8.35 (d, J = 5.5 Hz, 1H), 9.09 (s, 1H).

Synthesis example 6:
Synthesis of 1,4-bis (hexyloxy) -2,5-bis (thieno [3,2-c] pyridin-2-yl) benzene (step 11)

2,5-dibromo-1,4-hexyloxybenzene (143 mg, 0.33 mmol), 2-stannylthienopyridine (425 mg, 1.0 mmol), Pd (PPh ₃ ) ₄ (38 mg, 0.033 mmol), and anhydrous in pressure test tubes. Toluene (2 mL) was added, and the mixture was stirred at 180 ° C. for 10 minutes using a microwave reactor. After completion of the reaction, the solvent was concentrated and purified by silica gel column chromatography (Hexane / AcOEt = 5: 1) to obtain 71 mg (yield 38%) of the target compound (yellow solid).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.87 (t, J = 7.2 Hz, 3H), 1.28-1.40 (m, 4H), 1.90-1.99 (m, 2H), 4.16 (t, J = 6.5 Hz, 2H), 7.34 (s, 1H), 7.76 (d, J = 5.5 Hz, 1H), 7.87 (s, 1H), 8.42 (d, J = 5.5 Hz, 1H), 9.08 (s, 1H).

Synthesis example 7:
Synthesis of 1,4-bis (hexyloxy) -2,5-bis (thieno [3,2-c] pyridin-N-oxide-2-yl) benzene (step 12)

The mCPBA was changed from 1.5 equivalents to 3.0 equivalents, and the synthesis was carried out in the same manner as in Synthesis Example 4 except that the reaction temperature was room temperature and the reaction time was 14 hours (230 mg, yield 51%). ..
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.87 (t, J = 7.2 Hz, 3H), 1.28-1.40 (m, 4H), 1.90-1.99 (m, 2H), 4.16 (t, J = 6.5 Hz, 2H), 7.34 (s, 1H), 7.76 (d, J = 5.5 Hz, 1H), 7.87 (s, 1H), 8.42 (d, J = 5.5 Hz, 1H), 9.08 (s, 1H).

Example 2:
Synthesis of 1,4-bis (hexyloxy) -2,5-bis (thienotetrazolopyridine-2-yl) benzene (compound (Tz-2)) (step 13)

The compound (Tz-2) was synthesized in the same manner as in Example 1 except that DPPA was 10 equivalents and anhydrous pyridine was 4 equivalents (21 mg, yield 16%).

Synthesis example 8:
Synthesis of 4,4'-dihexyl-5,5'-bis (thieno [3,2-c] pyridin-2-yl) dithiophene (step 11)

The synthesis was carried out in the same manner as in Synthesis Example 6 except that the raw material of the tin body was 2.5 equivalents (53 mg, yield 14%).

Synthesis example 9:
Synthesis of 4,4'-dihexyl-5,5'-bis (thieno [3,2-c] pyridin-N-oxide-2-yl) dithiophene (step 12)

The mCPBA was changed from 1.5 equivalents to 3.0 equivalents, and the synthesis was carried out in the same manner as in Synthesis Example 4 except that the reaction temperature was set to room temperature (57 mg, yield 98%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.79-0.90 (m, 3H), 1.16-1.44 (m, 6H), 1.52-1.69 (m, 2H), 2.78 (t, J = 7.9 Hz, 2H), 7.29 (s, 1H), 7.65 (s, 1H), 7.71 (d, J = 5.5 Hz, 1H), 8.16 (d, J = 5.5 Hz, 1H), 8.74 (s, 1H).

Example 3:
Synthesis of 4,4'-dihexyl-5,5'-bis (thienotetrazolopyridine-2-yl) dithiophene (compound (Tz-3)) (step 13)

Compound (Tz-3) was synthesized in the same manner as in Example 1 except that DPPA was 10 equivalents and anhydrous pyridine was 4 equivalents (33 mg, yield 54%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.88 (t, J = 7.4 Hz, 3H), 1.30-1.46 (m, 6H), 1.68-1.78 (m, 2H), 2.86 (t, J = 7.9 Hz, 2H), 7.13 (s, 1H), 7.56 (d, J = 7.3 Hz, 1H), 8.07 (s, 1H), 8.65 (d, J = 7.3 Hz, 1H).

Synthesis example 10:
Synthesis of 1,3-bis (thieno [3,2-c] pyridin-2-yl) -6,7-dibutyl-naphtho [2,3-b] thiophene-4,9-dione (step 11)

Synthesis was carried out in the same manner as in Synthesis Example 6 (220 mg, quant.).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.90 (t, J = 7.4 Hz, 3H), 1.29-1.38 (m, 2H), 1.57-1.76 (m, 2H), 2.75 (t, J = 7.9 Hz, 2H), 7.80 (d, J = 5.5 Hz, 1H), 8.06 (s, 1H), 8.18 (s, 1H), 8.51 (d, J = 5.5 Hz, 1H), 9.17 (s, 1H).

Synthesis example 11:
Synthesis of 1,3-bis (thieno [3,2-c] pyridin-N-oxide-2-yl) -6,7-dibutyl-naphtho [2,3-b] thiophene-4,9-dione (step) 12)

The mCPBA was changed from 1.5 equivalents to 3.0 equivalents, and the synthesis was carried out in the same manner as in Synthesis Example 4 except that the reaction temperature was set to room temperature (134 mg, yield 58%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.90 (br t, 3H), 1.29-1.38 (br m, 2H), 1.57-1.76 (br m, 2H), 2.75 (br t, 2H), 7.80 (br d, 1H), 8.08 (br s, 1H), 8.38 (br s, 1H), 8.44 (br d, 1H), 8.99 (s, 1H).

Example 4:
Synthesis of 1,3-bis (thienotetrazolopyridine-2-yl) -6,7-dibutyl-naphtho [2,3-b] thiophene-4,9-dione (compound (Tz-4)) (step 13) )

The compound (Tz-4) was synthesized in the same manner as in Example 1 except that DPPA was 10 equivalents and anhydrous pyridine was 4 equivalents (39 mg, yield 28%).

Example 5:
It is considered that the compound (Tz-4-1) can be obtained by reacting the compound (Tz-4) obtained in Example 4 with the oxidizing agent.

Synthesis example 12:
Synthesis of dithienopyridine-N-oxide (step 1)

Dithienopyridine was synthesized with reference to the paper (Synthesis, 1989, 2, 130.). Next, the raw material was changed from thienopyridine to dithienopyridine, and synthesis was carried out in the same manner as in Synthesis Example 4 except that the reaction temperature was set to room temperature (333 mg, yield 80%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.40 (d, J = 5.5 Hz, 1H), 7.57 (d, J = 5.5 Hz, 1H), 7.61 (d, J = 5.5 Hz, 1H), 7.98 (d) , J = 5.5 Hz, 1H), 8.85 (s, 1H).

Example 6:
Synthesis of dithienotetrazolopyridine (compound (Tz-5)) (step 2)

Compound (Tz-5) was synthesized in the same manner as in Example 1 (94 mg, yield 81%). ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.70 (d, J = 5.5 Hz, 1H), 7.76 (d, J = 5.5 Hz, 1H), 8.08 (d, J = 5.5 Hz, 1H), 8.12 (d) , J = 5.5 Hz, 1H).

Synthesis example 13:
Synthesis of 1,3-bis (thieno [3,2-c] pyridin-2-yl) -6,7-dihexyl-naphtho [2,3-b] thiophene-4,9-dione (step 11)

The synthesis was carried out in the same manner as in Synthesis Example 6 except that the stirring time was changed to 20 minutes (103 mg, yield 51%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.88 (t, J = 7.4 Hz, 3H), 1.27-1.44 (m, 6H), 1.59-1.69 (m, 2H), 2.74 (t, J = 7.9 Hz, 2H), 7.80 (d, J = 5.5 Hz, 1H), 8.07 (s, 1H), 8.18 (s, 1H), 8.51 (d, J = 5.5 Hz, 1H), 8.17 (s, 1H).

Synthesis example 14:
Synthesis of 1,3-bis (thieno [3,2-c] pyridin-N-oxide-2-yl) -6,7-dihexyl-naphtho [2,3-b] thiophene-4,9-dione (step) 12)

The synthesis was carried out in the same manner as in Synthesis Example 4 except that the mCPBA was changed from 1.5 equivalents to 3.0 equivalents and the reaction temperature was changed from −5 ° C. to 0 ° C. (47 mg, 44%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.88 (m, 3H), 1.27-1.44 (m, 6H), 1.59-1.69 (m, 2H), 2.75 (t, J = 7.9 Hz, 2H), 7.39 ( br d, 1H), 7.53 (br d, 1H), 7.94 (s, 1H), 7.96 (s, 1H), 8.89 (s, 1H).

Example 7:
Synthesis of 1,3-bis (thienotetrazolopyridine-2-yl) -6,7-dihexyl-naphtho [2,3-b] thiophene-4,9-dione (compound (Tz-10)) (step 13) )

Compound (Tz-10) was synthesized in the same manner as in Example 1 except that DPPA was 10 equivalents and anhydrous pyridine was 10 equivalents (22 mg, 44%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.88 (t, J = 7.4 Hz, 3H), 1.27-1.44 (m, 6H), 1.59-1.69 (m, 2H), 2.77 (t, J = 7.9 Hz, 2H), 7.63 (d, J = 7.7 Hz, 1H), 8.10 (s, 1H), 8.70 (s, 1H), 8.73 (d, J = 7.7 Hz, 1H).

Example 8:
It is considered that the following compound (Tz-10-1) can be obtained by reacting the above compound (Tz-10) obtained in Example 7 with an oxidizing agent.

Example 9:
In an eggplant flask, Thienotetrazolopyridine (115 mg, 0.15 mmol), mCPBA (0.43 g, 1.5 mmol), and anhydrous dichloromethane (10 mL) shown in the following scheme are placed and stirred under reflux for 2 days. After completion of the reaction, saturated aqueous sodium hydrogen carbonate solution is added, the organic layer is extracted with dichloromethane, and dried over anhydrous sodium sulfate. After concentration, purification using silica gel column chromatography (CHCl ₃ / MeOH = 10: 1) is considered to give the mixture shown in the scheme below.

Synthesis example 15:
4,9-bis (thieno [3,2-c] pyridin-N-oxide-2-yl) -N, N-diazahexyl-1,2,3,6,7,8-hexahydropyrene-2, Synthesis of 7-diaza-1,3,6,8-tetraone

The synthesis was carried out in the same manner as in Synthesis Example 4, except that the mCPBA was changed from 1.5 equivalents to 3.0 equivalents and the reaction temperature was changed from −5 ° C. to 0 ° C. (98 mg, 77%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.76-1.00 (m, 6H), 1.14-1.45 (m, 8H), 1.74-1.97 (m, 2H), 4.05 (m, 2H), 7.35 (s, 1H) ), 7.50 (s, 1H), 7.75 (d, J = 6.3 Hz, 2H), 8.23 (d, J = 6.3 Hz, 2H), 8.76 (s, 1H).

Example 10:
4,9-Bis (thienotetrazolopyridine-2-yl) -N, N-diethylhexyl-1,2,3,6,7,8-hexahydropyrene-2,7-diaza-1,3,6 , 8-Tetraone (Compound (Tz-11))

Synthesis was carried out in the same manner as in Example 1 except that DPPA was 10 equivalents, anhydrous pyridine was 10 equivalents, and the reaction time was 20 hours (17 mg, yield 15%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.76-1.00 (m, 12H), 1.14-1.45 (m, 16H), 1.74-1.97 (m, 4H), 4.05 (m, 2H), 7.65 (d, J) = 7.2 Hz, 2H), 8.16 (s, 2H), 8.74 (d, J = 7.2 Hz, 2H), 8.84 (s, 2H).

Synthesis example 16:
Synthesis of dibromodithienopyridine

In a two-necked flask, butyl lithium (2.6 M, 0.7 mL) was added at −78 ° C. in dithienopyridine (100 mg, 0.5 mmol) and anhydrous THF (10 mL), and the mixture was stirred for 1 hour and then bromine. (0.06 mL, 1.1 mmol) was added, and the mixture was further stirred at room temperature for 2 hours. After stopping the reaction by adding water, extraction was performed with diethyl ether. The solvent was concentrated and purified by column chromatography (Hexane / AcOEt = 1: 1) to obtain the target compound (110 mg, 62% yield).
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.50 (s, 1H), 7.61 (s, 1H), 8.90 (s, 1H).

Synthesis example 17:
Synthesis of dibromodithienopyridine-N-oxide

The synthesis shown in the above scheme was carried out in the same manner as in Synthesis Example 4 except that the reaction temperature was set to room temperature (228 mg, yield 42%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.35 (s, 1H), 7.94 (s, 1H), 8.59 (s, 1H).

Example 11:
Synthesis of dibromodithienotetrapyridine

The synthesis shown in the above scheme was carried out in the same manner as in Example 1 (55 mg, yield 28%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.07 (s, 1H), 8.08 (s, 1H).

Synthesis example 18:
In a nitrogen atmosphere, in a screw cap test tube, 4-bromo-tert-butylbenzene (640 mg, 3 mmol), 2-stnnylthienopyridine (1.53 g, 3.6 mmol), Pd (PPh ₃ ) ₄ (346 mg, 0) shown in the following scheme. .3 mmol) and anhydrous toluene (5 mL) were added, and the mixture was heated and stirred at 180 ° C. for 10 minutes with a microwave reactor. After completion of the reaction, the solvent was concentrated and purified by silica gel column chromatography (Hexane / AcOEt = 5: 1) to obtain 876 mg of the target compound.

Synthesis example 19:
Thienopyridine (876 mg, 3 mmol), mCPBA (1.29 g, 4.5 mmol), and anhydrous dichloromethane (20 mL) shown in the following scheme were placed in an eggplant flask and stirred at room temperature for 16 hours. After completion of the reaction, saturated aqueous sodium hydrogen carbonate solution was added, the organic layer was extracted with dichloromethane, and dried over anhydrous sodium sulfate. After concentration, purification was performed using silica gel column chromatography (CHCl ₃ / MeOH = 20: 1) to obtain 607 mg of N-oxide (yield 71%).

Synthesis example 20:
N-oxide (607 mg, 2.1 mmol), H ₂ O ₂ (2 mL, ca. 21 mmol), and acetic acid (10 mL) shown in the following scheme were added to the screw cap examiner, and the mixture was stirred at 80 ° C. for 2 hours. Water was added to the reaction mixture, filtered, and washed with methanol to obtain 337 mg (yield 50%) of the target compound.

Example 12:
Under a nitrogen atmosphere, N-oxide (337 mg, 1 mmol), DPPA (1.2 g, 5 mmol), and anhydrous pyridine (395 mg, 5 mmol) shown in the following scheme were added to the screw cap examiner in a nitrogen atmosphere at 120 ° C. at 24 ° C. Stir for hours. As a result, it is considered that the target compound shown in the following scheme can be obtained.

Synthesis example 21:
Synthesis of 2,6-bis (trimethylstannyl-dithiophene (BDT-SnMe ₃ ))

The benzodithiophene derivative (360 mg, 0.59 mmol) and anhydrous THF (20 mL) shown in the above scheme are placed in a two-necked flask, butyllithium (2.6 M, 0.5 mL) is added at −78 ° C., and the mixture is stirred for 1 hour. did. Then, trimethyltin chloride (1M, 1.48 mL) was added, and the mixture was further stirred overnight at room temperature. After stopping the reaction by adding water, extraction was performed with diethyl ether. The solvent was concentrated and purified using alumina column chromatography (Hexane / AcOEt = 1: 1) to obtain 332 mg (yield 72%) of the target compound by GPC.

Example 13:
Synthesis of polymer compounds

Dibromodithienotetrazolopyridine (10 mg, 0.025 mmol), BDT-SnMe ₃ (1.0 eq), Pd ₂ (dba) ₃ (5 mol%), P (o-tol) ₃ (20 mol%) in a pressure resistant test tube. ), Anhydrous toluene (4 mL) and DMF (1 mL) were added, and the mixture was heated and stirred at 80 ° C. for 2 days. After completion of the reaction, reprecipitation was carried out with methanol, and the obtained solid was extracted with Soxhlet (methanol, acetone, methylene chloride, chloroform). Of these, the solvent extracted from chloroform was concentrated to obtain 11 mg ( _Mn = 2300, _Mw / _Mn = 1.47) of the target compound (red solid). Since this polymer has high solubility, only high molecular weight components were recovered using preparative GPC. Fraction 1 (Fr1) had M _n = 8900, M _w / M _n = 1.49, and fraction 2 (Fr2) had M _n = 4800, M _w / M _n = 1.40.

Simulation by Density Functional Theory The LUMO level and HOMO level were calculated by simulating the compounds represented by the following equations by the density functional theory, respectively. The results are shown in Table 9. In addition, because of the solubility, the synthesis of the above compound was carried out for the compound having a long-chain substituent. On the other hand, the energy level (HOMO / LUMO) does not change significantly depending on the length of the substituent, but it takes a long time to calculate when the number of molecules increases. Therefore, the simulation was performed for the short-chain substituent compound. ..

From the above simulation, it was clarified that the compound of the present invention was able to lower the LUMO level and was useful as an organic semiconductor material.

Since the compound of the present invention has high electron acceptability and can maintain a low LUMO level, organic electronic devices such as organic electroluminescence devices, organic thin film devices and other organic electrodevices, organic semiconductor materials, photoelectric conversion devices, and organic substances are used. It is useful for electronic devices, solar cells, solar cell modules, etc.

Claims (8)

A compound represented by any of the following formulas (1) to (3).

[In equations (1) to (3),
Y ¹ and Y ² each independently represent a 5-membered heterocycle containing at least one -SO _2- as a component of the ring. ] The compound according to claim 1, wherein Y ¹ and Y ² are heterocycles represented by the following formulas (Y1) or (Y2) independently.

[In equation (Y1) or (Y2),
R ¹ represents a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, or an alkyl halide group.
p1 represents an integer of 0 to 2, and p2 represents an integer of 0 to 1.
One of * a and * b is * 1 in the equations (1) to (3), and the other is * 2. ] A compound having a structural unit represented by any of the following formulas (I), (IIA), (IIB), (IIC) and (IID).

[In formulas (I), (IIA), (IIB), (IIC) and (IID),
Y ¹ , Y ² , Y ¹¹ and Y ¹² each independently represent a 5-membered heterocycle containing at least one —SO _2- as a ring component.
D represents a bond. ] The compound according to claim 3, which is represented by any of the following formulas (I-1) and (II-1A) to (II-1J).

[In formulas (I-1) and (II-1A) to (II-1J),
Y ¹ , Y ² , Y ¹¹ and Y ¹² each independently represent a 5-membered heterocycle containing at least one —SO _2- as a ring component.
A ¹ represents an aromatic ring which may have a substituent.
n1 and n2 each independently represent an integer of 1 or more.
R ³ independently represents a hydrogen atom or an alkyl group. ] A polymer compound having a structural unit represented by the formula (I) and one or more donor units.

[In formula (I), Y ¹¹ and Y ¹² each independently represent a 5-membered heterocycle containing at least one —SO _2- as a ring component. ] The polymer compound according to claim 5, wherein the donor unit is a structural unit represented by any of the formulas (Dn-1) to (Dn-15).

[In equations (Dn-1) to (Dn-15),
R ³⁰ each independently represents an aliphatic hydrocarbon group.
R ³¹ represents a hydrogen atom or an aliphatic hydrocarbon group.
* Represents a bond. ] An organic semiconductor material containing the compound according to any one of claims 1 to 4 or the polymer compound according to claim 5 or 6. An organic electronic device including the organic semiconductor material according to claim 7.