WO2019054402A1

WO2019054402A1 - Compound and organic semiconductor material containing same

Info

Publication number: WO2019054402A1
Application number: PCT/JP2018/033769
Authority: WO
Inventors: 俊輔丹波; 家　裕隆; 安蘇　芳雄; 一剛萩谷; 光田中
Original assignee: 国立大学法人大阪大学; 東洋紡株式会社
Priority date: 2017-09-13
Filing date: 2018-09-12
Publication date: 2019-03-21
Also published as: JPWO2019054402A1; JP7097573B2

Abstract

Provided is a tetrazolopyridine compound useful as an organic semiconductor material. A compound according to the present invention is characterized by being represented by any one of formulae (1)-(3). In formulae (1)-(3), Y1 and Y2, each independently represent a 5-membered heterocyclic ring containing at least one -SO2- as a constituent element of the ring.

Description

Compound, and organic semiconductor material containing the same

The present invention relates to tetrazolopyridine compounds. In particular, it relates to novel tetrazolopyridine compounds that can be used for organic semiconductor materials.

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.

Japanese Patent Publication 2001-526282

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

As a result of repeated studies to solve the above-mentioned problems, the present inventors condensed a 5-membered heterocyclic ring containing at least one —SO ₂ — as a ring constituent among tetrazolopyridine compounds. The compound was found to be low in LUMO level and useful as an organic semiconductor material, and completed the present invention.

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

Y ¹ and Y ² are preferably each independently a heterocycle represented by the following formula (Y1) or (Y2). In the following formula (Y1) or (Y2), R ¹ represents a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, or a halogenated alkyl group. p1 is an integer of 0 to 2, p2 is an integer of 0 to 1, and p3 is an integer of 0 to 3. One of * a and * b is * 1 in the formulas (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 are each independently -SO _2- as a ring component It represents a 5-membered heterocycle containing at least one. D represents a bond.

The compounds having a structural unit represented by any one of the compounds (I), (IIA), (IIB), (IIC) and (IID) can be represented by the following formulas (I-1) and (II-1A) It is preferable that it is 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 are each independently at least one of —SO ₂ — as a ring component It represents a 5-membered heterocyclic ring containing one. A ¹ represents an aromatic ring which may have a substituent. n1 and n2 each independently represent an integer of 1 or more. Each R ³ independently represents a hydrogen atom or an alkyl group.

The present invention also includes polymer compounds having a structural unit represented by formula (I) and one or more types of donor units. In formula (I), Y ¹¹ and Y ¹² each independently represent a 5-membered heterocyclic ring containing at least one —SO ₂ — as a ring component.

The donor unit is preferably a structural unit represented by any one of formulas (Dn-1) to (Dn-15). In the following formulas (Dn-1) to (Dn-15), each 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 the 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 which is condensed with a 5-membered heterocyclic ring containing at least one —SO ₂ — as a ring constituent, the LUMO level can be lowered and it is useful as an organic semiconductor material is there.

Hereinafter, the present invention will be described. In the following, “the compound represented by the formula (x)” may be simply referred to as “the compound (x)”. The compounds of the present invention also include their tautomers and salts thereof, and the components and functional groups exemplified below can be used alone or in combination.

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), each of Y ¹ and Y ² independently represents a 5-membered heterocyclic ring containing at least one —SO ₂ — as a ring component.

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

Among them, dioxothiophene ring and dioxothiazole ring are preferable.

The hetero ring represented by Y ¹ or Y ² 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; It is also preferable that it is substituted by at least one selected from a substituted alkyl group.

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

(Aliphatic hydrocarbon group)
The aliphatic hydrocarbon group may be linear or cyclic. When it is chained, it may be linear or branched.

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 carbon number of the chain aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 24, and still more preferably 1 to 20.

The alkyl group may be any of linear or branched alkyl group, and specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, 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-propyl hexyl group, 1-ethyl heptyl group, 2-ethyl heptyl group, 1-methyl octyl group, 2-methyl octyl group, 6-methyl octyl group, 2, , 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-butyl heptyl group, 1-n-propyl octyl group, 2-n-propyl octyl group, 1-ethyl nonyl group, 2-ethyl nonyl group, n-dodecyl group, 1-n-pentyl heptyl group, 2-n -Pentylheptyl group, 1-n-butyloctyl group, 2-n-butyloctyl group, 1-n-propylnonyl group, 2-n-propylnonyl group, n-tridecyl group, 1 n-Pentyloctyl, 2-n-Pentyloctyl, 1-n-butylnonyl, 2-n-butylnonyl, 1-methyldecyl, 2-methyldecyl, n-tetradecyl, 1-n-heptylheptyl 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-octyl nonyl group, n-octadecyl group, 1-n-nonyl nonyl group, n-nonadecyl group, n-eicosyl group, 2-octyl dodecyl group And n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, 2-decyltetradecyl group and the like.

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

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

The carbon number of the alicyclic hydrocarbon group is preferably 3 to 20, and more preferably 3 to 14.

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

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

The carbon number of the alkoxy group is preferably 1 to 30, and more preferably 1 to 24.

(Halogenated alkyl group)
As said halogenated alkyl group, the group by which the hydrogen atom of the said alkyl group was substituted by halogen atoms (especially preferably a fluorine atom), such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, is mentioned.

The carbon number of the halogenated alkyl group is preferably 1 to 30, more preferably 1 to 10, and still more preferably 1 to 4.

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

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

Specifically as a heterocyclic ring represented by Y ¹ or Y ² , 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 a halogenated alkyl group. p1 is an integer of 0 to 2, and p2 is an integer of 0 to 1. One of * a and * b is * 1 in the formulas (1) to (3), and the other is * 2.

(Halogen atom)
The halogen atom represented by R ^1, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a bromine atom, an iodine atom.

(Aliphatic hydrocarbon group)
The carbon number of the aliphatic hydrocarbon group represented by R ¹ is preferably 1 to 30, more preferably 1 to 24, and still more preferably 1 to 20.

Examples of the aliphatic hydrocarbon group represented by R ¹ include the same groups as the aliphatic hydrocarbon group which may substitute the heterocycle represented by Y ¹ or Y ² .

(Alkoxy group)
The carbon number of the alkoxy group represented by R ¹ is preferably 1 to 30, more preferably 1 to 24, and still more preferably 1 to 20.

Examples of the alkoxy group represented by R ¹ include the same groups as the alkoxy group which may substitute the heterocycle represented by Y ¹ or Y ² .

(Halogenated alkyl group)
The carbon number of the halogenated alkyl group represented by R ¹ is preferably 1 to 30, more preferably 1 to 10, and still more preferably 1 to 4.

Specific examples of the halogenated alkyl group represented by R ¹ include perfluoroalkyl groups such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group and nonafluorobutyl group, etc. Methyl is particularly preferred.

The compound (1) will be described in detail.

In formula (1), Y ¹ and Y ² are preferably a heterocycle represented by the following formula (Y1-1), (Y1-2), (Y2-1) or (Y2-2). In the following formulas, R ¹ , p ¹ and p 2 are as defined above, and * 1 and * 2 correspond to * 1 or * 2 in the above formula (1).

Among them, the heterocyclic ring represented by the formula (Y1-1) or (Y2-1) is preferable.

In addition, Y ¹ and Y ² may or may not be the same, and are more preferably the same heterocyclic ring.

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

The compound (2) will be described in detail.

In formula (2), Y ¹ is preferably a heterocycle represented by the above formula (Y1-1), (Y1-2), (Y2-1) or (Y2-2). Among them, the heterocyclic ring represented by formula (Y1-1) or (Y2-1) is more preferable. That is, the compounds shown in the following table are preferable, and the compounds (2-1) and (2-3) are more preferable.

The compound (3) will be described in detail.

In formula (3), Y ² is preferably a heterocycle represented by the above formula (Y1-1), (Y1-2), (Y2-1) or (Y2-2). Among them, the heterocyclic ring represented by formula (Y1-1) or (Y2-1) is more preferable. That is, the compounds shown in the following table are preferable, and the compounds (3-1) and (3-3) are more preferable.

2. Production method The outline of the production method of the present invention is represented by the following scheme. In the following schemes, Y ¹ and Y ² are each as defined above. In the following schemes, Z ¹ and Z ² each independently represent a 5-membered heterocyclic ring containing at least one S as a ring component.

That is, after oxidizing the compound (1-X2) (oxidation step: step 1), the compound (1) of the present invention is reacted with an azide compound in the presence of a base to the obtained compound (1-X1) Thus, the compound (Z1) can be produced (cyclization step (1): step 2), and can be produced by oxidation (oxidation step: step 21).

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

In the compound (3) of the present invention, after oxidizing the compound (3-X2) (oxidation step: step 1), the resulting compound (3-X1) is reacted with an azide compound in the presence of a base Thus, the compound (Z3) can be produced (cyclization step (1): step 2), and can be produced by oxidation (oxidation step: step 21).

Examples of the heterocycle represented by Z ¹ or Z ² include heterocycles represented by the following formulae.

Among them, thiophene ring and thiazole ring are preferable.

The heterocyclic group represented by Z ¹ or Z ² 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; It is also preferable that it is substituted by at least one selected from a substituted alkyl group.

As the halogen atom, aliphatic hydrocarbon group, alkoxy group and halogenated alkyl group which substitutes the heterocycle represented by Z ¹ or Z ² , halogen which substitutes the heterocycle represented by Y ¹ or Y ² The same atoms, aliphatic hydrocarbon groups, alkoxy groups, and halogenated alkyl groups can be used.

Examples of the heterocyclic ring represented by Z ¹ or Z ^2, specifically, the aromatic ring is preferably represented by the following formula.

In formulas (ZY1) or (ZY2), R ¹ , p1 and p2 are as defined above, and one of * a and * b is * 1 in formulas (Z1) to (Z3) and the other is * 2 is there.

2-1. Oxidation step: step 1
In step 1, the compound (1-X1), (2-X1) or (3-) is reacted by reacting the above 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, percarboxylic acid such as metachloroperbenzoic acid (mCPBA) and hydrogen peroxide can be used, and percarboxylic acid 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, per 1 mol of the compound (1-X2), (2-X2) or (3-X2). Above, it is 5 mol or less.

Said oxidation step: As a reaction solvent in step 1, for example, halogen solvents such as dichloromethane, chloroform, dichloroethane, dichloropropane; alcohol solvents such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, etc .; acetic acid And carboxylic acid solvents such as trifluoroacetic acid; water; or mixed solvents thereof; and halogen solvents are preferable.

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

2-2. Cyclization step: step 2
In step 2, the compound (Z1), (Z2) or (Z3) is reacted by reacting the azide compound with the compound (1-X1), (2-X1) or (3-X1) in the presence of a base. You can get

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 diaryl phosphoryl azides such as diphenyl phosphoryl azide (DPPA) and bis (4-nitrophenyl) phosphoryl azide; trialkylsilyl azides such as trimethylsilyl azide (TMSA); organic azide compounds such as 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, per 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, for example, supported by a polymer. Among them, trialkylsilyl azide compounds such as diphenyl phosphoryl azide (DPPA) and trimethylsilyl azide are preferable.

When a trialkylsilyl azide is used as the azide compound, a sulfonyl halide compound or a phosphoric acid halide compound may be allowed to coexist.

(Sulfonyl halide compounds)
Examples of the sulfonyl halide compounds include alkylsulfonyl chloride compounds such as methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, isopropane sulfonyl chloride, butane sulfonyl chloride, pentane sulfonyl chloride, hexane sulfonyl chloride and the like; benzene sulfonyl 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-iodobenzenes Phonyl chloride, 3-iodobenzenesulfonyl chloride, 4-iodobenzenesulfonyl chloride, 2-fluorobenzenesulfonyl chloride, 3-fluorobenzenesulfonyl chloride, 4-fluorobenzenesulfonyl chloride, 2-trifluoromethylbenzenesulfonyl chloride, 3-trifluoro Arylsulfonyl chloride compounds such as methylbenzenesulfonyl chloride and 4-trifluoromethylbenzenesulfonyl chloride; sulfonyl chloride compounds such as sulfuryl chloride; sulfonyl fluoride compounds such as nonafluorobutanesulfonic acid fluoride and phenylsulfonic acid fluoride; Be Among them, sulfonyl chloride compounds are preferable, arylsulfonyl chloride compounds are more preferable, and 4-methylbenzene sulfonyl chloride is more preferable.

The amount of the sulfonyl halide compound is preferably 0.5 mol or more and 20 mol or less, more preferably 1 mol, per 1 mol of the compound (1-X1), (2-X1) or (3-X1). The amount is 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 sulfonyl halide compound is in this range, the yield and the reaction efficiency are good.

(Phosphorus halide compound)
Examples of the phosphoric acid halide compound include dialkylphosphoryl chloride compounds such as dimethyl phosphoryl chloride, diethyl phosphoryl chloride, dipropyl phosphoryl chloride, diisopropyl phosphoryl chloride, dibutyl phosphoryl chloride and the like; bis (2,2,2-trichloroethyl) phosphoryl chloride Dihalogenated alkyl phosphoryl chloride compounds such as 2-chloro-2-oxo-1,3,2-dioxaphospholane; diphenyl phosphoryl 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 Rofeniru) phosphoryl chloride, bis (4-chlorophenyl) phosphoryl chloride, bis (3,5-dichlorophenyl) diaryl phosphoryl chloride compound such as phosphoryl chloride; 1,2-phenylene phosphorochloridate; and the like. Among them, dihalogenated alkyl phosphoryl chloride compounds and diaryl phosphoryl chloride compounds are preferable, and bis (2,2,2-trichloroethyl) phosphoryl chloride and diphenyl phosphoryl chloride are more preferable.

The amount of the phosphoric acid halide compound is preferably 0.5 mol or more and 20 mol or less, more preferably 1 per 1 mol of the compound (1-X1), (2-X1) or (3-X1). The molar amount is 15 to 1 mol, more preferably 1 to 13 mol, and particularly preferably 1 to 10 mol. 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 to be made to coexist when reacting the azide compound include, for example, pyridine; imidazole compounds such as N-methylimidazole and imidazole; lithium hydroxide, sodium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, Alkaline metal salt compounds such as cesium carbonate; alkaline earth metal salt compounds such as magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, and barium carbonate; lithium methoxide, sodium methoxide, potassium methoxide, Lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium isopropoxide, sodium isopropoxide, potassium isopropoxide, lithium tert-butoxide, sodium tert-butoxide, Alkoxy alkali metal compounds such as aluminum tert-butoxide, lithium tert-amyl alkoxide, sodium tert-amyl alkoxide, potassium tert-amyl alkoxide; Hydrogenated metal compounds such as lithium hydride, sodium hydride and potassium hydride; trimethylamine, triethylamine , Tripropylamine, diisopropylethylamine, tributylamine, tripentylamine, trihexylamine, trioctylamine, triarylamine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, N-methylmorpholine, N, N-dimethylcyclohexylamine, N, N-dimethylaniline, N-methylimidazole, 1,4-diazabicyclo [2.2.2] octane, 1,8-diaza Tertiary amines, such as cyclo [5.4.0] undec-7-ene; and the like. Among them, pyridine, an imidazole compound, an alkali metal salt compound and a tertiary amine are preferable, more preferably 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, per 1 mol of the compound (1-X1), (2-X1) or (3-X1). It is 8 mol or less, more preferably 1 mol or more and 7 mol or less, and particularly preferably 1 mol or more and 5 mol or less.

At the time of the above-mentioned reaction in step 2, it is preferred not to use a reaction solvent.

When a reaction solvent is used, it can be used in a range which does not affect the reaction. For example, ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents, amide solvents Etc. can be used.

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

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

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

Examples of the amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydrofuran And-(1H) -pyrimidine and the like.

In addition, nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethylsulfoxide, and sulfone solvents such as sulfolane can be used.

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

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

The specific structures and preferable structures of the compounds (Z1), (Z2) and (Z3) correspond to the specific structures and preferable 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, per 1 mol of the compound (Z1), (Z2) or (Z3) is there.

Said oxidation step: The reaction solvent in step 21 is, for example, halogen solvents such as dichloromethane, chloroform, dichloroethane, dichloropropane; alcohol solvents such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, etc .; acetic acid And carboxylic acid solvents such as trifluoroacetic acid; water; and mixed solvents thereof; and carboxylic acid solvents are preferable.

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

2-4. Preparation of Compounds (1-X2), (2-X2) and (3-X2) As the above compounds (1-X2), (2-X2) or (3-X2), commercially available products may be used. And those produced by the method represented by the following scheme may be used. In the following schemes, Z ¹ and Z ² are each as defined above. 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 an acid (cyclization step (2): step 3). The compound (2-X2) or (3-X2) can be produced by reacting an acid with the compound (2-X3) or the compound (3-X3) (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 group represented by each of R ^x1 to R ^x12 is a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 5 to 7 carbon atoms; ; -NHP ^x1; or -M ^{^x1} (L ^x1) _kx is preferably a methylene group contained in the alkyl group, -S -, - O-or -N (P ^x1) - may be replaced in the The hydrogen atom contained in the alkyl group may be substituted by -OP ^x2 or -SP ^x2 .

P ^x1 represents a protective group for an amino group, and specifically, tert-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, allyl A carbamate type protecting group such as an oxycarbonyl group; an amide type protecting group such as a trifluoroacetyl group; an imide type protecting group such as a phthaloyl group; a sulfonamide type protecting group such as a p-toluenesulfonyl group or a 2-nitrobenzenesulfonyl group; It can be mentioned. Among them, as a protecting group of an amino group, a carbamate protecting group or a sulfonamide protecting group is preferable, and a tert-butoxycarbonyl group or a p-toluenesulfonyl group is particularly preferable.

P ^x2 represents an alkyl group having a carbon number of 2 to 3, and when a plurality (preferably 2) of -OP ^x2 or -SP ^x2 is bonded to one carbon atom, a plurality (preferably 2) of P ^x2 may be taken together 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; ^x1 may form a ring with M ^x1 .

Examples of the alkyl group represented by L ^x1 include the same groups as the alkyl groups 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 ^x1 include groups in which -O- is bonded to the alkyl group exemplified as the aliphatic hydrocarbon group represented by R ¹ above, and the alkoxy group has 1 to 4 carbon atoms Is preferred. Examples of the aryloxy group represented by L ^x1 include a phenyloxy group and the like, and the aryloxy group preferably has 6 to 8 carbon atoms. Furthermore, examples of the aralkyloxy group represented by L ^x1 include a benzyloxy group and the like, and a carbon number of 7 to 8 is preferable.

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 formulae, 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, * -M ^x1 (L ^x1 ) _kx includes a group represented by the following formula (Om-5) or (Om-6). In the following formula, * represents a bond.

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

Cyclization process (2): Process 3
In step 3, a catalyst may be coexistent.

Examples of the catalyst include metal catalysts, and transition metal catalysts such as palladium catalysts, nickel catalysts, iron catalysts, copper catalysts, rhodium catalysts, and ruthenium catalysts. Among them, palladium catalysts are preferred.

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 the like. Palladium (II), palladium (II) selenide, palladium cyanide (II), palladium acetate (II), palladium trifluoroacetate (II), palladium acetylacetonate (II), diacetate bis (triphenylphosphine) palladium (II), tetrakis (triphenylphosphine) palladium (0), dichlorobis (triphenylphosphine) palladium (II), dichlorobis (acetonitrile) 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 (dibenzylidene Acetone) Palladium (0), Tris (dibenzylideneacetone) dipalladium (0), Tris (dibenzylideneacetone) dipalladium (0) chloroform adduct, dichloro [1,3-bis (2,6-diisopropylphenyl) imidazole -2-ylidene] (3-chloropyridyl Palladium (II), bis (tri-tert-butylphosphine) palladium (0), dichloro [2,5-norbornadiene] palladium (II), dichlorobis (ethylenediamine) palladium (II), dichloro (1,5-cyclooctadiene) And the like) palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II), dichlorobis (triphenylarsine) palladium (II) and the like. These catalysts may be used alone or in combination of two or more.

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 From the point of view of 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 more preferable.

The catalyst may be coordinated with a specific ligand.

Examples of the ligand include trimethyl phosphine, triethyl phosphine, tri (n-butyl) phosphine, tri (isopropyl) phosphine, tri (tert-butyl) phosphine, tri-tert-butyl phosphonium tetrafluoroborate, bis ( tert-Butyl) methyl phosphine, tricyclohexyl phosphine, diphenyl (methyl) phosphine, triphenis phosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-tolyl) phosphine, tris (2- furyl ) Phosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, 2-dicyclohexylphosphinobiphenyl, 2-dicyclo Xylphosphino-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) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis ( Phenylphosphino) butane, 1,2-bis (dicyclohexylphosphino) ethane, 1,3-bis (dicyclohexylphosphino) propane, 1,4-bis (dicyclohexylphosphino) butane, 1,2-bisdiphenylphosphino Ethylene, 1,1′-bis (diphenylphosphino) ferrocene, 1,2-ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 2,2′-bipyridyl, 1,3-diphenyldihydroimidazolyl Den, 1,3-dimethyldihydroimidazolylidene, diethyldihydroimidazolylidene, 1,3-bis (2,4,6-trimethylphenyl) dihydroimidazolylidene, 1,3-bis (2,6-diisopropylphenyl) ) Dihydroimidazolylidene, 1, 10-phenanthroline, 5, 6-dimethyl-1,10-phenanthroline, batophenanthroline and the like. One of these ligands may be used alone, or two or more thereof may be used.

When coordinating a ligand, the molar ratio of catalyst to ligand (catalyst: ligand) is generally about 1: 0.5 to 1:10 and is not particularly limited, but the yield and reaction efficiency In view of the above, 1: 1 to 1: 8 is preferable, 1: 1 to 1: 7 is more preferable, and 1: 1 to 1: 5 is 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 from the viewpoint of yield and reaction efficiency 1: 1.5 to 1: 8 is preferable, 1: 1.8 to 1: 6 is more preferable, and 1: 2 to 1: 5 is more preferable.

In the step 3, after reacting the compound (1-X3) with the compound (1-X4), the acid to be 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, for example, ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents And amide solvents can be used.

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

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

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

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

The reaction temperature is not particularly limited, but is preferably 0 ° C. or more and 200 ° C. or less from the viewpoint of enhancing 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 employed.

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

Cyclization process (3): Process 4
As the acid to be reacted with the compound (2-X3) or the compound (3-X3) in the step 4, cyclization step (2): The same acid as the acid exemplified as the acid used in the step 3 can be used. And inorganic acids are preferred, and hydrochloric acid is particularly preferred.

As the reaction solvent in step 4, a solvent similar to the reaction solvent used in cyclization step (2): step 3 can be used. For example, toluene, xylene, tetrahydrofuran, 1,4-dioxane, N, N- Dimethylformamide is particularly preferred.

The reaction temperature is preferably 0 ° C. or more and 200 ° C. or less from the viewpoint of enhancing 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 employed. In the following schemes, P ^x1 , P ^x2 and Z ¹ are as defined above.

Cyclization process (4): Process 5
As the oxidizing agent used in step 5, the same oxidizing agent as the oxidizing agent used in the above-mentioned oxidation 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-mentioned oxidation step: step 1 can be used, and a halogen-based solvent is preferable.

As Step 5, for example, a step represented by the following scheme can be preferably employed. In the following schemes, P ^x1 is as defined above.

3. Tetrazolopyridine multimer As a structural unit derived from the compound (1), (2) or (3) of the present invention, it is represented by the formula (I), (IIA), (IIB), (IIC) or (IID) Structural unit (hereinafter simply referred to as “structural unit (I)”, “structural unit (IIA)”, “structural unit (IIB)”, “structural unit (IIC)” or “structural unit (IID)” Also included within the technical scope of the present invention is a tetrazolopyridine multimer comprising

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

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

Structural units (I), (IIA), (IIB), (IIC), and specific examples and preferred ranges of Y ¹ and Y ² in the structural unit (IID) is and Y ¹ in the formula (1) to (3) is the same as the specific examples and preferred ranges of Y ^2.

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

Among them, dioxothiophene ring and dioxothiazole ring are preferable.

The heterocyclic group represented by Y ¹¹ or Y ¹² 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; It is also preferable to be substituted by at least one selected from a halogenated alkyl group.

As the halogen atom, aliphatic hydrocarbon group, alkoxy group and halogenated alkyl group for substituting the heterocyclic ring represented by Y ¹¹ or Y ¹² above, halogen for substituting the heterocyclic ring represented by Y ¹ or Y ² above The same atoms, aliphatic hydrocarbon groups, alkoxy groups, and halogenated alkyl groups can be used.

Examples of the heterocyclic ring represented by the above Y ¹¹ or Y ^12, specifically, the ring is preferably represented by the following formula.

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 of 0 to 1; One of * a and * b is * 1 in formula (I), (IIA), (IIB), (IIC) or (IID), and the other is * 2.

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

Examples of the compound containing any of the above structural units (IIA), (IIB), (IIC) and (IID) include compounds (II-1A) to (II-1J) represented by the following formulas. Among them, 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 above. Each A ¹ independently represents an aromatic ring which may be substituted. n2 represents an integer of 1 or more.

The aromatic ring represented by A ^1, an aromatic hydrocarbon ring, aromatic heterocyclic ring.

As said aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring etc. are mentioned, for example, A benzene ring is preferable.

As said aromatic heterocyclic ring, the aromatic heterocyclic ring represented by a following formula is mentioned, for example. In the following formulae, R ³ represents a hydrogen atom or an alkyl group, and R ⁴ represents a halogen atom, an alkyl group, an alkoxy group or a halogenated alkyl group.

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

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

The aromatic ring represented by the above A ¹ may have a substituent other than a halogen atom. As a substituent other than a halogen atom, an alkyl group, an alkoxy group, a halogenated alkyl group etc. are mentioned, for example.

Examples of the alkyl group include the same groups as the alkyl groups exemplified as the aliphatic hydrocarbon group of R ¹ , and the carbon number of the alkyl group is preferably 1 to 30, and more preferably 1 to 24.

Examples of the alkoxy group include groups in which -O- is bonded to the alkyl group, and the number of carbon atoms of the alkoxy group is preferably 1 to 30, and more preferably 1 to 24.

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

Among the aromatic rings represented by A ¹ above, the aromatic hydrocarbon ring is preferably bonded to the pyridine ring of tetrazolopyridine at the 2- or 5-position, and the aromatic heterocyclic ring is preferably in the 2-position. Preferably bonded to the pyridine ring of tetrazolopyridine.

The aromatic ring represented by A ^1, the aromatic ring is preferably represented by the following formula.

In formulas (Ar1) to (Ar16), each R ³ independently represents a hydrogen atom or an alkyl group. Each R ⁴ independently represents a halogen atom, an alkyl group, an alkoxy group, or a halogenated alkyl 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.

The halogen atom represented by R ^4, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a bromine atom, an iodine atom.

As the alkyl group represented by R ³ above, the alkyl group represented by R ⁴ above, the alkoxy group, and the halogenated alkyl group, aliphatic oxidation which the heterocycle represented by Y ¹ above may have, respectively The same groups as the alkyl group, the alkoxy group or the halogenated alkyl group exemplified as the hydrogen group can be mentioned.

As the A ^1, specifically, it is more preferably a structural unit represented by the following formula.

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 (Ar 3-1), X ² is at the 4-position It is preferred that they be linked.

In the above formulas (Ar1-1) to (Ar16-1), R ³ is as defined above. R ⁵ represents an alkyl group, an alkoxy group or a halogenated alkyl 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 preferred, and a bromine atom is more preferred. R ⁵ is respectively the same as the alkyl group, alkoxy group or halogenated alkyl group represented by R ⁴ above, preferably an alkoxy group or halogenated alkyl group. 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 (II).
H-A ¹⁰ -Y ⁴⁰ -A ¹¹ -H (I-I)

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

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

Preferably, A ¹⁰ and A ¹¹ are identical.

Specifically as a compound represented by said Formula (II), the compound shown by the following table is preferable. Among them, compounds (II-1) to (II-12) are preferable.

In the following table, (Y-I-1) to (Y-I-4) each represent a unit represented by the following formula.

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 formulae, Y ⁵⁰ and Y ⁵¹ each represent a structure represented by any one of formulas (IIA) to (IID).

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

Specifically as a compound represented by the said Formula (II-I), the compound shown by the following table is preferable. Among them, compounds (II-I-97) to (II-I-120) are more preferable, and compounds (II-I-98), (II-I-99), (II-I-105), (II-) More preferred are I-108), (II-I-110), (II-I-111), (II-I-117) and (II-I-120).

In the following table, (Y-II-1) to (Y-II-12) represent a unit represented by the following formula.

3-1. Method of Producing Tetrazolopyridine Multimer An outline of a method of producing the above compound (I-1) is represented by the following scheme. In the following formulae, X ³ represents a halogen atom. M ¹ has the same meaning as M ^x1 , L ¹ has the same meaning as L ^x1 , k1 has the same meaning as kx, and A ¹ has the same meaning as described above. R ³ , Y ¹¹ , Y ¹² , Z ¹¹ and Z ¹² are as defined 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 cycloaddition step (1): step 6), the compound (I-X5) obtained and oxidation are carried out The compound (ZI-1) is produced by reacting an azide compound with an agent (oxidation step: step 7), and reacting the resulting compound (I-X2) with an azide compound in the presence of a base (cyclization step (cyclization step 1): Step 8), can be manufactured by oxidation (oxidation step: step 31).

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

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

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

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

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

Further, the structure represented by the following formula (II-X3) is a structure represented by any one of the following formulas (IIA-X3), (IIB-X3), (IIC-X3) and (IID-X3) Shall be meant.

Furthermore, the structure represented by the following formula (II-X6) is a structure represented by any one of the following formulas (IIA-X6), (IIB-X6), (IIC-X6) and (IID-X6) Shall be meant.

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 cycloaddition step (2): step 11), oxidation with the compound (II-X5) obtained The compound (ZII-1) is produced by reacting the compound (II) with an agent (oxidation step: step 12), and reacting the resulting compound (II-X2) with an azide compound in the presence of a base (cyclization step (1 ): Step 13), can be produced by oxidation (oxidation step: step 32).

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

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

Aromatic cycloaddition step (1): Steps 6, 9, 10

(Step 6)
In step 6, compound (I-X5) can be produced by reacting compound (I-X6) with compound (I-X4).
M ¹ (L ¹ ) _k ^1- (A ¹ ) _{n 1} -R ³ (I-X 4)

In the formula, A ¹ , M ¹ , L ¹ , R ³ , k 1 and n 1 are as defined 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, compound (I-X2) can be produced by reacting compound (I-X3) with compound (I-X4).

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, compound (ZI-1) can be produced by reacting compound (I-X1) with compound (I-X4).

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

M ¹ , L ¹ and k ¹ in the formula (I-X4) are the same as M ^x1 , L ^x1 and kx in the formula (1-X4-1), and as the compound (I-X4), Compounds are mentioned.
M ¹⁰ (L ¹⁰ ) _k ¹⁰ -A ²⁰ -R ³ (I-X4-I)

However, in the formula, R ³ is as defined above. A ²⁰ represents a structure represented by any one of the following formulas (Ar1-1) ~ (Ar16-1), as the A ^20, the structure of Formula (Ar1-2) are preferred. * -M ¹⁰ (L ¹⁰ ) _k ¹⁰ 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 compound (I-X4) is preferably 0.6 to 10 moles, more preferably 0.8, per 1 mole of compound (I-X6), compound (I-X3) or (I-X1). ~ 6 moles.

Furthermore, when reacting the compound (I-X6), the compound (I-X3) or the compound (I-X1) with the compound (I-X4), the cyclization step (2): the catalyst exemplified in the step 3 The same catalysts can be used under the same conditions.

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

Furthermore, when reacting compound (I-X6), compound (I-X3) or compound (I-X1) with compound (I-X4), cyclization step (2): a base similar to the base exemplified in 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 temperature of steps 6, 9 and 10 is the same as in cyclization step (2): step 3.

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

(Step 11)
In step 11, compound (II-X5) can be produced by reacting compound (II-X6) with a compound represented by the following formula (II-X4).
^{^{_{X 4 - (A 2) n1}}} -X 4 (II-X4)

In the formula, A ² and n 1 are as defined 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), M ¹⁰ , L ¹⁰ and k ¹⁰ are respectively the same as M ^x1 , L ^x1 and k ^x in formula (1-X4-1) is there.

As the compound (II-X6), a group represented by any one of formulas (Om-1) to (Om-6) in the compound (1-X2), (2-X2) or (3-X2) The compound which couple | bonded is mentioned.

As the compound (II-X3), a group represented by any one of the formulas (Om-1) to (Om-6) in the compound (1-X1), (2-X1) or (3-X1) can be mentioned The compound which couple | bonded is mentioned.

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

The halogen atom in the formula (II-X4) includes 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 formulae.
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, compounds shown in the following table are preferable, and compounds (II-X4-I-2), (II-X4-I-3), (II-X4-I-9), (II-X4-I-12) (II-X4-I-14), (II-X4-I-15), (II-X4-I-21) and (II-X4-I-24) are more preferable.

The amount of compound (II-X4) is preferably 0.6 to 5 moles, more preferably 0. 1 mole per 1 mole of compound (II-X6), compound (II-X3) or compound (II-X1). 8 to 3 moles.

The catalyst coexisting when the compound (II-X6), the compound (II-X3) or the compound (II-X1) and the compound (II-X4) are reacted is exemplified in the cyclization step (2): step 3 It is 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 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 more preferable.

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

In Steps 11, 14 and 15, the cyclization step (2): the bases exemplified in Step 3 may be allowed to coexist under the same conditions.

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

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

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

As the oxidizing agent, compounds similar to the oxidizing agents exemplified in the oxidation step: step 1 can be used under the same conditions.

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

3-4. Cyclization process (1): processes 8 and 13
In step 8 or step 13, compound (Z-I-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, the same compounds as the azide compound exemplified in the cyclization step (1): step 2 can be used under the same conditions.

Moreover, the base to be made to coexist when making the azide compound react is also the same as the base exemplified in the cyclization step (1): step 2, and can be used under the same conditions.

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

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

As the oxidizing agent, compounds similar to the oxidizing agents exemplified in the oxidation step: step 21 can be used under the same conditions.

In addition, with regard to the reaction solvent and the reaction temperature, the same conditions as in the oxidation step: step 21 can be adopted.

4. Organic Semiconductor Material The compounds (1), (2) and (3) of the present invention can lower the LUMO level, have excellent thermal stability, and are easy to add various functional groups. Organic semiconductor materials which are excellent as organic semiconductor materials and obtained using the compound (1), (2) or (3) of the present invention are also included in the technical scope of the present invention. By having the structural units (I), (IIA), (IIB), (IIC) and (IID) derived from the formulas (1), (2) or (3), the LUMO tends to be lowered, n-type Alternatively, it is useful as an ambipolar semiconductor material.

As said organic-semiconductor material, the high molecular compound which has a structural unit represented by Formula (I), and 1 type, or 2 or more types of donor property units is preferable.

In formula (I), Y ¹ , Y ² , Y ¹¹ and Y ¹² are as defined above.

The structural units (I), (IIA), (IIB), (IIC) and (IID) derived from the above compounds (1) to (3) are electron accepting, and as an acceptor unit in the extended π conjugated system Preferably, one or more types of donor units are combined to form a donor-acceptor type semiconductor polymer compound, and structural units (I) and donor units are alternately arranged. Is preferred.

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

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

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

Such a polymer compound is particularly useful for organic electroluminescent devices, organic electrodevices such as organic thin film transistor devices, organic semiconductor materials, photoelectric conversion devices, organic electronic devices, solar cells, solar cell module applications and the like.

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

In formulas (Dn-1) to (Dn-15), each 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 which may substitute the heterocycle represented by Y ¹ , and the carbon number is 1 to 30 is preferable, more preferably 1 to 24, further preferably 1 to 20.

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

In the formula, A ¹ , M ¹ , L ¹ , k ¹ , Y ¹¹ , Y ¹² and X ³ are as defined 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 one of formulas (Dn-1) to (Dn-12) above, and any one of formulas (Dn-4), (Dn-6) and (Dn-7) The group represented is more preferable.

The halogen atom of X ^3, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a bromine atom.

N10 is preferably 0.

The molar ratio of the compound (I-1) to the 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 preferably 40:60 to 60:40. A range is more preferred.

As a 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.

Furthermore, in 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.

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

The compounds according to the present invention have high electron acceptability and can lower the LUMO level, and therefore organic electronic devices, for example, organic electroluminescent devices, organic electrodevices such as organic thin film transistor devices, organic semiconductor materials, photoelectric conversion devices, organic It is useful for electronic devices, solar cells, solar cell module applications and the like.

The present application claims the benefit of priority based on Japanese Patent Application No. 2017-176221 filed on Sep. 13, 2017. The entire content of the specification of the above-mentioned Japanese Patent Application No. 2017-176221 is incorporated herein by reference.

EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is of course not limited by the following examples, and appropriate modifications may be made as long as the present invention can be applied to the purpose. Of course, implementation is also possible, and all of them are included in the technical scope of the present invention. In the following, “parts” means “parts by mass” and “%” means “% by mass” unless otherwise noted.

Synthesis Example 1:
Synthesis of 2- (2,2-dimethoxyethylamino) methyl thiophene

In a three-necked flask, 2-thiophenecarbaldehyde (2.24 g, 20 mmol), aminoacetaldehydedimethylacetal (2.2 g, 20 mmol), p-toluenesulfonylsulfonic acid (10 mg), and absolute ethanol (20 mL) were added 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. The reaction was quenched by the addition of water and extracted 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 objective compound.

Synthesis Example 2:
Synthesis of 2- (2,2-dimethoxyethyl-p-toluenesulfonylamino) methyl thiophene

In a two-necked flask, thiophene derivative (4.05 g, 20 mmol), pyridine (4.7 g, 60 mmol) shown in the above scheme, and toluenesulfonic acid chloride (4.6 g, 24 mmol) at 0 ° C. in anhydrous dichloromethane (20 mL) ) Was added and 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 desired compound.

Synthesis Example 3:
Synthesis of thieno [3,2-c] pyridine (step 4)

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

Synthesis Example 4:
Synthesis of thieno [3,2-c] pyridine-N-oxide (step 1)

In an eggplant flask, thienopyridine (Thienopyridine) (1.37 g, 10.1 mmol), metachloroperbenzoic acid (mCPBA) (2.6 g, 15 mmol), and anhydrous dichloromethane (50 mL) were charged, and stirred at -5 ° C for 2 days. After completion of the reaction, a saturated aqueous solution of sodium hydrogen carbonate was added and the organic layer was extracted with dichloromethane and dried using anhydrous sodium sulfate. After concentration, the residue is purified by silica gel column chromatography (CHCl ₃ / MeOH = 20: 1) to obtain 520 mg (yield 34%) of thieno [3,2-c] pyridine-N-oxide (Thienopyridine N-oxide). The
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.29 (d, J = 5.5 Hz, 1 H), 7.66 (d, J = 5.5 Hz, 1 H), 7.72 (d, J = 7.0 Hz, 1 H), 8. 17 (dd , J = 1.6, 7.0 Hz, 1 H), 8. 76 (d, J = 1.6 Hz, 1 H).

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

Thieno [3,2-c] pyridine-N-oxide (520 mg, 3.45 mmol), diphenylphosphate azide (DPPA) (4.7 g, 17 mmol), and anhydrous pyridine in a screw-cap test tube (75 mL, 6.9 mmol) was added and stirred at 120 ° C. for 24 hours under a nitrogen atmosphere. The reaction solution is directly purified by silica gel column chromatography (CH ₂ Cl ₂ / MeOH = 50: 1) to obtain 288 mg (yield 47%) of thienotetrazolopyridine (compound (Tz-1)). The
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.61 (d, J = 7.3 Hz, 1 H), 7.83 (d, J = 5.4 Hz, 1 H), 8. 10 (d, J = 5.4 Hz, 1 H), 8. 66 (d , J = 7.3 Hz, 1 H).

Synthesis Example 5:
Synthesis of 2-tributylstannylthieno [3,2-c] pyridine

Dithioneamine (0.21 mL, 5.4 mmol) at −78 ° C. in a two-necked flask with thienopyridine (408 mg, 3.0 mmol) and anhydrous tetrahydrofuran (30 mL), butyl lithium (2.6 M, 1.7 mL) 2.) The generated lithium diisopropylamide (LDA) was added and 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. The reaction was quenched by the addition of water and extracted 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 objective 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, 1 H), 8. 35 (d, J = 5.5 Hz, 1 H), 9.09 (s, 1 H).

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-stannyl thienopyridine (425 mg, 1.0 mmol), Pd (PPh ₃ ) ₄ (38 mg, 0.033 mmol), and anhydrous in test tubes Toluene (2 mL) was charged and stirred at 180 ° C. for 10 minutes using a microwave reactor. After completion of the reaction, the solvent was concentrated and purified using silica gel column chromatography (Hexane / AcOEt = 5: 1) to obtain 71 mg (yield 38%) of a target compound (yellow solid).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.87 (t, J = 7.2 Hz, 3 H), 1.28-1.40 (m, 4 H), 1.90-1.99 (m, 2 H), 4.16 (t, J = 6.5 Hz, 2H), 7.34 (s, 1 H), 7. 76 (d, J = 5.5 Hz, 1 H), 7. 87 (s, 1 H), 8.42 (d, J = 5.5 Hz, 1 H), 9.08 (s, 1 H).

Synthesis Example 7:
Synthesis of 1,4-bis (hexyloxy) -2,5-bis (thieno [3,2-c] pyridine-N-oxid-2-yl) benzene (Step 12)

The synthesis was performed in the same manner as in Synthesis Example 4 except that mCPBA was changed from 1.5 equivalents to 3.0 equivalents, the reaction temperature was room temperature, and the reaction time was 14 hours (230 mg, 51% yield). .
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.87 (t, J = 7.2 Hz, 3 H), 1.28-1.40 (m, 4 H), 1.90-1.99 (m, 2 H), 4.16 (t, J = 6.5 Hz, 2H), 7.34 (s, 1 H), 7. 76 (d, J = 5.5 Hz, 1 H), 7. 87 (s, 1 H), 8.42 (d, J = 5.5 Hz, 1 H), 9.08 (s, 1 H).

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

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

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

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

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

The synthesis was performed in the same manner as in Synthesis Example 4 except that mCPBA was changed from 1.5 equivalents to 3.0 equivalents, and 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, 1 H), 8.16 (d, J = 5.5 Hz, 1 H), 8.74 (s, 1 H).

Example 3:
Synthesis of 4,4′-Dihexyl-5,5′-bis (thienotetrazolopyridin-2-yl) dithiophene (Compound (Tz-3)) (Step 13)

The compound (Tz-3) was synthesized in the same manner as in Example 1 except that 10 equivalents of DPPA and 4 equivalents of anhydrous pyridine were used (33 mg, 54% yield).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.88 (t, J = 7.4 Hz, 3 H), 1.30-1. 46 (m, 6 H), 1. 68-1. 78 (m, 2 H), 2. 86 (t, J = 7.9 Hz, 2H), 7.13 (s, 1 H), 7.56 (d, J = 7.3 Hz, 1 H), 8.07 (s, 1 H), 8. 65 (d, J = 7.3 Hz, 1 H).

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)

The synthesis was performed 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, 3 H), 1.29-1.38 (m, 2 H), 1.57-1.76 (m, 2 H), 2.75 (t, J = 7.9 Hz, 2H), 7.80 (d, J = 5.5 Hz, 1 H), 8.06 (s, 1 H), 8.18 (s, 1 H), 8.51 (d, J = 5.5 Hz, 1 H), 9.17 (s, 1 H).

Synthesis Example 11:
Synthesis of 1,3-Bis (thieno [3,2-c] pyridine-N-oxido-2-yl) -6,7-dibutyl-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 mCPBA was changed from 1.5 equivalents to 3.0 equivalents and the reaction temperature was changed to room temperature (134 mg, yield 58%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.90 (br t, 3 H), 1.29-1.38 (br m, 2 H), 1.57-1.76 (br m, 2 H), 2.75 (br t, 2 H), 7.80 (br d, 1 H), 8.08 (br s, 1 H), 8. 38 (br s, 1 H), 8.44 (br d, 1 H), 8.99 (s, 1 H).

Example 4:
Synthesis of 1,3-Bis (thienotetrazolopyridin-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 10 equivalents of DPPA and 4 equivalents of anhydrous pyridine were used (39 mg, yield 28%).

Example 5:
It is thought that the compound (Tz-4-1) can be obtained by reacting the compound (Tz-4) obtained in Example 4 with an 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 the reaction was performed in the same manner as in Synthesis Example 4 except that the reaction temperature was changed to room temperature (333 mg, yield 80%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.40 (d, J = 5.5 Hz, 1 H), 7.57 (d, J = 5.5 Hz, 1 H), 7.61 (d, J = 5.5 Hz, 1 H), 7.98 (d , J = 5.5 Hz, 1 H), 8. 85 (s, 1 H).

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

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

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, 51% yield).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.88 (t, J = 7.4 Hz, 3 H), 1.27-1.44 (m, 6 H), 1.59-1.69 (m, 2 H), 2.74 (t, J = 7.9 Hz, 2H), 7.80 (d, J = 5.5 Hz, 1 H), 8.07 (s, 1 H), 8.18 (s, 1 H), 8.51 (d, J = 5.5 Hz, 1 H), 8.17 (s, 1 H).

Synthesis Example 14:
Synthesis of 1,3-Bis (thieno [3,2-c] pyridine-N-oxido-2-yl) -6,7-dihexyl-naphtho [2,3-b] thiophene-4,9-dione (step) 12)

Synthesis was carried out in the same manner as in Synthesis Example 4 except that 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, 3 H), 1.27-1.44 (m, 6 H), 1.59-1.69 (m, 2 H), 2.75 (t, J = 7.9 Hz, 2 H), 7.39 ( br d, 1 H), 7.53 (br d, 1 H), 7. 94 (s, 1 H), 7. 96 (s, 1 H), 8. 89 (s, 1 H).

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

The compound (Tz-10) was synthesized in the same manner as in Example 1 except that 10 equivalents of DPPA and 10 equivalents of anhydrous pyridine were used (22 mg, 44%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.88 (t, J = 7.4 Hz, 3 H), 1.27-1.44 (m, 6 H), 1.59-1.69 (m, 2 H), 2.77 (t, J = 7.9 Hz, 2H), 7.63 (d, J = 7.7 Hz, 1 H), 8. 10 (s, 1 H), 8. 70 (s, 1 H), 8. 73 (d, J = 7.7 Hz, 1 H).

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

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

Synthesis Example 15:
4,9-Bis (thieno [3,2-c] pyridine-N-oxid-2-yl) -N, N-diethylhexyl-1,2,3,6,7,8-hexahydropyrene-2, Synthesis of 7-diaza-1,3,6,8-tetraone

The synthesis was performed in the same manner as in Synthesis Example 4 except that 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, 1 H), 7. 75 (d, J = 6.3 Hz, 2 H), 8.23 (d, J = 6.3 Hz, 2 H), 8. 76 (s, 1 H).

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

The synthesis was performed in the same manner as in Example 1 except that 10 equivalents of DPPA and 10 equivalents of anhydrous pyridine were used, and the reaction time was 20 hours (17 mg, 15% yield).
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.76-1.00 (m, 12 H), 1.14-1.45 (m, 16 H), 1.74-1.97 (m, 4 H), 4.05 (m, 2 H), 7.65 (d, J = 7.2 Hz, 2 H), 8. 16 (s, 2 H), 8. 74 (d, J = 7.2 Hz, 2 H), 8.84 (s, 2 H).

Synthesis Example 16:
Synthesis of dibromodithienopyridine

In a two-necked flask, dithienopyridine (100 mg, 0.5 mmol) and butyl lithium (2.6 M, 0.7 mL) in anhydrous THF (10 mL) at -78 ° C and stirred for 1 hour, then bromine (0.06 mL, 1.1 mmol) was added and the mixture was further stirred at room temperature for 2 hours. The reaction was quenched by the addition of water and extracted with diethyl ether. The solvent was concentrated and purified by column chromatography (Hexane / AcOEt = 1: 1) to obtain the desired compound (110 mg, yield 62%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.50 (s, 1 H), 7.61 (s, 1 H), 8. 90 (s, 1 H).

Synthesis Example 17:
Synthesis of dibromodithienopyridine-N-oxide

The synthesis shown in the above scheme was performed in the same manner as in Synthesis Example 4 except that the reaction temperature was set to room temperature (228 mg, 42% yield).
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.35 (s, 1 H), 7.94 (s, 1 H), 8. 59 (s, 1 H).

Example 11:
Synthesis of dibromodithienotetrapyridine

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

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

Synthesis Example 19:
In an eggplant flask, Thienopyridine (876 mg, 3 mmol), mCPBA (1.29 g, 4.5 mmol), and anhydrous dichloromethane (20 mL) shown in the following scheme were placed, and stirred at room temperature for 16 hours. After completion of the reaction, a saturated aqueous solution of sodium hydrogen carbonate was added and the organic layer was extracted with dichloromethane and dried using 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:
A screw tester was charged with 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, and stirred at 80 ° C. for 2 hours. The reaction solution was poured into water, filtered, and washed with methanol to obtain 337 mg (yield 50%) of a target compound.

Example 12:
In a nitrogen atmosphere, the screw point tester is charged with N-oxide (337 mg, 1 mmol), DPPA (1.2 g, 5 mmol) and anhydrous pyridine (395 mg, 5 mmol) shown in the following scheme, and 24 at 120 ° C. in a nitrogen atmosphere. Stir for hours. As a result, it is considered that the target compound shown in the following scheme is obtained.

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

In a two-necked flask, the benzodithiophene derivative (360 mg, 0.59 mmol) shown in the above scheme and anhydrous THF (20 mL) were added, butyl lithium (2.6 M, 0.5 mL) was added at -78.degree. C. and stirred for 1 hour did. After that, trimethyltin chloride (1 M, 1.48 mL) was added and further stirred overnight at room temperature. The reaction was quenched by the addition of water and extracted 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 macromolecular compounds

Dibromodithieno tetrazolopyridine (10 mg, 0.025 mmol), BDT-SnMe ₃ (1.0 equivalent), 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 performed with methanol, and the obtained solid was Soxhlet extracted (methanol, acetone, methylene chloride, chloroform). Among them, the solvent of the chloroform extract was concentrated to obtain 11 mg ( _Mn = 2300, _Mw / _Mn = 1.47) of the target compound (red solid). Since this polymer is highly soluble, only high molecular weight components were recovered using preparative GPC. The fraction 1 (Fr1) was _Mn = 8900, _Mw / _Mn = 1.49, and the fraction 2 (Fr2) was _Mn = 4800, _Mw / _Mn = 1.40.

Simulation by Density Functional Theory The density functional theory simulation was performed for each of the compounds represented by the following formulas to calculate the LUMO level and the HOMO level. The results are shown in Table 9. From the viewpoint of solubility, the above compounds were synthesized for long chain substituents. On the other hand, the energy level (HOMO / LUMO) does not change largely due to the length of the substituent, but the calculation time is long as the number of molecules increases, so the simulation was performed on the compound of the short chain substituent .

From the above simulation, it was revealed that the compound of the present invention can lower the LUMO level and is useful as an organic semiconductor material.

Since the compound of the present invention has high electron acceptability and can maintain the LUMO level low, organic electronic devices such as organic electroluminescent devices, organic electrodevices such as organic thin film transistor devices, organic semiconductor materials, photoelectric conversion devices, organic compounds It is useful for electronic devices, solar cells, solar cell module applications and the like.

Claims

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

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

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

[In the formulas (I), (IIA), (IIB), (IIC) and (IID),
Y 1 , Y 2 , Y 11 and Y 12 each independently represent a 5-membered heterocyclic ring 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 one of the following formulas (I-1) and (II-1A) to (II-1J).

[In the formulas (I-1) and (II-1A) to (II-1J),
Y 1 , Y 2 , Y 11 and Y 12 each independently represent a 5-membered heterocyclic ring 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.
Each R 3 independently represents a hydrogen atom or an alkyl group. ]
A high molecular compound having a structural unit represented by the formula (I) and one or more types of donor units.

[In formula (I), Y 11 and Y 12 each independently represent a 5-membered heterocyclic ring 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 one of formulas (Dn-1) to (Dn-15).

[In the formulas (Dn-1) to (Dn-15),
Each 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 comprising 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 comprising the organic semiconductor material according to claim 7.