WO2016143823A1

WO2016143823A1 - Compound, and organic semiconductor material containing same

Info

Publication number: WO2016143823A1
Application number: PCT/JP2016/057383
Authority: WO
Inventors: 俊輔丹波; 家　裕隆; 安蘇　芳雄; 一剛萩谷
Original assignee: 国立大学法人大阪大学; 東洋紡株式会社
Priority date: 2015-03-10
Filing date: 2016-03-09
Publication date: 2016-09-15
Also published as: JP6706822B2; JPWO2016143823A1

Abstract

The objective of the present invention is to provide a tetrazolopyridine compound that is useful as an organic semiconductor material, is also useful as a gas generating agent due to the excellent heat stability thereof, and is further useful as a raw material for various compounds. The compound according to the present invention is characterized by being represented by formula (1). (In formula (1), R¹ represents a hydrogen atom, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group, A¹ represents an aromatic ring which may be substituted or a halogen atom, m represents an integer of 0-2, n represents an integer of 2-4, m+n is 4.)

Description

Compound and organic semiconductor material containing the same

The present invention relates to a tetrazolopyridine compound. In detail, it is related with the novel tetrazolopyridine compound which can be used for an organic semiconductor, a pharmaceutical composition, and a gas generating agent.

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. Non-Patent Document 1 proposes tetrazolopyridine compounds having various substituents.

JP-T-2001-526282

However, the effect of using the above compound as an organic semiconductor material has not been known. In addition, the above compounds may not have sufficient thermal stability.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that among tetrazolopyridine compounds, those having two or more specific functional groups have a HOMO level while keeping the LUMO level low. It has been found that it is useful as an organic semiconductor material. And, the tetrazolopyridine compound having two or more specific functional groups is found to be excellent in thermal stability and useful as a gas generating agent, and also useful as a raw material for various compounds, The present invention has been completed.

That is, the compound of the present invention is represented by the formula (1).

In Expression (1), R ¹ represents a hydrogen atom, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group. A ¹ represents an optionally substituted aromatic ring or a halogen atom. m represents an integer of 0 to 2, and n represents an integer of 2 to 4. However, m + n is 4. ]

The compound of the present invention is also represented by the formula (1-I).

[In formula (1-I), A ¹ represents an optionally substituted aromatic ring or a halogen atom. ]

In the above compound, it is preferable that two or more A ¹ are an aromatic ring substituted with a halogen atom or a halogen atom. In the above compound, two or more A ¹ are preferably halogen atoms, and two or more A ¹ are also preferably aromatic rings substituted with a halogen atom.

A ¹ is more preferably any aromatic ring selected from the following formulas (Ar1) to (Ar8).

[In the formulas (Ar1) to (Ar8), R ² represents a halogen atom, an alkyl group, an alkoxy group, or a halogenated alkyl group. R ³ represents a hydrogen atom or an alkyl group. p1 represents an integer of 0 to 3, p2 represents an integer of 0 to 2, p3 represents an integer of 0 to 5, and p4 represents an integer of 0 to 4. ]

The present invention also includes a method for producing a compound represented by the formula (1), in which a compound represented by the following formula (2) is reacted with an azide compound in the presence of a base.

[In formula (2), R ¹ represents a hydrogen atom, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group. A ¹ represents an optionally substituted aromatic ring or a halogen atom. m represents an integer of 0 to 2, and n represents an integer of 2 to 4. However, m + n is 4. ]

The present invention also includes a process for producing a compound represented by the formula (1-I), in which a compound represented by the following formula (2-I) is reacted with an azide compound in the presence of a base.

[In the formula (2-I), A ¹ represents an optionally substituted aromatic ring or a halogen atom. ]

Furthermore, the present invention includes a compound represented by the following formula.

[In Formula (II), R ¹ represents a hydrogen atom, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group. A ²⁰ represents an optionally substituted aromatic ring. m represents an integer of 0 to 2, n7 represents an integer of 1 or more, and r represents an integer of 1 or more. However, either n7 or r is 2 or more. ]

Furthermore, an organic semiconductor material containing the above compound and an organic electronic device containing this organic semiconductor material are also included in the scope of the present invention.

Since the compound of the present invention is a tetrazolopyridine compound having two or more specific functional groups, the HOMO level can be raised while keeping the LUMO level low, and it is useful as an organic semiconductor material, and has thermal stability. And is also useful as a raw material for various compounds.

FIG. 1 shows the results of differential scanning calorimetry of the compounds (Tz-6), (Tz-8) and (Tz-9). FIG. 2 shows the results of differential scanning calorimetry of compound (Tz-11). FIG. 3 shows the results of differential scanning calorimetry of the compounds (Tz-1) and (Tz-7). FIG. 4 shows the results of differential scanning calorimetry of the compounds (Tz-14) and (Tz-15). FIG. 5 shows the results of differential scanning calorimetry of the compounds (Tz-3) and (Tz-4). FIG. 6 shows the results of differential scanning calorimetry of the compounds (Tz-2) and (Tz-16). FIG. 7 represents an ultraviolet-visible absorption spectrum of the compound (Tz-3). FIG. 8 shows an ultraviolet-visible absorption spectrum of the compound (Tz-6). FIG. 9 represents an ultraviolet-visible absorption spectrum of the compound (Tz-9). FIG. 10 represents an ultraviolet-visible absorption spectrum of the compound (Tz-8). FIG. 11 represents an ultraviolet-visible absorption spectrum of the compound (Tz-1). FIG. 12 represents an ultraviolet-visible absorption spectrum of the compound (Tz-14). FIG. 13 shows an ultraviolet-visible absorption spectrum of the compound (Tz-15). FIG. 14 shows the results of cyclic voltammetry measurement of the compound (Tz-3). FIG. 15 shows the results of cyclic voltammetry measurement of the compounds (Tz-6), (Tz-8) and (Tz-9). The solid line represents the compound (Tz-8), the broken line represents the compound (Tz-6), and the dotted line represents the compound (Tz-9). FIG. 16 shows the results of cyclic voltammetry measurement of the compounds (Tz-1), (Tz-14) and (Tz-15). The solid line represents the compound (Tz-1), the broken line represents the compound (Tz-14), and the dotted line represents the compound (Tz-15).

The present invention will be described below. Hereinafter, the “compound represented by the formula (x)” may be simply referred to as “compound (x)”.
1. Compound The compound of the present invention is represented by the following formula (1).

[In Formula (1),
R ¹ represents a hydrogen atom, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group.
A ¹ represents an optionally substituted aromatic ring or a halogen atom.
m represents an integer of 0 to 2, and n represents an integer of 2 to 4. However, m + n is 4. ]

In the formula (1), m is more preferably 1 to 2, particularly preferably 2, and n is more preferably 2. R ¹ and A ¹ may be bonded to any of the 2 to 5 positions, for example, the following arrangements.

[In the formulas (1-1) to (1-11), R ¹ and A ¹ are as defined above. ]

Of these, the formulas (1-1) to (1-6) are preferable, the formulas (1-1), (1-2), and (1-4) are more preferable, and the formula (1-1) is particularly preferable. It is.

In the formula (1), all of A ¹ may be a halogen atom (the following formula (1A)), or all of A ¹ may be an optionally substituted aromatic ring (the following formula (1B)), any ^one of A ¹ may be a halogen atom, and any of them may be an optionally substituted aromatic ring (the following formula (1C)).

[In the formulas (1A) to (1B)
R ¹ and m are as defined above.
A ² represents an optionally substituted aromatic ring.
X ¹ represents a halogen atom.
n1 represents an integer of 2 to 4, n2 represents an integer of 1 to 3, and n3 represents an integer of 1 to 3. However, m + n1 and m + n2 + n3 are 4 or less. ]

In the formula, the halogen atom of X ^{1 is the same as} the halogen atom of A ¹ , and the optionally substituted aromatic ring of A ^{2 is} the same as the optionally substituted aromatic ring of A ^1. .
n1 is preferably 2 to 3, and particularly preferably 2. n2 and n3 are each preferably 1 to 2, and particularly preferably 1.

Furthermore, in the compound (1), two or more A ¹ are preferably an aromatic ring substituted with a halogen atom or a halogen atom. When A ¹ is an aromatic ring substituted with a halogen atom or a halogen atom, it can be bonded to various substituents starting from the halogen atom, and it is easy to synthesize various compounds. Become.
It is also preferable that two or more A ¹ are all halogen atoms, or that two or more A ¹ are both aromatic rings substituted with a halogen atom. When two or more A ¹ is an aromatic ring substituted with a halogen atom, it is particularly useful as an organic semiconductor material described later.

In the formula (1), the aliphatic hydrocarbon group or alicyclic hydrocarbon group represented by R ¹ preferably has 1 to 30 carbon atoms.
Further, the aliphatic hydrocarbon group for R ¹ may be either linear or branched. The aliphatic hydrocarbon group for R ¹ may be an alkyl group, or an unsaturated aliphatic hydrocarbon group such as an alkenyl group or an alkynyl group, and is preferably an alkyl group. The carbon number of the aliphatic hydrocarbon group for R ¹ is preferably 1 to 24, and more preferably 1 to 20 carbon atoms.
Specific examples of the aliphatic hydrocarbon group for R ¹ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. 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-trimethyl Hexyl, n-decyl, 1-n-pentylpentyl, 1-n-butylhexyl, 2-n-butylhexyl, 1-n-propylheptyl, 1-ethyloctyl, 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, 2-n- Butyloctyl 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 -Nonylnonyl group, n-nonadecyl group, n-eicosyl group, 2-octyldodecyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group n- tetracosyl group, 2-decyl tetradecyl group and the like.

The alicyclic hydrocarbon group for R ¹ may be monocyclic or polycyclic. The alicyclic hydrocarbon group for R ¹ may be any of a cycloalkyl group, or an unsaturated alicyclic hydrocarbon group such as a cycloalkenyl group or a cycloalkynyl group, and is a cycloalkyl group. preferable. The carbon number of the alicyclic hydrocarbon group of R ¹ is preferably 3 to 20, more preferably 3 to 14.
Specific examples of the alicyclic hydrocarbon group for R ¹ include monocyclic cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group; And polycyclic cycloalkyl groups such as a bicyclohexyl group, a bicycloheptyl group, and a bicyclooctyl group.

Among them, R ¹ is preferably a hydrogen atom or an aliphatic hydrocarbon group, and more preferably a hydrogen atom.

Examples of the halogen atom for A ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a bromine atom and an iodine atom, and more preferably a bromine atom.

Examples of the aromatic ring for A ¹ include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
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, and among them, a thiophene ring, a thiazole ring, a pyridine ring, a pyrrole ring, an imidazole ring, a furan ring, and an oxazole ring are preferable.

The aromatic ring of A ¹ is preferably substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an 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 halogen atom substitutions is preferably 1 to 2, particularly preferably 1.
The aromatic ring of A ¹ may have a substituent other than a halogen atom. Examples of substituents other than halogen atoms include alkyl groups, alkoxy groups, and halogenated alkyl groups. Examples of the alkyl group include the same groups as the alkyl groups exemplified as the aliphatic hydrocarbon group for R ¹ , and preferably have 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms. Examples of the alkoxy group include groups in which —O— is bonded to the alkyl group, and preferably has 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms. Furthermore, examples of the halogenated alkyl group include groups in which a hydrogen atom of the alkyl group is substituted with a halogen atom (particularly preferably a fluorine atom) such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, It has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 4 carbon atoms, and specifically includes a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group. And a trifluoromethyl group is particularly preferable.

Of the aromatic rings of 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 heterocyclic ring is tetrazolo at the 2-position. It is preferably bonded to the pyridine ring of pyridine.

Specifically, the aromatic ring represented by A ¹ is preferably an aromatic ring represented by the following formula.

Examples of the halogen atom for R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom and an iodine atom are preferable.
Alkyl group R ^2, an alkoxy group, halogenated alkyl group, the alkyl group of R ^3, is the same as the substituent which may be an aromatic ring of the A ¹ optionally has, alkoxy group, halogenated alkyl group Is preferred.

In the above formulas (Ar1) to (Ar8), at least one R ² is preferably a halogen atom. The substitution position of the halogen atom is preferably the 5-position in the formulas (Ar1) to (Ar2) and (Ar5) to (Ar8), the 4-position in the formula (Ar3), and the 6-position in the formula (Ar4). It is preferable.
p1, p2, p3, and p4 are each preferably 0 to 2.

Of the formulas (Ar1) to (Ar8), the formulas (Ar1) to (Ar4) are preferable, and the formulas (Ar1) to (Ar4) are respectively the following formulas (Ar1-1) to (Ar4-1) Is more preferable.
In (Ar1-1) to (Ar1-2) and (Ar4-1), X ² is preferably bonded to the 2-position, and in (Ar3-1), X ² is bonded to the 4-position. It is preferable.

[In the formulas (Ar1-1) to (Ar4-2),
R ⁴ represents an alkyl group, an alkoxy group, or a halogenated alkyl group.
X ² represents a halogen atom.
p5 represents an integer of 0 to 2, p6 represents an integer of 0 to 1, p7 represents an integer of 0 to 4, and p8 represents an integer of 0 to 3. p9 represents an integer of 0 to 3, p10 represents an integer of 0 to 2, p11 represents an integer of 0 to 5, and p12 represents an integer of 0 to 4.
* Represents a bond. ]

The halogen atom for X ^{2 is the same as} the halogen atom for R ² described above, preferably a bromine atom or an iodine atom, and more preferably a bromine atom.
R ⁴ is the same as the alkyl group, alkoxy group, and halogenated alkyl group of R ² above, and is preferably an alkoxy group or a halogenated alkyl group.
p5, p6, p7, p8, p9, p10, p11, and p12 are preferably 0 to 1.

Examples of the compound represented by the formula (1) include a compound represented by the following formula (1-I).

In the table, each formula number means a group represented by the following formula. In the following formula, R ⁴ has the same meaning as above, and * represents a bond.

Among these, compounds (1-I-1) to (1-I-107) are more preferable, compounds (1-I-1) to (1-I-16) are more preferable, and compound (1-I-1) More preferable is (1-I-10).

2. Production Method The outline of the production method of the present invention is represented by the following scheme.

[Where:
R ¹ , A ¹ , A ² , X ¹ , m, n, n1, n2, and n3 are as defined above.
A ³ represents an aromatic ring not substituted with a halogen atom.
A ^x1 represents an aromatic ring substituted with a halogen atom.
M ¹ represents a boron atom or a tin atom.
L ¹ represents an aliphatic hydrocarbon group, a hydroxyl group, an alkoxy group, or an aryloxy group, and a plurality of L ¹ may form a ring together with M ¹ .
n4 represents an integer of 1 to 3, and n5 represents an integer of 1 to 3.
k1 represents an integer of 2 or 3. ]

That is, the compound (1) of the present invention oxidizes the compound (3) (oxidation step: step 1) and adds an aromatic ring as necessary (aromatic ring addition step 1: steps 3, 5). 7), compound (2) is obtained, and this compound (2) can be produced by reacting an azide compound in the presence of a base (cyclization step 1:

steps

2, 4, 6, 8). 11).

When the compound (1) is a compound represented by the formula (1E) containing an aromatic ring in which A ¹ is substituted with a halogen atom, the compound (1E) is represented by the following formula (2E). May be prepared by reacting the compound to be reacted with an azide compound in the presence of a base (cyclization step 1: step 11),

[In the formula (1E), R ¹ , A ^x1 , X ¹ , m, n4, and n5 have the same meanings as described above. ]

Alternatively, the compound (2D) having an aromatic ring not substituted with a halogen atom is reacted with an azide compound in the presence of a base (cyclization step 1: step 8), and the aromatic not substituted with a halogen atom After making the compound (1D) having a ring, the aromatic ring may be substituted with a halogen atom (halogenation step: step 9).

[In the formula (2D), R ¹ , A ³ , X ¹ , m, n4 and n5 have the same meanings as described above. ]

Hereinafter, each process will be described.

2-1. Oxidation process (process 1)
The compound (2) can be obtained by reacting the compound (3) with an oxidizing agent. As the compound (3), for example, a compound represented by the following formula (3-I) is preferable.

As the oxidizing agent, a percarboxylic acid such as metachloroperbenzoic acid can be 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 (3A).
As the reaction solvent in the oxidation step, halogen solvents such as dichloromethane, chloroform, dichloroethane, dichloropropane and the like are preferable.

2-2. Aromatic ring addition step 1 (

steps

3, 5, and 7)
In the aromatic ring addition step 1, the compound (2) and the following formula (4)

[In formula (4), A ² , M ¹ , L ¹ and k ^{1 have} the same meanings as described above. ]

The compound (2) which has an aromatic ring can be manufactured by making it react with the compound (henceforth "compound (4)") represented by these. As the compound (2) used in this step, for example, a compound represented by the following formula (2-I) is preferable, and a compound (2A) is preferable. In the table, each formula number has the same meaning as described above.

When a compound (2) in which a plurality of A ¹ are the same halogen atom is used, a compound (2B) having no halogen atom and having an aromatic ring can be produced, and the plurality of A ¹ are different halogen atoms. When the compound (2) is used, a compound (2C) having a halogen atom and an aromatic ring can be produced. Even when a plurality of compounds (2) in which A ¹ is the same halogen atom are used, compound (4) is less than 1.2 mol, preferably 1.1 mol or less, relative to 1 mol of compound (2). Thus, the compound (2C) can be produced.
Furthermore, when the compound (2) in which A ¹¹ is an aromatic ring is used, a compound (2B) having different types of aromatic rings bonded to the 2-position and 5-position can be obtained.

In the above formula (4), the number of carbon atoms of L ¹ is an aliphatic hydrocarbon group, the alkoxy group, respectively, an aliphatic hydrocarbon group R ^1, the same groups exemplified as the alkoxy group R ² Can be mentioned. The number of carbon atoms of the aliphatic hydrocarbon group represented by L ¹ is preferably 1 to 6, and more preferably 1 to 4. Further, the number of carbon atoms of the alkoxy group of L ¹ is preferably 1 to 6, and more preferably 1 to 2. The number of carbon atoms of the aryloxy group of L ¹ is preferably 6 to 10, more preferably 6 to 10, and specific examples include a phenyloxy group, a benzyloxy group, and a phenylenebis (methyleneoxy) group. .
k1 is 2 or 3, depending on the type of M ^1, a 2 when M ¹ is a boron atom, a 3 when M ¹ is a tin atom.

When M ¹ is a boron atom, examples of * -M ¹ (L ¹ ) _k1 include groups represented by the following formulae. In the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (preferably a hydrogen atom). * Represents a bond.

When M ¹ is a tin atom, examples of * -M ¹ (L ¹ ) _k1 include groups represented by the following formulae. In the formula, * represents a bond.

Of these, groups represented by the above formulas (Om-1), (Om-2), (Om-5), and (Om-6) are preferable.
Examples of the compound (4) include compounds represented by the following formula (4-I). In the table, each formula number has the same meaning as described above.

Of these, compounds (4-I-1) to (4-I-28) and (4-I-57) to (4-I-84) are preferable.

The amount of the compound (4) is preferably 1.2 to 10 mol, more preferably 2 to 7 mol, relative to 1 mol of the compound (2).

When reacting compound (2) and compound (4), a catalyst may coexist. 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 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, palladium hydroxide ( II), palladium selenide (II), 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 (dibenzylideneacetone) palladium ( 0), tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct, dichloro [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene ] (3-chloropyridyl) paradi (II), bis (tri-tert-butylphosphine) palladium (0), dichloro [2,5-norbornadiene] palladium (II), dichlorobis (ethylenediamine) palladium (II), dichloro (1,5-cyclooctadiene ) Palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II). These catalysts may be used individually by 1 type, and may mix and use 2 or more types. Of these, tetrakis (triphenylphosphine) palladium (0) or dichlorobis (triphenylphosphine) palladium (II) is preferable.

The molar ratio of the compound (2) to the catalyst (compound (2): catalyst) is generally about 1: 0.0001 to 1: 0.5, and is 1: 0.001 from the viewpoint of yield and reaction efficiency. ˜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.

A specific ligand may be coordinated with the catalyst. The ligands include trimethylphosphine, triethylphosphine, tri (n-butyl) phosphine, tri (isopropyl) phosphine, tri (tert-butyl) phosphine, tri-tert-butylphosphonium tetrafluoroborate, bis (tert-butyl) ) Methylphosphine, tricyclohexylphosphine, diphenyl (methyl) phosphine, triphenisphosphine, 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-dicyclohexylphosphine No-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 (diphenylphosphine) Dino) 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-diphenyldihydroimidazolylidene 1,3-dimethyldihydroimidazolidene, diethyldihydroimidazolylidene, 1,3-bis (2,4,6-trimethylphenyl) dihydroimidazolidene, 1,3-bis (2,6-diisopropylphenyl) Dihydroimidazolidene, 1,10-phenanthroline, 5,6-dimethyl- Examples include 1,10-phenanthroline and butophenanthroline. Only 1 type may be used for a ligand and 2 or more types may be used for it.

When the ligand is coordinated, the molar ratio of the catalyst to the ligand (catalyst: ligand) is generally about 1: 0.5 to 1:10, and 1 from the viewpoint of yield and reaction efficiency. Is preferably 1: 1 to 1: 8, more preferably 1: 1 to 1: 7, and still more preferably 1: 1 to 1: 5.

When reacting compound (2) and compound (4), a base may be allowed to coexist. In particular, when M ¹ is a boron atom, a base is preferably allowed to coexist, and when M ¹ is a tin atom, the base may not be allowed to coexist.

Examples of the base include lithium metal hydride, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate and other alkali metal salt compounds; magnesium hydroxide, calcium hydroxide, barium hydroxide, Alkaline earth metal salt compounds such as magnesium carbonate, calcium carbonate, 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, potassium tert-butoxide, lithium tert-amyl alkoxide, sodium tert-amyl alkoxide Alkoxymethyl alkali metal compounds such as potassium tert- amyl alkoxide; lithium hydride, sodium hydride, metal hydride compounds such as potassium hydride. Among them, as the base, an alkoxyalkali metal compound is preferable, and lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, and cesium carbonate are more preferable.

The molar ratio of compound (2) to base (compound (2): base) is generally about 1: 1 to 1:10, and from the viewpoint of yield and reaction efficiency, 1: 1.5 to 1: 8 Preferably, 1: 1.8 to 1: 6 is more preferable, and 1: 2 to 1: 5 is more preferable.

As the reaction solvent, a solvent that does not affect the reaction can be used, and ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents, amide solvents, and the like are used. be able to. Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane. Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate. Examples of the hydrocarbon solvent include pentane, hexane, and heptane. Examples of the halogen solvent include dichloromethane, chloroform, dichloroethane, and dichloropropane. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl3,4,5,6-tetrahydro- (1H ) -Pyrimidine. 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, dioxane, and N, N-dimethylformamide are particularly preferable.

The amount of the reaction solvent is generally about 1 mL or more and 100 mL or less with respect to 1 g of the compound (2), preferably 5 mL or more and 80 mL or less, more preferably 8 mL or more and 70 mL or less from the viewpoint of yield or reaction efficiency. 10 mL or more and 60 mL or less are more preferable.

The reaction temperature is preferably 0 ° C. or higher and 200 ° C. or lower from the viewpoint of increasing the reaction yield. When obtaining the said compound (2B) especially, it is more preferable that they are 30 degreeC or more and 180 degrees C or less, and it is further more preferable that they are 40 degreeC or more and 150 degrees C or less. Moreover, when obtaining a compound (2C), it is preferable that it is 0 to 200 degreeC, and it is more preferable that it is 30 to 180 degreeC.
Microwave may be used for the reaction.

2-3. Cyclization step 1 (

steps

2, 4, 6, 8, 11)
Compound (1) can be obtained by reacting compound (2) with an azide compound in the presence of a base.
In the compound (2) used in this step, R ¹ and R ² are each preferably bonded to any of the 2 to 5 positions, and examples thereof include the following arrangements.

[In the formulas (2-1) to (2-11), R ¹ and A ¹ are as defined above. ]

Among them, the formulas (2-1) to (2-6) are preferable, the formulas (2-1), (2-2), and (2-4) are more preferable, and the formula (2-1) is particularly preferable. It is.

In the formula (2), all of A ¹ may be a halogen atom (the following formula (2A)), or all of A ¹ may be an optionally substituted aromatic ring (the following formula (2B)), any ^one of A ¹ may be a halogen atom, and any of them may be an optionally substituted aromatic ring (the following formula (2C)).

[In the formulas (2A) to (2C), R ¹ , A ² , X ¹ , m, n1, n2, and n3 are as defined above. ]

Examples of the compound represented by the formula (2) include a compound represented by the following formula (2-I). In the table, R ³ has the same meaning as above, and * represents a bond. In the table, each formula number has the same meaning as described above.

The above compounds (2-I-1) to (2-I-2) correspond to the compound (2A), and the compounds (2-I-3) to (2-I-107) correspond to the compound (2B). Compounds (2-I-108) to (2-I-121) correspond to the compound (2C). Further, at least one of A ¹⁰ and A ¹¹ has the formula (Ar1-1-1), (Ar1-1-2), (Ar2-1-1), (Ar2-1-2), (Ar3-1) -1), (Ar3-1-2), (Ar4-1-1), (Ar4-1-2) and the like, which is an aromatic ring substituted with a halogen atom, corresponds to compound (2D), All of A ¹⁰ and A ¹¹ are represented by the formulas (Ar1-2-1), (Ar2-2-1), (Ar3-2-1), (Ar3-2-2), (Ar3-2-3), A compound that is an aromatic ring not substituted with a halogen atom, such as (Ar4-2-1), corresponds to compound (2E). Of these, compounds (2-I-1) to (2-I-107) are preferable, and compounds (2-I-1) to (2-I-10) are more preferable.

Examples of the azide compounds include diarylphosphoryl azides such as diphenylphosphoryl azide (DPPA) and bis (4-nitrophenyl) phosphoryl azide; trialkylsilyl azides such as trimethylsilyl azide (TMSA); organic azide compounds such as sodium azide and the like Inorganic azide compounds are preferred. The organic azide compound may be polymer-supported. Among these, trialkylsilyl azide compounds such as trimethylsilyl azide are preferable.

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

When a trialkylsilyl azide compound is used as the azide compound, it is preferable that a sulfonyl halide compound or a phosphoric acid halide compound coexist.
Examples of the sulfonyl halide compound include methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, isopropanesulfonyl chloride, butanesulfonyl chloride, pentanesulfonyl chloride, hexanesulfonyl chloride; alkylsulfonyl chloride compounds such as benzenesulfonyl chloride, 2-methyl Benzenesulfonyl 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, 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; It is done. Of these, sulfonyl chloride compounds are preferable, arylsulfonyl chloride compounds are more preferable, and 4-methylbenzenesulfonyl 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 or more and 15 mol or less, further preferably 1 mol, per 1 mol of the compound (2). The amount is 13 mol or less, particularly preferably 1 mol or more and 10 mol or less. When the amount of the sulfonyl halide compound is within this range, the yield and reaction efficiency are good.

Examples of the phosphoric acid halide compound include dialkyl phosphoryl chloride compounds such as dimethyl phosphoryl chloride, diethyl phosphoryl chloride, dipropyl phosphoryl chloride, diisopropyl phosphoryl chloride, dibutyl phosphoryl chloride; bis (2,2,2-trichloroethyl) phosphoryl chloride and the like. Dihalogenated alkylphosphoryl chloride compounds; 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) Yl) 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. Of these, 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 phosphate halide compound is preferably 0.5 mol or more and 20 mol or less, more preferably 1 mol or more and 15 mol or less, and further preferably 1 with respect to 1 mol of the compound (2). It is at least 1 mol and at most 13 mol, particularly preferably at least 1 mol and not more than 10 mol. When the amount of the phosphate halide compound is in this range, the yield and reaction efficiency are good.

Bases that coexist when the azide compound is reacted include pyridine; imidazole compounds such as N-methylimidazole and imidazole; lithium hydroxide, sodium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, etc. Alkali metal salt compounds; alkaline earth metal salt compounds such as magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, 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, potassium ter Alkoxy alkali metal compounds such as butoxide, lithium tert-amyl alkoxide, sodium tert-amyl alkoxide, potassium tert-amyl alkoxide; metal hydride compounds such as lithium hydride, sodium hydride, potassium hydride; trimethylamine, triethylamine, tri Propylamine, diisopropylethylamine, tributylamine, tripentylamine, trihexylamine, trioctylamine, triallylamine, 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-diazabicyclo [5 4.0] tertiary amine such as undec-7-ene; and the like. Of these, pyridine, imidazole compounds, alkali metal salt compounds and amines 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 and 8 mol or less, further preferably 1 mol or more, 7 mol per 1 mol of the compound (2). The amount is not more than mol, particularly preferably not less than 1 mol and not more than 5 mol.

In the above reaction, it is preferable not to use a reaction solvent. When using a reaction solvent, it can be used as long as it does not affect the reaction. For example, an ether solvent, an aromatic solvent, a hydrocarbon solvent, a halogen solvent, a ketone solvent, an amide solvent or the like can be used. it can. Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrophthalane, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane. Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate. Examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, and heptane. Examples of the halogen solvent include dichloromethane, chloroform, dichloroethane, and dichloropropane. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl3,4,5,6-tetrahydro- (1H ) -Pyrimidine. A nitrile solvent such as acetonitrile, a sulfoxide solvent such as dimethyl sulfoxide, and a sulfone solvent such as sulfolane can be used.

From the viewpoint of increasing the reaction yield, 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 further preferably 40 ° C. or higher and 150 ° C. or lower. preferable. The reaction temperature may be adjusted using a microwave.

2-4. Halogenation process (process 9, 10)
Halogenation can be carried out by various methods, for example, by bringing compound (1D) into contact with a halogenating reagent in the presence of an acid. The acid is preferably an organic acid such as acetic acid, and the halogenating reagent is preferably N-bromosuccinimide, N-chlorosuccinimide, pyridine bromine complex salt, bromine, chlorine or the like.
Reaction solvents include dichloromethane, chloroform, dichloroethane, dichloropropane and other halogen solvents, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and other ester solvents, pentane, hexane, cyclohexane, heptane and other hydrocarbons. Preference is given to aromatic solvents such as benzene solvents, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene.

3. Tetrazolopyridine multimer A tetrazolopyridine multimer containing a structural unit derived from the compound (1) of the present invention (hereinafter sometimes simply referred to as “structural unit (I)”) is also encompassed in the scope of the present invention. .

[In the formula (I), R ¹ and m are as defined above. A ²⁰ represents a group having one hydrogen atom of the optionally substituted aromatic ring of A ² as a bond.
n7 represents an integer of 1 or more. ]

Specific examples of the compound containing the structural unit (I) include compounds represented by the following formula (II).

[In the formula (II), R ¹ , A ²⁰ and m are as defined above.
n7 represents an integer of 1 or more.
r represents an integer of 1 or more.
However, either n7 or r is 2 or more. ]

In the above formula, n7 is preferably 1 or 2.
r is preferably 1 or 2.

As the compound (II), for example, a compound represented by the following formula is preferable.

[In formulas (IIA) and (IIB), R ¹ , A ²⁰ , m and n8 have the same meanings as described above.
n9 represents an integer of 2 or more, and r1 represents an integer of 2 or more. ]

Compounds (IIA) and (IIB) are preferably compounds represented by the following formulas (IIA-I) and (IIB-I).

In the table, (ArI-1) means a group represented by the following formula. * Represents a bond.

The outline of the production method of the compound (IIA) is represented by the following scheme.

[Where:
R ¹ , A ²⁰ , m, n9, and r1 are as defined above.
X ¹⁰ represents a halogen atom.
M ¹⁰ represents a boron atom or a tin atom.
L ¹⁰ represents an aliphatic hydrocarbon group, a hydroxyl group, an alkoxy group, or an aryloxy group, and a plurality of L ¹ may form a ring together with M ¹ .
n10 represents an integer of 1 or more.
k10 represents an integer of 2 or 3. ]

That is, compound (IIA) adds an aromatic ring to compound (IIA3) (aromatic ring addition step 2: step 12) to obtain compound (IIA2), and this compound (IIA2) is added to compound (IIA2) in the presence of a base. It can be produced by reacting an azide compound (cyclization step 2: step 13). Compound (IIA) can be produced by adding an aromatic ring to compound (IIA5) (aromatic ring addition step 2: step 14).

Furthermore, the outline of the production method of the compound (IIB) is represented by the following scheme.

[Where:
R ¹ , A ²⁰ , m, n8, and n9 are as defined above.
X ¹¹ and X ¹² represent a halogen atom.
M ¹¹ and M ¹² represent a boron atom or a tin atom.
L ¹¹ and L ¹² represent an aliphatic hydrocarbon group, a hydroxyl group, an alkoxy group, or an aryloxy group, and a plurality of L ¹¹ or L ¹² may form a ring together with M ¹¹ or M ¹² .
k11 and k12 represent an integer of 2 or 3. ]

That is, compound (IIB) can be produced by the following three routes.
In route 1, compound (IIB3), compound (IIB4), and compound (IIB5) are reacted (aromatic ring addition step 3: step 15) to obtain compound (IIB2). It can be produced by reacting an azide compound in the presence (cyclization step 2: step 16).
In route 2, compound (IIC) is reacted with a base and a halogenated organometallic compound to give compound (IID) (organometallic compound addition step: step 17), and then this compound (IID) and compound (IIE) ) In the presence of a metal catalyst (multimerization step 1: step 18).
Route 3 can be produced by reacting compound (IIC) and compound (IIF) in the presence of a base and a metal catalyst (multimerization step 2: step 19).
Hereinafter, each step will be described.

3-1. Aromatic ring addition step 2 (steps 12 and 14)
In the aromatic ring addition step 2, compound (IIA3) and compound (IIA4)

[Wherein, R ¹ , A ²⁰ , M ¹⁰ , L ¹⁰ , k10 are as defined above. ]
Can be reacted to produce compound (IIA2). Examples of compound (IIA3) used in this step include compound (2E) having an aromatic ring substituted with a halogen atom among compounds (2) exemplified above.
Furthermore, compound (IIA) can be produced by reacting compound (IIA5) with compound (IIA4). As compound (IIA5) used at this process, the compound which has the aromatic ring substituted by the halogen atom among the compound (1) illustrated above is mentioned.
M ¹⁰ , L ¹⁰ , and k10 in the formula (IIA4) are the same as M ¹ , L ¹ , and k1 in the formula (4). Examples thereof include those in which the group ring is not substituted with a halogen atom.

Furthermore, when reacting compound (IIA3) or compound (IIA5) and (IIA4), the same catalyst as that exemplified in the aromatic ring addition step 1 can be used under the same conditions. A specific ligand similar to the ligand exemplified in the aromatic ring addition step 1 may be coordinated with the catalyst under the same conditions. Furthermore, when reacting compound (IIA3) or compound (IIA5) with compound (IIA2), a base similar to the base exemplified in the aromatic ring addition step 1 may coexist under the same conditions.
The reaction solvent used in the aromatic ring addition step 2 is the same as the reaction solvent used in the aromatic ring addition step 1 and can be used under the same conditions.
Furthermore, the reaction temperature in the aromatic ring addition step 2 is the same as that in the aromatic ring addition step 1.

3-2. Aromatic ring addition step 3 (step 15)
In the aromatic ring addition step 3, the compound (IIB3) and the compound (IIB4) are converted into the following formula (IIB5)

[Wherein, A ²⁰ , M ¹¹ , L ¹¹ , n8, and k11 have the same meanings as described above. ]
Compound (IIB2) can be produced by reacting with the compound represented by the formula: Compound (IIB3) or compound (IIB4) used in this step can be produced by this step using compound (2A) or (2C) as a starting material.

Compounds (IIB3) and (IIB4) are preferably compounds represented by the following formula. In the table, (ArI-1) has the same meaning as above.

In formula (IIB5), M ¹¹ , L ¹¹ and k11 are the same as M ¹ , L ¹ and k1 in formula (4), respectively. Examples of compound (IIB5) include compounds represented by the following formulas, etc. Is mentioned. In the table, (Om-1) to (Om-6) and (ArI-1) are as defined above.

The amount of compound (IIB5) is preferably 0.6 to 5 mol, more preferably 0.8 to 3 mol, relative to 1 mol of compound (IIB3).
The amount of compound (IIB4) is preferably 0.1 to 10 mol, more preferably 0.5 to 2 mol, relative to 1 mol of compound (IIB3).

The catalyst that coexists when the compounds (IIB3), (IIB4), and (IIB5) are reacted is the same as the catalyst exemplified in the aromatic ring addition step 1, and the molar ratio of the compound (IIB5) to the catalyst (compound ( IIB5): catalyst) is generally about 1: 0.0001 to 1: 1.0, preferably 1: 0.001 to 1: 0.8, and preferably 1: 0.005 from the viewpoint of yield and reaction efficiency. ˜1: 0.6 is more preferred, and 1: 0.01 to 1: 0.4 is even more preferred.

The ligand exemplified in the aromatic ring addition step 1 may be coordinated with the catalyst under the same conditions. In the aromatic ring addition step 3, the bases exemplified in the aromatic ring addition step 1 may coexist on the same conditions. In this step, the same solvent as in the aromatic ring addition step 1 can be used under the same conditions as the reaction solvent. Further, the reaction temperature can be adjusted in the same manner as in the aromatic ring addition step 1.

3-3. Cyclization step 2 (steps 13 and 15)
Compound (IIA) or (IIB) can be obtained by reacting compound (IIA2) or (IIB2) with an azide compound in the presence of a base.
The azide compound is the same as the azide compound exemplified in the cyclization step 1 and can be used under the same conditions. Furthermore, the base coexisting when the azide compound is reacted is the same as the base exemplified in the cyclization step 1, and can be used under the same conditions. Moreover, the same conditions as in the cyclization step 1 can be employed for the reaction solvent and the reaction temperature.

3-4. Organometallic compound addition step (step 16)
Compound (IID) can be obtained by reacting compound (IIC) with a base and a halogenated organometallic compound. In the formula (IID), M ¹² is preferably a tin atom.

As the compound (IIC), for example, a compound represented by the following formula is preferable. In the table, (ArI-1) has the same meaning as above.

Examples of the base include alkyl lithium, alkyl metal amide, alkyl magnesium, magnesium complex, alkali metal hydride and the like.

Examples of the alkyl lithium include n-butyl lithium, sec-butyl lithium, and tert-butyl lithium. Examples of the alkyl metal amide include lithium diisopropylamide, lithium diethylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, lithium-2,2,6,6-tetramethylpiperidide , Lithium amide, sodium amide, potassium amide. Examples of the alkylmagnesium and the magnesium complex include tert-butylmagnesium chloride, ethylmagnesium chloride, 2,2,6,6-tetramethylpiperidinylmagnesium chloride, and lithium chloride complex. Examples of the alkali metal hydride include lithium hydride, sodium hydride, and potassium hydride. Of these, alkyl metal amides are preferable from the viewpoint of regioselectivity, and n-butyllithium and lithium diisopropylamide are particularly preferable.

The molar ratio of compound (IIC) to base (compound (IIC): base) is generally about 1: 1 to 1: 5, and from the viewpoint of yield and reaction efficiency, 1: 1.1 to 1: 4 Preferably, 1: 1.5 to 1: 3 is more preferable, and 1: 1.8 to 1: 2.5 is more preferable.

Also, examples of the halogenated organometallic compound to be reacted with the compound (IIC) together with a base include a halogenated alkyltin compound, a halogenated cycloalkyltin compound, and a halogenated aryltin compound. Examples of the halogenated alkyltin compounds include triethyltin chloride, tripropyltin chloride, tributyltin chloride, trimethyltin bromide, triethyltin bromide, tripropyltin bromide, and tributyltin bromide. Examples of the halogenated cycloalkyl tin compound include tricyclohexyl tin chloride and tricyclohexyl tin bromide. Examples of the halogenated aryl tin compound include triphenyl tin chloride, tribenzyl tin chloride, triphenyl tin bromide, and tribenzyl tin bromide. Among these, a halogenated alkyltin compound is preferable, and trimethyltin chloride and tributyltin chloride are more preferable.

The molar ratio of compound (IIC) to halogenated organometallic compound (compound (IIC): halogenated organometallic compound) is generally about 1: 1 to 1: 5. From the viewpoint of yield and reaction efficiency, 1: 1.1 to 1: 4 is preferable, 1: 1.5 to 1: 3 is more preferable, and 1: 1.8 to 1: 2.5 is more preferable.
The molar ratio of the base to the halogenated organometallic compound (base: halogenated organometallic compound) is, for example, about 1: 0.5 to 1: 2.0, and 1: 0.6 to 1: 1.7. Preferably, 1: 0.7 to 1: 1.5 is more preferable, and 1: 0.8 to 1: 1.2 is more preferable.

The base and the halogenated organometallic compound may be reacted with the compound (IIC) at the same time, but from the viewpoint of the reaction yield, the base is first reacted with the compound (IIC) and then the tin halide compound is reacted. Is preferred. The reaction temperature is preferably room temperature or lower, more preferably 0 ° C. or lower, from the viewpoint of suppressing the formation of by-products.

As the reaction solvent, an ether solvent, a hydrocarbon solvent, or the like can be used. Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane. Examples of the hydrocarbon solvent include pentane, hexane, heptane, benzene, toluene, and xylene. Of these, tetrahydrofuran is preferred. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.

The amount of the solvent is generally about 1 mL or more and 70 mL or less with respect to 1 g of the compound (IIC). The following is more preferable.

3-5. Multimerization process 2 (process 17)
Compound (IIB) can be obtained by reacting compound (IID) with compound (IIE) in the presence of a metal catalyst.

In the above formula (IID), M ¹² , L ¹² and k12 are the same as M ¹ , L ¹ and k1, respectively, and M ¹² is preferably a tin atom. * -M ¹² (L ¹² ) _k12 is the same as * -M ¹ (L ¹ ) _k1, and the groups exemplified as the group when M ¹ is a tin atom are preferable.
Specifically, the compound (IID) is preferably a compound represented by the following formula. In the table, (Om-5) to (Om-6) and (ArI-1) are as defined above.

Further, as the compound (IIE), a compound represented by the following formula is preferable. In the table, (ArI-1) has the same meaning as above.

The amount of compound (IID) is preferably 0.6 to 5 mol, more preferably 0.8 to 4 mol, relative to 1 mol of compound (IIE).
Examples of the catalyst include the same catalysts as those exemplified in the aromatic ring addition step 1, and they can be used under the same conditions. Moreover, the same ligand as the ligand illustrated in the aromatic ring addition step 1 can be coordinated with the catalyst, and the catalyst can be used under the same conditions as in the aromatic ring addition step 1. The reaction solvent and the reaction temperature can be the same as in the aromatic ring addition step 1.

3-6. Multimerization process 2 (process 18)
In addition, compound (IIB) can be obtained by reacting compound (IIC) with compound (IIF) in the presence of a base and a metal catalyst.
As the compound (IIF), a compound represented by the following formula is preferable. In the table, (ArI-1) has the same meaning as above.

Compound (IIF) is preferably 0.1 to 10 mol, more preferably 0.5 to 2 mol, relative to 1 mol of compound (IIC).

As the base, the same bases as exemplified in the organometallic compound addition step can be used. The molar ratio of compound (IIC) to base (compound (IIC): base) is generally about 1: 1 to 1: 5, and from the viewpoint of yield and reaction efficiency, 1: 1.1 to 1: 4 Preferably, 1: 1.5 to 1: 3 is more preferable, and 1: 1.8 to 1: 2.5 is more preferable.

Further, examples of the metal catalyst include transition metal catalysts such as a palladium catalyst, a nickel catalyst, an iron catalyst, a copper catalyst, a rhodium catalyst, and a ruthenium catalyst. Among these, a copper catalyst is preferable.

Examples of the copper-based catalyst include copper, copper fluoride (I), copper chloride (I), copper bromide (I), copper iodide (I), copper fluoride (II), copper chloride (II), Copper halide compounds such as copper (II) bromide and copper (II) iodide; copper (I) oxide, copper (I) sulfide, copper oxide (II), copper sulfide (II), copper acetate (I), Examples include copper acetate (II) and copper (II) sulfate, and copper halide compounds are preferred. You may coordinate a ligand with these metal catalysts as needed.

In the first step, the molar ratio of the compound (IIC) to the metal catalyst (compound (IIC): metal catalyst) is generally about 1: 0.0001 to 1: 0.5, from the viewpoint of yield and reaction efficiency. To 1: 0.001 to 1: 0.4, more preferably 1: 0.005 to 1: 0.3, and even more preferably 1: 0.01 to 1: 0.2.

As the reaction solvent and reaction temperature, the same conditions as in the organometallic compound addition step can be employed.

4). Organic Semiconductor Material The compound (1) of the present invention can raise the HOMO level while keeping the LUMO level low, has excellent thermal stability, and can easily add various functional groups. Therefore, it is excellent as an organic semiconductor material, and an organic semiconductor material obtained using the compound (1) of the present invention is also included in the technical scope of the present invention.
In particular, the structural unit (I) derived from the compound (1)

[In the formula (I), R ¹ , A ²⁰ , m, and n7 are as defined above. ]
Since it is electron accepting and can be expected to function as an acceptor unit in an extended π-conjugated system, it may be combined with a donor unit to form a donor-acceptor semiconductor polymer compound, and the structural unit (I) It is more preferable to arrange the donor units alternately. In particular, it is useful for organic electro devices such as organic electroluminescence elements and organic thin film transistor elements, organic semiconductor materials, photoelectric conversion elements, 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-12).

[In the formulas (Dn-1) to (Dn-12), R ³⁰ represents an aliphatic hydrocarbon group, and R ³¹ represents a hydrogen atom or an aliphatic hydrocarbon group. ]

The aliphatic hydrocarbon group for R ^{30 is the same as} the aliphatic hydrocarbon group for R ¹ and preferably has 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms, still more preferably 1 carbon atom. ~ 20.

In order to alternately arrange the structural unit derived from the compound (1) and the donor unit, for example, the following formula (1E)

[In the formula (1E), R ¹ , A ^x1 , X ¹ , m, n4 and n5 have the same meanings as described above. ]

It is preferable to use the compound represented by this, It is preferable to make this compound (1E) and the compound represented by following formula (5) react.

[In Formula (5),
A ⁶ represents a divalent electron donating group M ² represents a boron atom or a tin atom.
L ² represents an aliphatic hydrocarbon group, a hydroxyl group, an alkoxy group, or an aryloxy group.
k2 represents an integer of 2 or 3. ]

A ⁶ is preferably a divalent electron-donating group containing an aromatic ring, and is preferably a divalent group represented by any one of the above formulas (Dn-1) to (Dn-12). More preferred.
M ² , L ² and k2 are the same as M ¹ , L ¹ and k1, respectively. * -M ² (L ² ) _k2 is the same as * -M ¹ (L ¹ ) _k1 .

The molar ratio of the compound (1) to the compound represented by the formula (5) is preferably in the range of 1:99 to 99: 1, and preferably in the range of 20:80 to 80:20. 40:60 to 60:40 is preferable.

As the catalyst for coupling, the same catalyst as that used in the aromatic ring addition step 1 can be used. Palladium catalyst, nickel catalyst, iron catalyst, copper catalyst, rhodium catalyst And metal catalysts such as ruthenium catalysts, among which palladium catalysts are preferred. The palladium of the palladium-based catalyst may be zero-valent or divalent.

As the palladium-based catalyst, any of the palladium-based catalysts exemplified in the above aromatic ring addition step 1 can be used, and these catalysts may be used alone or in combination of two or more. Among these, dichlorobis (triphenylphosphine) palladium (II), tris (dibenzylideneacetone) dipalladium (0), and tris (dibenzylideneacetone) dipalladium (0) chloroform adduct are particularly preferable.

In the coupling step, the molar ratio of the compound (1) to the catalyst (compound (1): catalyst) is generally about 1: 0.0001 to 1: 0.5, and 1 from the viewpoint of yield and reaction efficiency. : 0.001 to 1: 0.3 is preferable, 1: 0.005 to 1: 0.2 is more preferable, and 1: 0.01 to 1: 0.1 is more preferable.

In the coupling reaction, a specific ligand may be coordinated with the catalyst. As the ligand, any of the ligands exemplified in the aromatic ring addition step 1 can be used, and a catalyst coordinated with any of these ligands may be used in the reaction. A ligand may be used individually by 1 type and may be used in mixture of 2 or more types. Of these, triphenylphosphine, tris (o-tolyl) phosphine, and tris (2-methoxyphenyl) phosphine are preferable.

When the ligand is coordinated to the catalyst in the coupling step, the molar ratio of the catalyst to the ligand (catalyst: ligand) is generally about 1: 0.5 to 1:10, From the viewpoint of reaction efficiency, 1: 1 to 1: 8 is preferable, 1: 1 to 1: 7 is more preferable, and 1: 1 to 1: 5 is further preferable.

As the solvent used in the coupling step, a solvent that does not affect the reaction can be used. For example, ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents An amide solvent or the like can be used. Examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, tert-butyl methyl ether, and dioxane. Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and tetralin. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate. Examples of the hydrocarbon solvent include pentane, hexane, heptane, octane, and decalin. Examples of the halogen solvent include dichloromethane, chloroform, dichloroethane, and dichloropropane. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro- (1H ) -Pyrimidinone. In addition, nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethyl sulfoxide, and sulfone solvents such as sulfolane can be used. Among these, tetrahydrofuran, toluene, chlorobenzene, and N, N-dimethylformamide are preferable, and chlorobenzene is particularly preferable. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.

In the coupling step, the amount of the solvent used relative to the total 1 g of the compounds represented by the compound (1) and the compound (5) is generally about 1 mL or more and about 150 mL or less, and 5 mL or more from the viewpoint of yield or reaction efficiency. 100 mL or less is preferable, 8 mL or more and 90 mL or less are more preferable, and 10 mL or more and 80 mL or less are more preferable.

Since the organic semiconductor material of the present invention has high thermal stability and high electron acceptability, it is an organic electronic device, for example, an organic electro device such as an organic electroluminescence element and an organic thin film transistor element, an organic semiconductor material, and a photoelectric conversion. It is useful for devices, organic electronic devices, solar cells, solar cell module applications and the like. Useful for organic electronic devices.

This application claims the benefit of priority based on Japanese Patent Application No. 2015-047661 filed on Mar. 10, 2015. The entire contents of the specification of Japanese Patent Application No. 2015-047661 filed on Mar. 10, 2015 are incorporated herein by reference.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

Example 1: Synthesis of 2,5-bis (5-bromothiophenyl) tetrazolopyridine (Compounds (Tz-1), (Tz-2))
Step 1: Synthesis of 2,5-dibromopyridine-N-oxide

In a 300 mL eggplant flask, 2,5-dibromopyridine (11.8 g, 50 mmol), metachloroperbenzoic acid (mCPBA) (18.5 g, 75 mmol), and anhydrous dichloromethane (100 mL) were added and stirred at room temperature 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 using anhydrous sodium sulfate. After concentration, the residue was purified using silica gel column chromatography (Hexane / AcOEt = 5: 1) to obtain 6.74 g (yield 53%) of 2,5-dibromopyridine N-oxide (white solid).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.23 (dd, J = 2.1, 8.7 Hz, 1H), 7.52 (d, J = 8.7 Hz, 1H), 8.50 (d, J = 2.1 Hz, 1H).

Step 3: Synthesis of 2,5- (dithiophen-2-yl) pyridine-N-oxide

2,5-Dibromopyridine N-oxide (500 mg, 2 mmol), 2- (Tributylstannyl) thiophene (1.79 g, 4.8 mmol), Pd (PPh ₃ ) ₄ (165 mg, 0.14 mmol), and anhydrous Toluene (4 mL) was added and stirred at 180 ° C. for 20 minutes using a microwave reactor. After completion of the reaction, the solvent was concentrated and purified using silica gel column chromatography (CHCl ₃ / Hexane / AcOEt = 2: 1: 1) to purify 2,5- (dithiophen-2-yl) pyridine N-oxide (yellow solid). 450 mg (yield 88%) was obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.14 (dd, J = 4.0, 5.0 Hz, 1H), 7.22 (dd, J = 4.0, 5.0 Hz, 1H), 7.39 (dd, J = 1.0, 4.0 Hz, 1H), 7.41 (dd, J = 1.0, 5.0 Hz, 1H), 7.52 (dd, J = 1.9, 8.6 Hz, 1H), 7.58 (dd, J = 1.0, 5.0 Hz, 1H), 7.85 (dd, J = 1.0, 4.0 Hz, 1H), 7.92 (d, J = 8.6 Hz, 1H), 8.61 (d, J = 1.9 Hz, 1H).

Step 4: Synthesis of dithiophenyltetrazolopyridine (compound (Tz-1))

2,5- (dithiophen-2-yl) pyridine N-oxide (390 mg, 1.5 mmol), DPPA (1.6 mL, 7.5 mmol), and anhydrous pyridine (0.24 mL, 3.0 mmol) ) And stirred at 120 ° C. for 24 hours under a nitrogen atmosphere. The reaction solution was directly purified using silica gel column chromatography (CH ₂ Cl ₂ / MeOH = 20: 1) to obtain 198 mg (yield 46%) of dithiophenyltetrazolopyridine (yellow solid).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.25 (m, 1H), 7.29 (dd, J = 4.0, 5.0 Hz, 1H), 7.51 (dd, J = 1.0, 5.0 Hz, 1H), 7.55 (d, J = 7.7 Hz, 1H), 7.63 (dd, J = 1.0, 5.0 Hz, 1H), 7.89 (d, J = 7.7 Hz, 1H), 8.39 (dd, J = 1.0, 4.0 Hz, 1H), 8.41 ( dd, J = 1.0, 4.0 Hz, 1H).

Step 9: Synthesis of 2,5-bis (5-bromothiophenyl) tetrazolopyridine (Compound (Tz-2))

Dithiophenyltetrazolopyridine (30 mg, 0.1 mmol), N-bromosuccinimide (NBS) (36 mg, 0.2 mmol), anhydrous chloroform 2 mL), and acetic acid (0.4 mL) are placed in a screw test tube, and a nitrogen atmosphere The mixture was stirred at 60 ° C. for 24 hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was added for neutralization, and the organic layer was extracted with dichloromethane and dried using anhydrous sodium sulfate. After concentration, the residue was purified by silica gel column chromatography (CH ₂ Cl ₂ / MeOH = 20: 1) to obtain 37 mg (yield 84%) of the corresponding brominated product (yellow solid).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.19 (d, J = 4.0 Hz, 1H), 7.25 (m, 1H), 7.47 (d, J = 7.8 Hz, 1H), 7.78 (d, J = 7.8 Hz , 1H), 8.07 (d, J = 4.0 Hz, 1H), 8.13 (d, J = 4.0 Hz, 1H).

Example 2: Step 14: Synthesis of tetrazolopyridine pentamer (compound (Tz-3))

Brominated dithienyltetrazolopyridine (133 mg, 0.3 mmol), 2-Hexyl-5- (tributylstannyl) thiophene (411 mg, 0.9 mmol), Pd (PPh ₃ ) ₄ (35 mg, 0. 03 mmol) and anhydrous toluene (10 mL) were added, and the mixture was stirred at 120 ° C. for 60 minutes. After completion of the reaction, the solvent was concentrated and purified using silica gel column chromatography (CH ₂ Cl ₂ / MeOH = 20: 1) to obtain 53 mg (yield 27%) of tetrazolopyridine pentamer (red solid). .

¹ H NMR (400 MHz, CDCl ₃ ) δ 0.90 (t, J = 6.8 Hz, 6H), 1.28-1.45 (m, 12H), 1.65-1.75 (m, 4H), 2.77-2.86 (m, 4H), 6.72 (d, J = 3.6 Hz, 1H), 6.74 (d, J = 3.6 Hz, 1H), 7.10 (d, J = 3.6 Hz, 1H), 7.15 (d, J = 3.6 Hz, 1H), 7.19 ( d, J = 3.9 Hz, 1H), 7.21 (d, J = 3.9 Hz, 1H), 7.46 (d, J = 7.8 Hz, 1H), 7.77 (d, J = 7.8 Hz, 1H), 8.24 (d, J = 3.9 Hz, 1H), 8.29 (d, J = 3.9 Hz, 1H)

Example 3: Synthesis 1 of tetrazolopyridine hexamer (compound (Tz-4))
Step 5: Synthesis of 5-bromo-2- (5-hexylthiophen-2-yl) pyridine-N-oxide

2,5-Dibromopyridine N-oxide (3.0 g, 12 mmol), 2-Hexyl-5- (tributylstannyl) thiophene (5.48 g, 12 mmol), Pd (PPh ₃ ) ₄ (1.38 g, 1.2 mmol) and anhydrous toluene (48 mL) were added, and the mixture was heated and stirred at 120 ° C. for 16 hours. After completion of the reaction, the solvent was concentrated and purified using silica gel column chromatography (CH ₂ Cl ₂ / MeOH = 50: 1) to give 5-bromo-2- (5-hexylthiophen-2-yl) pyridine N-oxide (A ) (Yellow solid) was obtained (yield 64%).

¹ H NMR (400 MHz, CDCl3) δ 0.88 (t, J = 7.0 Hz, 3H), 1.27-1.40 (m, 6H), 1.58-1.68 (m, 2H), 2.86 (t, J = 7.6 Hz, 2H ), 6.90 (d, J = 4.1 Hz, 1H), 7.39 (dd, J = 1.8, 8.8 Hz, 1H), 7.67 (d, J = 4.1 Hz, 1H), 7.73 (dd, J = 8.8 Hz, 1H) ), 8.43 (d, J = 1.8 Hz, 1H).

Step 15: Synthesis of pyridine-N-oxide hexamer

5,5′-dibutylbutanyl-2,2′-bithiophene (58 mg, 0.078 mmol), 5-brom-2- (5-hexylthiophene-2-yl) pyridine N-oxide (A) (53 mg) 0.156 mmol), Pd (PPh ₃ ) ₄ (9 mg, 0.008 mmol), and anhydrous toluene (2 mL) were added, and the mixture was heated and stirred at 180 ° C. for 20 minutes using a microwave reactor. After completion of the reaction, the solvent was concentrated and purified using silica gel column chromatography (Hexane / AcOEt = 1: 1) to obtain 74 mg (yield 100%) of pyridine-N-oxide hexamer (orange solid).

¹ H NMR (400 MHz, CDCl ₃ ) δ 0.85-0.92 (m, 6H), 1.23-1.43 (m, 12H), 1.64-1.78 (m, 4H), 2.78-2.91 (m, 4H), 6.78 (d , J = 3.6 Hz, 1H), 6.89 (d, J = 4.0 Hz, 1H), 7.18 (d, J = 3.6 Hz, 1H), 7.43 (dd, J = 1.9, 8.7 Hz, 1H), 7.66 (d , J = 4.0 Hz, 1H), 7.81 (d, J = 8.7 Hz, 1H), 8.52 (d, J = 1.9 Hz, 1H).

Step 16: Synthesis of tetrazolopyridine hexamer (compound (Tz-4))

Pyridine-N-oxide hexamer (74 mg, 0.11 mmol), DPPA (600 mg, 2.2 mmol), and anhydrous pyridine (71 μL, 0.88 mmol) are placed in a screw-cap test tube, and 24 ° C. at 120 ° C. in a nitrogen atmosphere. Stir for hours. The reaction solution was directly purified by silica gel column chromatography (CH ₂ Cl ₂ / MeOH = 20: 1) and preparative GPC (CHCl ₃ ) to obtain 7 mg (yield) of tetrazolopyridine hexamer (red solid). 8%).

¹ H NMR (400 MHz, CDCl ₃ ) 0.90 (m, 6H), 1.30-1.37 (m, 8H), 1.38-1.45 (m, 4H), 1.72-1.79 (m, 4H), 2.91 (t, J = 7.6 Hz, 4H), 6.94 (d, J = 3.6 Hz, 1H), 7.05 (m, 1H), 7.43 (d, J = 7.9 Hz, 1H), 7.80 (d, J = 7.9 Hz, 1H), 8.22 (d, J = 4.0 Hz, 1H), 8.27 (d, J = 4.0 Hz, 1H).

Example 4: Synthesis of 2- (thiophen-2-yl) tetrazolopyridine (Compound (Tz-5))
Step 1: Synthesis of 2-bromopyridine-N-oxide

Synthesis was carried out in the same manner as in Step 1 of Example 1 except that the raw material was changed from 2,5-dibromopyridine to 2-bromopyridine and the reaction time was 3 days.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.11 (td, J = 1.4, 8.0 Hz, 1H), 7.25 (td, J = 1.9, 6.4 Hz, 1H), 7.67 (dd, J = 1.9, 8.0 Hz, 1H), 7.67 (dd, J = 1.4, 6.4 Hz, 1H).

Step 3: Synthesis of 2- (thiophen-2-yl) pyridine-N-oxide

2-Bromopyridine N-oxide (174 mg, 1 mmol), 2- (Tributylstannyl) thiophene (560 mg, 1.5 mmol), Pd (PPh ₃ ) ₄ (116 mg, 0.1 mmol), and anhydrous toluene (2 mL) And stirred at 180 ° C. for 20 minutes using a microwave reactor. After completion of the reaction, the solvent was concentrated and purified using silica gel column chromatography (Hexane / AcOEt = 1: 1) to purify 117 mg of 2- (Thiophen-2-yl) pyridine N-oxide (white solid) (yield 66%). )Obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.14 (td, J = 2.0, 7.0 Hz, 1H), 7.21 (dd, J = 4.0, 5.0 Hz, 1H), 7.32 (td, J = 1.3, 8.0 Hz, 1H), 7.58 (d, J = 5.0 Hz, 1H), 7.86 (dd, J = 1.0, 4.0 Hz, 1H), 7.95 (dd, J = 2.0, 8.0 Hz, 1H), 8.32 (d, J = 7.0 Hz, 1H).

Step 4: Synthesis of 2- (thiophen-2-yl) tetrazolopyridine (Compound (Tz-5))

Synthesis was performed in the same manner as in Step 4 of Example 1 (white solid, 41 mg, 41%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.29 (dd, J = 3.8, 5.0 Hz, 1H), 7.54 (dd, J = 0.9, 7.1 Hz, 1H), 7.65 (dd, J = 1.2, 5.0 Hz, 1H), 7.72 (dd, J = 7.1, 8.9 Hz, 1H), 7.97 (dd, J = 0.9, 8.9 Hz, 1H), 8.39 (dd, J = 1.2, 3.8 Hz, 1H).

Example 5: Synthesis of 2,5-diphenyltetrazolopyridine (Compound (Tz-6))
Step 3: Synthesis of 2,5-diphenylpyridine-N-oxide

2,5-dibromopyridine N-oxide (250 mg, 1 mmol), phenylboronic acid (366 mg, 3.0 mmol), Pd (PPh ₃ ) ₄ (115 mg, 0.1 mmol), 2MK ₂ CO ₃ aqueous solution ( 3 mL) and THF (6 mL) were added, and the mixture was stirred at 60 ° C. for 24 hours. After completion of the reaction, the organic layer was extracted with dichloromethane, the solvent was concentrated, and then purified using silica gel column chromatography (Hexane / AcOEt = 1: 2) to purify 2,5-diphenylpyridine N-oxide (white solid) (311 mg). (Yield 100%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.42-7.54 (m, 8H), 7.59 (d, J = 8.0 Hz, 2H), 7.85 (d, J = 8.0 Hz, 2H).

Step 4: Synthesis of 2,5-diphenyltetrazolopyridine (Compound (Tz-6))

Synthesis was performed in the same manner as in Step 4 of Example 1 (white solid, 55 mg, 40%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.41 (d, J = 7.2 Hz, 1H), 7.47-7.64 (m, 6H), 7.91 (d, J = 7.2 Hz, 1H), 8.03-8.07 (m, 2H), 8.16-8.20 (m, 2H).

Example 6: Synthesis of 5-bromo-2- (thiophen-2-yl) tetrazolopyridine (Compound (Tz-7))
Step 5: Synthesis of 5-bromo-2- (thiophen-2-yl) pyridine-N-oxide

5-bromo-2- (5-hexylthiophen-2-yl) pyridine N-oxide was synthesized in the same manner as in Step 3 of Example 1 except that 1 equivalent of 2- (Tributylstanny) thiophene was used (yellow solid, 1.98 g, 77%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.21 (t, J = 4.6 Hz, 1H), 7.44 (dd, J = 1.8, 8.8 Hz, 1H), 7.59 (d, J = 5.1 Hz, 1H), 7.80 (d, J = 8.8 Hz, 1H), 7.84 (d, J = 4.0 Hz, 1H), 8.47 (d, J = 1.8 Hz, 1H).

Step 6: Synthesis of 5-bromo-2- (thiophen-2-yl) tetrazolopyridine (Compound (Tz-7))

5-Bromo-2- (thiophen-2-yl) tetrazolopyridine was synthesized in the same manner as in Step 4 of Example 1 (pale yellow solid, 10 mg, 10%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30 (dd, J = 4.0, 5.0 Hz, 1H), 7.41 (d, J = 7.8 Hz, 1H), 7.67 (dd, J = 1.2, 5.0 Hz, 1H) , 7.91 (d, J = 7.8 Hz, 1H), 8.39 (dd, J = 1.2, 4.0 Hz, 1H).

Example 7: Synthesis of 2,5-bis (4-methoxyphenyl) tetrazolopyridine (Compound (Tz-8))
Step 3: Synthesis of 2,5-bis (4-methoxyphenyl) pyridine-N-oxide

Synthesis was carried out in the same manner as in Step 3 of Example 1 except that 2 equivalents of 2- (Tributylstannyl) thiophene was used instead of 3 equivalents of 2- (Tributylstannyl) -4-methoxybenzene (white solid, 335 mg, 100 %).

¹ H NMR (400 MHz, CDCl ₃ ) δ 3.87 (s, 6H), 7.01 (d, J = 7.8 Hz, 4H), 7.45 (br s, 2H), 7.52 (d, J = 8.5 Hz, 2H), 7.86 (d, J = 8.5 Hz, 2H), 8.55 (s, 1H).

Step 4: Synthesis of 2,5-bis (4-methoxyphenyl) tetrazolopyridine (Compound (Tz-8))

2,5-bis (4-methoxyphenyl) tetrazolopyridine was synthesized in the same manner as in Step 4 of Example 1 (white solid, 111 mg, 92%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 3.90 (s, 3H), 3.92 (s, 3H), 7.09 (d, J = 8.8 Hz, 2H), 7.10 (d, J = 8.8 Hz, 2H), 7.32 (d, J = 7.4 Hz, 1H), 7.83 (d, J = 7.4 Hz, 1H), 8.03 (d, J = 8.8 Hz, 2H), 8.17 (d, J = 8.8 Hz, 2H).

Example 8: Synthesis of 2,5-bis (4-trifluoromethylphenyl) tetrazolopyridine (Compound (Tz-9))
Step 3: Synthesis of 2,5-bis (4-trifluoromethylphenyl) pyridine-N-oxide

Instead of phenylboronic acid (366 mg, 3.0 mmol), 4-trifluoromethylphenylboronic acid was used, and instead of stirring reaction conditions at 60 ° C. for 24 hours, microwave heating was performed at 130 ° C. for 20 minutes. Except for the change, 2,5-bis (4-trifluoromethylphenyl) pyridine-N-oxide was synthesized in the same manner as in Step 3 of Example 5 (white solid, 208 mg, 100%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.55 (d, J = 1.2 Hz, 2H), 7.72 (d, J = 8.0 Hz, 2H), 7.77 (t, J = 7.2 Hz, 4H), 7.99 (d , J = 8.0 Hz, 2H), 8.62 (t, J = 1.2 Hz, 1H).

Step 4: Synthesis of 2,5-bis (4-trifluoromethylphenyl) tetrazolopyridine (Compound (Tz-9))

Synthesis was performed in the same manner as in Step 4 of Example 1 (white solid, 134 mg, 82%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.50 (d, J = 7.4 Hz, 1H), 7.85 (d, J = 8.3 Hz, 2H), 7.89 (d, J = 8.3 Hz, 2H), 8.00 (d , J = 7.4 Hz, 1H), 8.20 (d, J = 8.2 Hz, 2H), 8.32 (d, J = 8.2 Hz, 2H).

Example 9 Synthesis of 2,5-bis (piperidin-2-yl) tetrazolopyridine (Compound (Tz-10))
Step 3: Synthesis of 2,5-bis (piperidin-2-yl) pyridine-N-oxide

Synthesis was performed in the same manner as in Step 3 of Example 1, except that 3.0 equivalents of 2- (Tributylstannyl) pyridine were used instead of 2.4 equivalents of 2- (Tributylstannyl) thiophene, and the amount of catalyst was changed. (White solid, 237 mg, 63%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.33-7.39 (m, 2H), 7.74-7.78 (m, 1H), 7.81-7.88 (m, 2H), 8.02 (dd, J = 1.9, 8.7 Hz, 4H ), 8.32 (d, J = 8.7 Hz, 1H), 8.75 (m, 1H), 8.98 (d, J = 1.8 Hz, 1H), 9.01 (d, J = 8.2 Hz, 1H)

Step 4: 2,5-bis (piperidin-2-yl) tetrazolopyridine (compound (Tz-10))

Synthesis was performed in the same manner as in Step 4 of Example 1 (pale yellow solid, 66 mg, 44%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.30 (t, J = 6.8 Hz, 1H), 7.36 (dd, J = 4.9, 7.6 Hz, 1H), 7.49 (t, J = 7.8 Hz, 1H), 7.88 (td, J = 1.6, 7.6 Hz, 1H), 8.16 (d, J = 8.7 Hz, 1H), 8.45 (d, J = 8.5 Hz, 1H), 8.56 (d, J = 8.5 Hz, 1H), 8.72 (br d, J = 4.9Hz, 1H), 8.79 (d, J = 8.0 Hz, 1H), 8.89 (d, J = 6.8 Hz, 1H).

Example 10 Synthesis of 2,5-bis (piperidin-4-yl) tetrazolopyridine (Compound (Tz-11))
Step 3: Synthesis of 2,5-bis (piperidin-4-yl) pyridine-N-oxide

The process of Example 5 except that 4-pyridineboronic acid was used instead of phenylboronic acid and the reaction conditions were changed to heating and stirring at 130 ° C. for 20 minutes using microwave instead of stirring at 60 ° C. for 24 hours. Synthesis was performed as in 3 (white solid, 107 mg, 43%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.51 (d, J = 6.2 Hz, 2H), 7.60 (br d, 2H), 7.81 (d, J = 6.2 Hz, 2H), 8.64 (s, 1H), 8.76-8.82 (m, 4H).

Step 4: Synthesis of 2,5-bis (piperidin-4-yl) tetrazolopyridine (Compound (Tz-11))

Synthesis was performed in the same manner as in Step 4 of Example 1 (white solid, 75 mg, 50%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.59 (d, J = 7.4 Hz, 1H), 8.02 (d, J = 6.3 Hz, 2H), 8.11 (d, J = 7.4 Hz, 1H), 8.19 (d , J = 6.2 Hz, 2H), 8.86 (d, J = 6.2 Hz, 2H), 8.92 (d, J = 6.2 Hz, 2H).

Example 11: Synthesis of 2- (piperidin-2-yl) -5- (piperidin-4-yl) tetrazolopyridine (Compound (Tz-12))
Step 5: Synthesis of 5-bromo (2-piperidin-2-yl) pyridine-N-oxide

Synthesis was performed in the same manner as in Step 3 of Example 9, except that 1.0 equivalent of 2- (Tributylstanny) Pyridine was used instead of 1.0 equivalent, and the mixture was heated and stirred at 120 ° C. for 18 hours without using a microwave apparatus. Performed (white solid, 337 mg, 67%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.32-7.38 (m, 1H), 7.36 (dd, J = 4.9, 7.6 Hz, 1H), 7.79-7.86 (m, 1H), 8.12 (d, J = 8.7 Hz, 1H), 8.46 (d, J = 1.8 Hz, 1H), 8.71 (d, J = 4.9 Hz, 1H), 8.88 (d, J = 8.0 Hz, 1H).

Step 3: Synthesis of 2- (piperidin-2-yl) -5- (piperidin-4-yl) pyridine-N-oxide

Synthesis was performed in the same manner as in Step 3 of Example 8 except that 1.5 equivalents of 4-pyridineboronic acid was used instead of 3 equivalents of 4-trifluoromethylphenylboronic acid (white solid, 165 mg, 55% ).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.36-7.41 (m, 1H), 7.52 (d, J = 6.3 Hz, 2H), 7.60 (dd, J = 1.8, 8.4 Hz, 1H), 7.86 (td, J = 1.7, 7.8 Hz, 1H), 8.35 (d, J = 8.5 Hz, 1H), 8.62 (d, J = 1.6 Hz, 1H), 8.74-8.79 (m, 1H), 8.98 (d, J = 8.2 Hz, 1H).

Step 4: Synthesis of 2- (piperidin-2-yl) -5- (piperidin-4-yl) tetrazolopyridine (Compound (Tz-12))

Synthesis was performed in the same manner as in Step 4 of Example 1 (white solid, 84 mg, 56%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.47-7.52 (m, 1H), 7.95 (td, J = 1.8, 8.0 Hz, 1H), 8.13 (d, J = 7.4 Hz, 1H), 8.16 (d, J = 6.0 Hz, 1H), 8.37 (d, J = 7.4 Hz, 1H), 8.82-8.85 (m, 1H), 7.86 (td, J = 1.7, 7.8 Hz, 3H), 9.02 (d, J = 7.9 Hz, 1H).

Example 12: Synthesis of 2- (piperidin-4-yl) -5- (piperidin-2-yl) tetrazolopyridine (Compound (Tz-13))
Step 5: Synthesis of 5-bromo (2-piperidin-2-yl) pyridine-N-oxide

Synthesis was performed in the same manner as in Step 3 of Example 5 except that 4-pyridineboronic acid was used instead of phenylboronic acid and the reaction time was changed to heating and stirring for 17 hours instead of stirring for 24 hours (white color) Solid, 466 mg, 46%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.34 (d, J = 8.7 Hz, 1H), 7.48 (dd, J = 1.6, 8.2 Hz, 1H), 7.72 (d, J = 6.3 Hz, 1H), 8.49 (d, J = 1.6 Hz, 1H), 8.76 (d, J = 6.3 Hz, 1H).

Step 3: Synthesis of 2- (piperidin-2-yl) -5- (piperidin-4-yl) pyridine-N-oxide

Synthesis was performed in the same manner as in Step 3 of Example 9 except that 2.0 equivalents of 2- (Tributylstanny) Pyridine were used instead of 3 equivalents (white solid, 186 mg, 47%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.36-7.40 (m, 1H), 7.58 (d, J = 8.3 Hz, 1H), 7.75 (d, J = 7.9 Hz, 1H), 7.82-7.87 (m, 3H), 8.01 (dd, J = 1.6, 8.3 Hz, 1H), 8.74-8.76 (m, 1H), 8.78 (d, J = 6.3 Hz, 1H), 9.00 (d, J = 1.7 Hz, 1H).

Step 4: Synthesis of 2- (piperidin-4-yl) -5- (piperidin-2-yl) tetrazolopyridine (Compound (Tz-13))

Synthesis was performed in the same manner as in Step 4 of Example 1 (white solid, 45 mg, 30%).

¹ H NMR (400 MHz, CDCl ₃ ) δ7.35 (td, J = 1.5, 7.0 Hz, 1H), 7.54 (t, J = 7.6 Hz, 1H), 7.74 (d, J = 8.5 Hz, 1H), 8.15 (d, J = 6.2 Hz, 1H), 8.18 (d, J = 8.6 Hz, 1H), 8.56 (d, J = 8.5 Hz, 1H), 8.77 (d, J = 6.2 Hz, 1H), 8.92 ( d, J = 6.9 Hz, 1H).

Example 13: Synthesis of 2- (thiophen-2-yl) -5- (pyridin-2-yl) tetrazolopyridine 3: 2- (thiophen-2-yl) -5- (pyridin-2-yl) Synthesis of pyridine-N-oxide (compound (Tz-14))

Synthesis was performed in the same manner as in Step 3 of Example 12 (pale yellow solid, 347 mg, 73%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.24-7.26 (m, 1H), 7.32-7.35 (m, 1H), 7.61 (dd, J = 1.0, 5.0 Hz, 1H), 7.72 (d, J = 7.8 Hz, 1H), 7.82 (td, J = 1.7, 7.7 Hz, 1H), 7.92 (dd, J = 1.0, 4.0 Hz, 1H), 7.98-8.05 (m, 3H), 8.71-8.75 (m, 1H) , 8.97 (d, J = 1.0Hz, 1H).

Step 4: Synthesis of 2- (piperidin-4-yl) -5- (piperidin-2-yl) tetrazolopyridine (Compound (Tz-14))

Synthesis was performed in the same manner as in Step 4 of Example 1 (pale yellow solid, 70 mg, 63%).

¹ H NMR (400 MHz, CDCl ₃ ) δ7.25-7.26 (m, 1H), 7.28-7.32 (m, 1H), 7.67 (dd, J = 1.0, 5.0 Hz, 1H), 7.70 (d, J = 7.8 Hz, 1H), 7.93 (td, J = 1.8, 7.8 Hz, 1H), 8.44 (dd, J = 1.0, 4.0 Hz, 1H), 8.76 (d, J = 4.0 Hz, 1H), 8.81 (d, J = 7.8 Hz, 1H), 9.14 (d, J = 8.2 Hz, 1H).

Example 14: Synthesis of 2- (pyridin-2-yl) -5- (thiophen-2-yl) tetrazolopyridine 3: 2- (Pyridin-2-yl) -5- (thiophen-2-yl) Synthesis of pyridine-N-oxide (compound (Tz-15))

Synthesis was performed in the same manner as in Step 5 of Example 6 (pale yellow solid, 138 mg, 27%).

¹ H NMR (400 MHz, CDCl ₃ ) δ7.15 (dd, J = 4.0, 5.0 Hz, 1H), 7.32-7.37 (m, 1H), 7.42-7.45 (m, 2H), 7.55 (dd, J = 1.8, 8.6 Hz, 1H), 7.84 (td, J = 1.8, 7.8 Hz, 1H), 8.22 (d, J = 8.5 Hz, 1H), 8.61 (d, J = 1.7 Hz, 1H), 8.71-8.74 ( m, 1H), 8.96 (d, J = 8.2 Hz, 1H).

Step 4: Synthesis of 2- (piperidin-4-yl) -5- (piperidin-2-yl) tetrazolopyridine (Compound (Tz-15))

Synthesis was performed in the same manner as in Step 4 of Example 1 (pale yellow solid, 73 mg, 57%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.27 (dd, J = 4.0, 5.0 Hz, 1H), 7.43-7.47 (m, 1H), 7.55 (dd, J = 1.4, 5.3 Hz, 1H), 7.97 (td, J = 1.8, 7.8 Hz, 1H), 8.01 (d, J = 7.9 Hz, 1H), 8.26 (d, J = 7.9 Hz, 1H), 8.48 (dd, J = 1.0, 4.0 Hz, 1H) , 8.80-8.83 (m, 1H), 8.99 (d, J = 8.2 Hz, 1H).

Example 15: Synthesis of tetrazolopyridine hexamer 2 (compound (Tz-4), compound (Tz-16))
Step 3: Synthesis of 2- (thiophen-2-yl) -5- (5-hexylthiophen-2-yl) pyridine-N-oxide

Instead of using 2.4 equivalents of 2- (Tributylstannyl) thiophene, use 1.5 equivalents of 2- (Tributylstannyl) -5-hexylthiophene and change the reaction temperature and time in the same manner as in Step 3 of Example 1. (Orange solid, 2.56 g (92%)).

¹ H NMR (400 MHz, CDCl ₃ ) 0.89 (t, J = 7.1 Hz, 3H), 1.30-1.36 (m, 4H), 1.38-1.44 (m, 2H), 1.70-1.79 (m, 2H), 2.83 (t, J = 7.6 Hz, 2H), 6.80 (d, J = 3.6 Hz, 1H), 7.19-7.27 (m, 2H), 7.45 (dd, J = 2.0, 8.7 Hz, 1H), 7.56 (dd, J = 1.0, 5.0 Hz, 1H), 7.83 (dd, J = 1.0, 4.0 Hz, 1H), 7.89 (d, J = 8.7 Hz, 1H), 8.54 (d, J = 1.8 Hz, 1H).

Step 4: Synthesis of 2- (thiophen-2-yl) -5- (5-hexylthiophen-2-yl) tetrazolopyridine (Compound (Tz-16))

Synthesis was performed in the same manner as in Step 4 of Example 1 (orange solid, 590 mg (22%)).

¹ H NMR (400 MHz, CDCl ₃ ) 0.90 (m, 3H), 1.30-1.37 (m, 4H), 1.38-1.45 (m, 2H), 1.72-1.79 (m, 2H), 2.91 (t, J = 7.6 Hz, 2H), 6.94 (d, J = 3.6 Hz, 1H), 7.05 (m, 1H), 7.43 (d, J = 7.9 Hz, 1H), 7.80 (d, J = 7.9 Hz, 1H), 8.22 (d, J = 4.0 Hz, 1H), 8.27 (d, J = 4.0 Hz, 1H).

Step 19: Synthesis of pyridine-N-oxide hexamer (compound (Tz-4))

Add 2- (thiophen-2-yl) -5- (5-hexylthiophen-2-yl) tetrazolopyridine (110 mg, 0.3 mmol) and tetrahydrofuran (3 mL), cool to -78 ° C., diisopropylamine ( 1.65 eq) and lithium diisopropylamide prepared from n-butyllithium (1.5 eq) were added dropwise and stirred for 30 minutes. Thereafter, CuCl ₂ ( ₂ eq) was added and the temperature was raised to 0 ° C. and stirred for 4 hours. After completion of the reaction, the solvent was concentrated and purified using silica gel column chromatography (CH ₂ Cl ₂ / MeOH = 30: 1) to obtain a tetrazolopyridine hexamer (red solid).

Example 16: Synthesis of tetrazolopyridine hexamer 3
Step 3: Synthesis of 2- (5-hexylthiophen-2-yl) -5- (hexylthiophen-2-yl) pyridine-N-oxide

Synthesis was performed in the same manner as in Step 3 of Example 1 except that 1.0 equivalent was used instead of 2.4 equivalent of 2- (Tributylstannyl) thiophene, and the reaction temperature and time were changed (yellow solid, 2.56 g (5.9 mmol)).

¹ H NMR (400 MHz, CDCl ₃ ) 0.90 (m, 3H), 1.30-1.37 (m, 4H), 1.38-1.45 (m, 2H), 1.72-1.79 (m, 2H), 2.87 (t, J = 7.6 Hz, 2H), 6.90 (d, J = 4.0 Hz, 1H), 7.13 (dd, J = 4.0, 5.0 Hz, 1H), 7.38 (m, 2H), 7.47 (dd, J = 1.8, 8.7 Hz, 1H), 7.69 (d, J = 4.0 Hz, 1H), 7.84 (d, J = 8.6 Hz, 1H), 8.57 (d, J = 1.7 Hz, 1H).

Step 3: Synthesis of 2- (5-hexylthiophen-2-yl) -5- (thiophen-2-yl) tetrazolopyridine

Synthesis was performed in the same manner as in Step 4 of Example 1 (yellow solid, 530 mg (23%)).

Step 17: Synthesis of 2- (5-tributylstannylthiophen-2-yl) -5- (5-hexylthiophen-2-yl) tetrazolopyridine

To 2- (thiophen-2-yl) -5- (5-hexylthiophen-2-yl) tetrazolopyridine (110 mg, 0.3 mmol) was added tetrahydrofuran (5 mL), and the mixture was cooled to −78 ° C. and diisopropylamine ( 1.65 equivalents) and lithium diisopropylamide prepared from n-butyllithium (1.5 equivalents) were added and reacted at −78 ° C. for 30 minutes. Subsequently, tributyltin chloride (2 equivalents) was added and reacted at 0 ° C. for 4 hours. After completion of the reaction, the mixture was warmed to room temperature and purified to obtain the target compound (yellow solid, 133 mg, 66%).

¹ H NMR (400 MHz, CDCl ₃ ) 0.91 (m, 12H), 1.07-1.80 (m, 26H), 2.88 (t, J = 7.6 Hz, 2H), 6.90 (d, J = 3.8 Hz, 1H), 7.32 (d, J = 3.3 Hz, 1H), 7.51 (d, J = 7.8 Hz, 1H), 7.77 (d, J = 7.8 Hz, 1H), 8.21 (d, J = 3.8 Hz, 1H), 8.47 ( d, J = 3.5 Hz, 1H).

Step 9: Synthesis of 2- (5-hexylthiophen-2-yl) -5- (5-bromothiophen-2-yl) tetrazolopyridine

2- (5-hexylthiophen-2-yl) -5- (thiophen-2-yl) tetrazolopyridine (38 mg, 0.1 mmol), N-butylsuccinimide (1.0 eq), and tetrahydrofuran were added, The reaction was performed at −10 ° C. for 6 hours. After completion of the reaction, the mixture was warmed to room temperature and purified to obtain the target compound (yellow solid, 48 mg, 100%).

¹ H NMR (400 MHz, CDCl ₃ ) 0.91 (m, 3H), 1.30-1.37 (m, 4H), 1.38-1.45 (m, 2H), 1.72-1.79 (m, 2H), 2.92 (t, J = 7.6 Hz, 2H), 6.96 (d, J = 4.0 Hz, 1H), 7.19 (d, J = 4.0 Hz, 1H), 7.43 (d, J = 7.7 Hz, 1H), 7.75 (d, J = 7.7 Hz , 1H), 8.09 (d, J = 4.0 Hz, 1H), 8.25 (d, J = 4.0 Hz, 1H).

Step 18: Synthesis of pyridine-N-oxide hexamer (compound (Tz-4))

2- (5-Tributylstannylthiophen-2-yl) -5- (5-hexylthiophen-2-yl) tetrazolopyridine (67 mg, 0.1 mmol), 2- (5-hexylthiophen-2-yl) Add 5- (5-bromothiophen-2-yl) tetrazolopyridine (48 mg, 0.1 mmol), Pd (PPh ₃ ) ₄ (6 mg, 0.005 mmol), and toluene (10 mL), DMF (1 mL) The mixture is stirred at 120 ° C. for 60 minutes in a nitrogen atmosphere and purified to obtain a tetrazolopyridine hexamer (red solid).

Differential scanning calorimetry The obtained compounds (Tz-1), (Tz-2), (Tz-3), (Tz-4), (Tz-6), (Tz-7), (Tz-8), For (Tz-9), (Tz-11), (Tz-14), (Tz-15), and (Tz-16), a differential scanning calorimeter (“DSC-60” manufactured by Shimadzu Corporation) was used. Differential scanning calorimetry was performed. The results are shown in FIGS.

Thermogravimetric Analysis Measurement The compound (Tz-3) was subjected to thermogravimetric analysis measurement using a thermogravimetric analyzer (“TGA-50” manufactured by Shimadzu Corporation). As a result, it has been clarified that all the compounds of the present invention have excellent thermal stability and are useful as gas generating agents.

UV-Vis absorption spectrum measurement Compound (Tz-1,1.44 × 10 ⁻⁵ M), (Tz-3,8.21 × 10 ⁻⁶ M), (Tz- ⁶ , 1.86 × 10 ⁻⁵ M) , (Tz-8, 7.83 × 10 ⁻⁶ M), (Tz-9, 2.70 × 10 ⁻⁵ M), (Tz-14, 4.53 × 10 ⁻⁵ M), (Tz-15 , 1.47 × 10 ⁻⁵ M) in each concentration, and UV-visible using an ultraviolet / visible spectroscope (manufactured by Shimadzu Corporation, “UV-3100PC”) and a cell with an optical path length of 1 cm. Absorption spectrum measurement was performed. The results are shown in FIGS.

Cyclic voltammetry For compounds (Tz-1), (Tz-3), (Tz-6), (Tz-8), (Tz-9), (Tz-14), (Tz-15), cyclic voltammetry Cyclic voltammetry measurement was performed using a measuring apparatus (manufactured by BAS, “CV-620C voltammetric analyzer”) and a mixed solvent of o-dichlorobenzene / MeCN (5: 1). The results are shown in FIGS. In addition, Table 25 shows the obtained numerical values.

Simulation by Density Functional Method For the compounds represented by the following formulas, the LUMO level and the HOMO level were calculated by performing a simulation by the density functional method, respectively. The results are shown in Table 26.

From the cyclic voltammetry measurement and simulation, the compound of the present invention raises the HOMO level while keeping the LUMO level low compared with the compounds (Tz-5) and (Tz-20) of Comparative Examples. It has become clear that it is useful as an organic semiconductor material.

FET measurement The above compound (Tz-3) was dissolved in chloroform to a concentration of 10 mg / mL, and spin-coated (1000 rpm, 1 minute) on a SiO ₂ / Si substrate treated with ODTS (octadecyltrichlorosilane). Then, a bottom gate-bottom contact type FET element was fabricated, and FET measurement was performed. The channel length was 5 μm. Next, the obtained device was annealed at each temperature of 80 ° C., 120 ° C., 150 ° C., and 180 ° C. for 1 hour, and the FET characteristics were evaluated in the same manner. The obtained numerical values are shown in Table 27.

From the above results, it was revealed that the compound of the present invention has a high ON / OFF ratio and is useful as a semiconductor material. Further, the compound of the present invention is stable even without being decomposed even when heated to 200 ° C. or higher from the results of differential scanning calorimetry, and even when heated to 180 ° C. As a result, the thermal stability of the device was found to be good.

Since the compound of the present invention has high thermal stability and high electron acceptability, organic electrodevices such as organic electroluminescence elements and organic thin film transistor elements, organic semiconductor materials, photoelectric conversion elements, organic electronic devices, solar cells, Useful for solar cell modules.

Claims

The compound represented by Formula (1).

[In Formula (1),
R 1 represents a hydrogen atom, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group.
A 1 represents an optionally substituted aromatic ring or a halogen atom.
m represents an integer of 0 to 2, and n represents an integer of 2 to 4. However, m + n is 4. ]
A compound represented by formula (1-I).

[In the formula (1-I),
A 1 represents an optionally substituted aromatic ring or a halogen atom. ]
The compound according to claim 1 or 2, wherein two or more A 1 are an aromatic ring substituted with a halogen atom, or a halogen atom.
The compound according to any one of claims 1 to 3, wherein two or more of A 1 are halogen atoms.
The compound according to any one of claims 1 to 3, wherein two or more A 1 are aromatic rings substituted with a halogen atom.
A 1 is A compound according to any one of claims 1 to 5, which is one of the aromatic ring selected from the following formulas (Ar1) ~ (Ar8).

[In the formulas (Ar1) to (Ar8),
R 2 represents a halogen atom, an alkyl group, an alkoxy group, or a halogenated alkyl group.
R 3 represents a hydrogen atom or an alkyl group.
p1 represents an integer of 0 to 3, p2 represents an integer of 0 to 2, p3 represents an integer of 0 to 5, and p4 represents an integer of 0 to 4. ]
Following formula (2)

[In Formula (2),
R 1 represents a hydrogen atom, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group.
A 1 represents an optionally substituted aromatic ring or a halogen atom.
m represents an integer of 0 to 2, and n represents an integer of 2 to 4. However, m + n is 4. ]
A compound represented by the formula (1) is reacted with an azide compound in the presence of a base:

In Expression (1), R 1, A 1, m, n are as defined above. ]
The manufacturing method of the compound represented by these.
The following formula (2-I)

[In the formula (2-I),
A 1 represents an optionally substituted aromatic ring or a halogen atom. ]
The compound represented by formula (1-I) is reacted with an azide compound in the presence of a base.

[In the formula (1-I), A 1 has the same meaning as described above. ]
The manufacturing method of the compound represented by these.
A compound represented by the following formula.

[In the formula (II),
R 1 represents a hydrogen atom, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group.
A 20 represents an optionally substituted aromatic ring.
m represents an integer of 0 to 2, n7 represents an integer of 1 or more, and r represents an integer of 1 or more.
However, either n7 or r is 2 or more. ]
An organic semiconductor material comprising the compound according to any one of claims 1 to 6 or 9.
An organic electronic device comprising the organic semiconductor material according to claim 10.