Compound and method for producing same

Abstract

Provided is a compound obtained by simply and easily extending the π electron system of a tetrazolopyridine compound. This compound is represented by formula (1). [In formula (1), R1 represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, m represents an integer of 0-2. If there are multiple occurrences of R1, R1 may be different at each occurrence. Each occurrence of A1 independently represents an optionally substituted aromatic ring, n represents an integer of 1-5, and each occurrence of R2 independently represents a hydrogen atom or an alkyl group.]

Description

[Technical field]

[0001] The present invention relates to a compound and a method for producing the same, and more particularly to a novel tetrazolopyridine compound that can be used in organic semiconductors and the like, and a method for producing the same. [Background technology]

[0002] Patent Document 1 discloses the following tetrazolopyridine compounds.

[0003] [ka]

[0004] [In the above formula, A 1 represents an optionally substituted aromatic ring or a halogen atom. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2016 / 143823 Summary of the Invention [Problem to be solved by the invention]

[0006] However, it is not easy to expand the π electron system of the tetrazolopyridine compound, and there is a demand for a simple method for expanding the π electron system. [Means for solving the problem]

[0007] As a result of intensive research to solve the above problems, the present inventors have found that 1 The present inventors have found that, by making an aromatic ring of the formula (I) and introducing an aldehyde group or a ketone group therein, the π electron system can be easily expanded, and that although the introduction of an aldehyde group or a ketone group is not easy, an aldehyde group or a ketone group can be easily introduced by an appropriate production method, and have thus completed the present invention.

[0008] That is, the present invention includes the following inventions. [1] A compound represented by formula (1). [ka] [In formula (1), R 1 represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and m represents an integer of 0 to 2. 1 When multiple A are present, they may be different from each other. 1 each independently represents an aromatic ring which may have a substituent; n represents an integer of 1 to 5; R 2 each independently represents a hydrogen atom or an alkyl group.

[0009] [2] A compound having a carbonyl group protected by the following formula (2), and an aromatic ring A of the formula (2) 1 to produce a tin compound represented by the following formula (4), a step of reacting the tin compound represented by the formula (4) with a pyridine-N-oxide compound represented by the following formula (5) to produce a coupling compound represented by the following formula (6), and a step of deprotecting a carbonyl group of the coupling compound of the following formula (6) and cyclizing the pyridine-N-oxide. [ka] [In the formula, A 1 , n, R 1 , m, R 2 are the same as above, and R 6 , R 7 represents an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom.

[0010] [3] A method for producing a condensation product, comprising condensing a compound represented by formula (1) described in [1] above with a first electron-withdrawing compound represented by formula (8a) below or a second electron-withdrawing compound represented by formula (8b) below. [ka] [In the formula, R c represents an aromatic ring, E 1a each independently represents an electron-withdrawing group or a group represented by the following formula (X), 1b represents an electron-withdrawing group, an aromatic ring, or a group represented by the following formula (X), and p represents an integer of 1 to 3. 1a and E 1b may be bonded to each other to form a heterocycle having a carbonyl group or a thiocarbonyl group as a ring member. 1a and E 1b is a group represented by the following formula (X), R 11 may be bonded together to form a ring. ·· indicates a carbon atom which forms a double bond by a condensation reaction.] [ka] [In the formula, E 2 each independently represents an electron-withdrawing group; R 11 represents an organic group, and * represents a bond.

[0011] [4] A method for producing the condensate according to the above [3], wherein the condensate of the compound represented by the formula (1) and the compound represented by the formula (8a) is represented by the following formula (9a): [ka] [In the formula, A 1 , n, R 1 , m, R 2 , E 1a , E 1b are the same as above.]

[0012] [5] The method for producing a condensation product according to the above [3] or [4], wherein the compound represented by the formula (8a) is at least one selected from the following compound group (8A): [ka] [In the formula, Ar represents an aromatic ring; R 12 , R 13 , and R 14 Each of E independently represents a hydrogen atom or an organic group. 1a , ·· have the same meaning as above.]

[0013] [6] A method for producing the condensation product according to the above item [3], wherein the condensation product of the compound represented by formula (1) and the compound represented by formula (8b) in which p is 1 is represented by the following formula (9b): [ka] [In the formula, A 1 , n, R 1 , m, R 2 , E 1a , R c are the same as above.]

[0014] [7] A compound represented by the following formula (9a): [ka] [In the formula, A 1 , n, R 1 , m, R 2 , E 1a , E 1b are the same as above.]

[0015] [8] A compound represented by the following formula (9b): [ka] [In the formula, A 1 , n, R 1 , m, R 2 , E 1a , R c are the same as above.] Effect of the Invention

[0016] According to the compound represented by formula (1), the aldehyde group or ketone group can be converted to a carbon-carbon double bond by reacting with a compound having an active methylene group, and the π electron system can be easily expanded. By expanding the π electron system, the usefulness as an organic semiconductor compound is expanded. In addition, according to the production method of the present invention, the compound represented by formula (1) can be easily produced. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention will be described below. Note that hereinafter, "a compound represented by formula (x)" may be simply referred to as "compound (x)".

[0018] 1.Compound The compound of the present invention is a compound represented by the following formula (1).

[0019] [ka]

[0020] [In formula (1), R 1 represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and m represents an integer of 0 to 2. 1 When multiple A are present, they may be different from each other. 1 each independently represents an aromatic ring which may have a substituent; n represents an integer of 1 to 5; R 2 each independently represents a hydrogen atom or an alkyl group.

[0021] In the above formula (1), m is preferably 0 or 1, and more preferably 0. 1 When there are a plurality of (m is 2), they may be different from each other, but are preferably the same.

[0022] In the above formula (1), R 1 The aliphatic hydrocarbon group or alicyclic hydrocarbon group preferably has 1 to 30 carbon atoms, and the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms.

[0023] (Aliphatic hydrocarbon group) R 1 The aliphatic hydrocarbon group may be either linear or branched.

[0024] R 1 The aliphatic hydrocarbon group may be either an alkyl group or an unsaturated aliphatic hydrocarbon group such as an alkenyl group or an alkynyl group, with an alkyl group being preferred.

[0025] R 1 The aliphatic hydrocarbon group preferably has 1 to 24 carbon atoms, and more preferably has 1 to 20 carbon atoms. 1Specific examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 1-n-butylbutyl group, a 1-n-propylpentyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, a 4-ethylhexyl group, a 1-methylheptyl group, a 2-methylheptyl group, a 6-methylheptyl group, a 2,4,4-trimethylpentyl group, a 2,5-dimethylhexyl group, and an n-nonyl group. , 1-n-propylhexyl group, 2-n-propylhexyl group, 1-ethylheptyl group, 2-ethylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 6-methyloctyl group, 2,3,3,4-tetramethylpentyl group, 3,5,5-trimethylhexyl group, n-decyl group, 1-n-pentylpentyl group, 1-n-butylhexyl group, 2-n-butylhexyl group, 1-n-propylheptyl group, 1-ethyloctyl group, 2-ethyloctyl group, 1-methylnonyl group, 2-methylnonyl group, 3,7-Dimethyloctyl group, n-undecyl group, 1-n-butylheptyl group, 2-n-butylheptyl group, 1-n-propyloctyl group, 2-n-propyloctyl group, 1-ethylnonyl group, 2-ethylnonyl group, n-dodecyl group, 1-n-pentylheptyl group, 2-n-pentylheptyl group, 1-n-butyloctyl group, 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-heptyl Examples of the aryl group include xyloctyl 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, and 2-decyltetradecyl group.

[0026] (alicyclic hydrocarbon group) R 1 The alicyclic hydrocarbon group may be either monocyclic or polycyclic.

[0027] R 1 The alicyclic hydrocarbon group may be either a cycloalkyl group or an unsaturated alicyclic hydrocarbon group such as a cycloalkenyl group or a cycloalkynyl group, with a cycloalkyl group being preferred.

[0028] R 1 The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 14 carbon atoms. 1Specific examples of the alicyclic hydrocarbon group 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.

[0029] (aromatic hydrocarbon group) R 1 The aromatic hydrocarbon group means a group having an aromatic ring. Specific examples of the aromatic ring include non-benzene aromatic rings, benzene rings, and condensed aromatic rings such as naphthalene rings, anthracene rings, and pyrene rings. The aromatic hydrocarbon group includes both unsubstituted aromatic hydrocarbon groups and aromatic hydrocarbon groups substituted with a substituent. Examples of the aromatic hydrocarbon group substituted with a substituent include heteroaromatic rings (pyrrole ring, pyridine ring, thiophene ring, furan ring, etc.) in which one or more carbon atoms of the non-benzene aromatic ring, benzene ring, or condensed aromatic ring are replaced with heteroatoms such as oxygen atoms, nitrogen atoms, and sulfuric acid atoms.

[0030] In the above formula (1), A 1 are each independently an aromatic ring which may have a substituent, and may be different from each other, but are preferably the same. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle.

[0031] (aromatic hydrocarbon ring) Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, and among these, a benzene ring is preferable.

[0032] (Aromatic heterocycle) Examples of the aromatic heterocycle include those represented by the following formulae. Among these, a thiophene ring, a thiazole ring, a pyridine ring, a pyrrole ring, an imidazole ring, a furan ring, an oxazole ring, and the like are preferable.

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] A 1 The aromatic ring may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and when substituted, it is preferably substituted with a fluorine atom.

[0039] The number of the halogen atoms substituted is preferably one or two.

[0040] A 1 The aromatic ring may have a substituent other than a halogen atom. Examples of the substituent other than a halogen atom include an alkyl group, an alkoxy group, and a halogenated alkyl group. Examples of the alkyl group include R 1Examples of the alkyl group include the same alkyl groups as those exemplified as the aliphatic hydrocarbon group of the above. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 24. Examples of the alkoxy group include the above alkyl group bonded with -O-. The number of carbon atoms in the alkoxy group is preferably 1 to 30, more preferably 1 to 24. Examples of the halogenated alkyl group include the above alkyl group in which a hydrogen atom is substituted with a halogen atom (preferably a fluorine atom) such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The number of carbon atoms in the halogenated alkyl group is preferably 1 to 30, more preferably 1 to 10, and even more preferably 1 to 4. Specific examples of the halogenated alkyl group include perfluoroalkyl groups such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group, and the like, with a trifluoromethyl group being particularly preferred.

[0041] Above A 1 Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocycle. 1 The aromatic hydrocarbon ring and aromatic heterocycle are the same as those described above. 1 Of the aromatic rings, the aromatic hydrocarbon ring is preferably bonded to the pyridine ring of the tetrazolopyridine at the 2-position or 5-position, and the aromatic heterocycle is preferably bonded to the pyridine ring of the tetrazolopyridine at the 2-position.

[0042] In the above formula (1), n ​​is preferably 1 to 3, and more preferably 1.

[0043] Above A 1 As the aromatic ring, aromatic rings represented by the following formulae (Ar1) to (Ar8) are preferable.

[0044] [ka]

[0045] [In formulas (Ar1) to (Ar8), R 3 R represents a halogen atom, an alkyl group, an alkoxy group, or a halogenated alkyl group.4 represents a hydrogen atom or an alkyl group. p1 represents an integer of 0 to 2, p2 represents an integer of 0 to 1, p3 represents an integer of 0 to 4, and p4 represents an integer of 0 to 3.]

[0046] Above R 3 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom is preferred.

[0047] Above R 3 The alkyl group, alkoxy group, halogenated alkyl group, and the above R 4 The alkyl group of A 1 The substituents are the same as the alkyl group, alkoxy group, and halogenated alkyl group exemplified as the substituents that may be possessed by the aromatic ring of R 1 As the alkyl group, an alkoxy group or a halogenated alkyl group is preferable.

[0048] Above A 1 As the aromatic ring, the rings represented by the above formulae (Ar1) to (Ar4) are more preferable, and the units represented by the following formulae (Ar1-1) to (Ar4-1) are further preferable.

[0049] [ka]

[0050] [In formulas (Ar1-1) to (Ar4-1), R 3 , p1, p2, p3, and p4 are the same as above. * represents a bond.]

[0051] In the above formula (1), R 2 are each independently a hydrogen atom or an alkyl group, and may be different from each other, but are preferably the same. 2 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and further preferably a hydrogen atom.

[0052] An example of the unit represented by the above formula (1) is a unit represented by the following formula (1A).

[0053] [ka]

[0054] [In formula (1A), R 2 is the same as above, and A 10 , A 11 is the above A 1 and each n11 independently represents an integer of 1 to 5.

[0055] In the unit represented by the above formula (1A), n11 is preferably an integer of 1 to 3, and when n11 is 1, the combinations in the table below are preferable.

[0056] [Table 1]

[0057] [Table 2]

[0058] In the above table, each formula number represents a structure represented by the following formulae (Ar1-1-1) to (Ar4-1-2), respectively.

[0059] [ka]

[0060] In the above formulas (Ar1-1-1) to (Ar4-1-2), R 5 represents an alkyl group. As the alkyl group, R 1 Examples of the aliphatic hydrocarbon group include the same alkyl groups as those exemplified above. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 24, and even more preferably 1 to 12. * represents a bond to the tetrazolopyridine unit.

[0061] Among the units (IA-1) to (IA-144) shown in the above table, the units (IA-1) to (IA-48) are more preferable, the units (IA-1), (IA-14), (IA-27) and (IA-40) are further preferable, and the unit (IA-1) is particularly preferable.

[0062] 2. Manufacturing method The method for producing the compound (1) of the present invention comprises protecting the carbonyl group of an aromatic carbonyl compound represented by the following formula (2) and annealing the aromatic ring A of the formula (2) 1 to produce a tin compound represented by the following formula (4), a step of reacting the tin compound represented by formula (4) with a pyridine-N-oxide compound represented by the following formula (5) to produce a coupling compound represented by the following formula (6), and a step of deprotecting the carbonyl group of the coupling compound of formula (6) and cyclizing the pyridine-N-oxide. Specifically, compound (1) of the present invention can be produced by a production method represented by the following scheme.

[0063] [ka]

[0064] [In the formula, A 1 , n, R 1 , m, R 2 are the same as above, and R 6 , R 7 represents an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom.

[0065] A more preferred method for producing the compound (1) of the present invention comprises the steps of: protecting the carbonyl group of the aromatic carbonyl compound represented by the above formula (2) to produce the following compound (3) (step A: protection step); 1to produce a tin compound represented by the following formula (4) (Step B: a trialkyltin group providing step), a step of reacting the tin compound represented by the above formula (4) with a pyridine-N-oxide compound represented by the above formula (5) to produce a coupling compound represented by the above formula (6) (Step C: a coupling step), a step of cyclizing the pyridine-N-oxide in the coupling compound of the above formula (6) to produce the following compound (7) (Step D: a cyclization step), and a step of deprotecting the carbonyl group in the following compound (7) (Step E: a deprotection step). Specifically, compound (1) of the present invention can be produced by the production method represented by the following scheme.

[0066] [ka]

[0067] [In the formula, A 1 , n, R 1 , m, R 2 , R 6 , R 7 , X are as defined above.]

[0068] Each of the above steps A to E will be described below.

[0069] [Process A: Protection process] In step A, as shown in the following formula, a protecting group is introduced to protect the carbonyl group of the aromatic carbonyl compound represented by formula (2) above, thereby producing a compound represented by formula (3) above having a protecting group introduced therein.

[0070] [ka]

[0071] [In the formula, A 1 , n, R 2 , R 6 are the same as above.]

[0072] The protecting group to be introduced into the above compound (3) is not particularly limited, and the protecting group can be introduced using one selected from diol compounds such as pinacol, 1,3-propanediol, and 1,3-propanedithiol, and among these, it is preferable to use pinacol.

[0073] [Step B: Trialkyltin Group Addition Step] In step B, as shown in the following formula, an organolithium compound such as n-butyllithium or lithium diisopropylamide (LDA), or a Grignard reagent is reacted with the compound (3) in a solvent to form an aromatic ring A 1 After activating R 7 3 By reacting with SnCl, the tin compound represented by the above formula (4) can be obtained.

[0074] [ka]

[0075] [In the formula, A 1 , n, R 2 , R 6 , R 7 are the same as above.]

[0076] Examples of the solvent include tetrahydrofuran (THF), hexane, diethyl ether, etc. The reaction temperature can be, for example, −70 to −90° C. 7 Each of R independently represents an alkyl group having 1 to 4 carbon atoms, and is preferably a methyl group or a butyl group. 7 may be the same or different, but from the viewpoint of ease of synthesis, they are preferably the same, and the three R 7 More preferably, all of are butyl groups.

[0077] [Step C: Coupling step] In step C, as shown in the following formula, the tin compound represented by the above formula (4) is reacted with the pyridine-N-oxide compound represented by the above formula (5) to produce the coupling compound represented by the above formula (6). The method for producing compound (5) will be described later in step C'.

[0078] [ka]

[0079] [In the formula, A 1 , n, R 1 , m, R 2 , R 6 , R 7 , X are as defined above.]

[0080] The two X's in the compound (5) may be the same or different, but are preferably the same. Examples of the halogen atom of X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and it is preferable that the two X's are bromine atoms.

[0081] The amount of the compound (5) is preferably 1.2 to 10 mol, more preferably 2 to 7 mol, per 1 mol of the compound (4).

[0082] When reacting the compound (4) with the compound (5), a catalyst may be present. Examples of the catalyst in the coupling step include metal catalysts, and preferably metal catalysts such as palladium catalysts, nickel catalysts, iron catalysts, copper catalysts, rhodium catalysts, and ruthenium catalysts. Among these, palladium catalysts are more preferred. The palladium of the palladium catalyst may be zero-valent or divalent.

[0083] Examples of the palladium catalyst include palladium chloride (II), palladium bromide (II), palladium iodide (II), palladium oxide (II), palladium sulfide (II), palladium telluride (II), palladium hydroxide (II), palladium selenide (II), palladium cyanide (II), palladium acetate (II), palladium trifluoroacetate (II), palladium acetylacetonate (II), and bis(triphenylphosphine) palladium diacetate. Radium(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) Examples of the catalyst include bis(tri-tert-butylphosphine)palladium(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), and dichlorobis(triphenylarsine)palladium(II). These catalysts may be used alone or in combination of two or more.Among these, tetrakis(triphenylphosphine)palladium(0), tris(dibenzylideneacetone)dipalladium(0), dichlorobis(triphenylphosphine)palladium(II), and tris(dibenzylideneacetone)dipalladium(0) chloroform adduct are particularly preferred.

[0084] The molar ratio of the compound (4) to the catalyst [compound (4):catalyst] is preferably about 1:0.0001 to 1:0.5, and from the viewpoint of yield and reaction efficiency, is more preferably 1:0.001 to 1:0.4, further preferably 1:0.005 to 1:0.3, and particularly preferably 1:0.01 to 1:0.2.

[0085] In the coupling step, a specific ligand may be coordinated to the catalyst. Examples of the ligand 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, triphenylphosphine, tris(o-tolyl)phosphine, tris(m-tolyl)phosphine, tris(p-tolyl)phosphine, tris(2-furyl)phosphine, and the like. , tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, 2-dicyclohexylphosphinobiphenyl, 2-dicyclohexylphosphino-2'-methylbiphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino-2'-(N,N'-dimethylamino)biphenyl, 2 -Diphenylphosphino-2'-(N,N'-dimethylamino)biphenyl, 2-(di-tert-butyl)phosphino-2'-(N,N'-dimethylamino)biphenyl, 2-(di-tert-butyl)phosphinobiphenyl, 2-(di-tert-butyl)phosphino-2'-methylbiphenyl, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(dicyclohexylphosphino)ethane, 1,3-bis(dicyclohexylphosphino)ethane, xylphosphino)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-dimethyldihydroimidazolylidene, diethyldihydroimidazolylidene, 1,3-bis(2,4,6-trimethylphenyl)dihydroimidazolylidene, 1,3-bis(2,6-diisopropylphenyl)dihydroimidazolylidene, 1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, and bathophenanthroline can be used alone or in combination. Among these, triphenylphosphine, tris(o-tolyl)phosphine, and tris(2-methoxyphenyl)phosphine are preferred.

[0086] When the above-mentioned ligand is coordinated, the molar ratio of the catalyst to the ligand (catalyst:ligand) is generally about 1:0.5 to 1:10, and from the viewpoint of yield and reaction efficiency, it is preferably 1:1 to 1:8, more preferably 1:1 to 1:7, and even more preferably 1:1 to 1:5.

[0087] Examples of the base include alkali metal salt compounds such as lithium hydride, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; alkaline earth metal salt compounds such as magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, and barium carbonate; alkoxy alkali metal compounds such as 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, and potassium tert-amyl alkoxide; and metal hydride compounds such as lithium hydride, sodium hydride, and potassium hydride. Among these, the base is preferably an alkali metal salt compound or an alkoxy alkali metal compound, and more preferably sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, sodium tert-butoxide, or potassium tert-butoxide.

[0088] The molar ratio of the compound (4) to the base [compound (4):base] is generally about 1:1 to 1:10, and from the viewpoint of yield and reaction efficiency, is preferably 1:1.5 to 1:8, more preferably 1:1.8 to 1:6, and even more preferably 1:2 to 1:5.

[0089] As the solvent in the coupling step, a solvent that does not affect the reaction can be used, and for example, an ether solvent, an aromatic solvent, an ester solvent, a hydrocarbon solvent, a halogenated solvent, a ketone solvent, an amide solvent, etc. 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, dioxane, etc. Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, etc. Examples of the hydrocarbon solvent include pentane, hexane, heptane, etc. Examples of the halogenated solvent include dichloromethane, chloroform, dichloroethane, dichloropropane, etc. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-(1H)-pyrimidine. 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, dioxane, toluene, xylene, and N,N-dimethylformamide are preferred.

[0090] In the coupling step, the amount of the solvent is generally about 1 mL or more and 100 mL or less per 1 g of compound (4), and from the viewpoint of yield and reaction efficiency, it is preferably 5 mL or more and 80 mL or less, more preferably 8 mL or more and 70 mL or less, and even more preferably 10 mL or more and 60 mL or less.

[0091] In the above coupling step, the reaction temperature is preferably from 0° C. to 220° C., more preferably from 30° C. to 200° C., and even more preferably from 40° C. to 180° C., from the viewpoint of increasing the reaction efficiency. The reaction temperature may be adjusted using microwaves.

[0092] [Step C': Oxidation step] In step C', the following compound (5') is reacted with an oxidizing agent to obtain the pyridine-N-oxide compound represented by the above formula (5).

[0093] [ka]

[0094] [In the formula, R 1 , m, and X are as defined above.

[0095] The two X's in the compound (5') may be the same or different, but are preferably the same. Examples of the halogen atom of X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and it is preferable that the two X's are bromine atoms.

[0096] As the oxidizing agent, for example, a percarboxylic acid such as metachloroperbenzoic acid can be used.

[0097] The amount of the oxidizing agent is preferably 0.1 mol or more and 10 mol or less, and more preferably 0.5 mol or more and 5 mol or less, relative to 1 mol of the compound (5').

[0098] The solvent used in the oxidation step is preferably a halogen-based solvent such as dichloromethane, chloroform, dichloroethane, or dichloropropane.

[0099] [Step D: Cyclization step] In step D, the above compound (7) can be obtained by cyclization of pyridine-N-oxide in the coupling compound of the above formula (6), as shown below.

[0100] [ka]

[0101] [In the formula, A 1 , n, R 1 , m, R 2 , R 6 are the same as above.]

[0102] The cyclization reaction is preferably carried out by reacting an azide compound in the presence of a base. As the azide compound, for example, an organic azide compound such as diarylphosphoryl azide, such as diphenylphosphoryl azide (DPPA) or bis(4-nitrophenyl)phosphoryl azide; a trialkylsilyl azide, such as trimethylsilyl azide (TMSA); and an inorganic azide compound, such as sodium azide, are preferable. The organic azide compound may be supported by a polymer. Among these, diarylphosphoryl azide is preferable, and diphenylphosphoryl azide (DPPA) is more preferable.

[0103] 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 even more preferably 1 mol or more and 5 mol or less, relative to 1 mol of the compound (6). When the amount of the azide compound is within this range, the yield and reaction efficiency are good.

[0104] Examples of the base that can be present when reacting the azide compound include imidazole compounds such as N-methylimidazole and imidazole; alkali metal salt compounds such as lithium hydroxide, sodium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; alkaline earth metal salt compounds such as magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, and barium carbonate; lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium isopropoxide, sodium isopropoxide, potassium isopropoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, and lithium tert-amyl Alkoxy alkali metal compounds such as alkoxide, sodium tert-amyl alkoxide, and potassium tert-amyl alkoxide; hydride alkali metal compounds such as lithium hydride, sodium hydride, and potassium hydride; amines (particularly tertiary amines) such as trimethylamine, triethylamine, tripropylamine, 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, and 1,8-diazabicyclo[5.4.0]undec-7-ene; and the like. Among these, at least one selected from imidazole compounds, alkali metal salt compounds, and amines is preferable, at least one selected from N-methylimidazole, potassium carbonate, triethylamine, and pyridine is more preferable, and pyridine is even more preferable.

[0105] 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, even more preferably 2 mol or more and 7 mol or less, and particularly preferably 3 mol or more and 5 mol or less, relative to 1 mol of the compound (6).

[0106] In the cyclization step, it is preferable not to use a solvent, but a solvent may be used. When a solvent is used, a solvent that does not affect the reaction can be used, and for example, an ether solvent, an aromatic solvent, an ester solvent, a hydrocarbon solvent, a halogen solvent, a ketone solvent, an amide solvent, etc. 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, dioxane, etc. Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, etc. Examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, heptane, etc. Examples of the halogen solvent include dichloromethane, chloroform, dichloroethane, dichloropropane, etc. 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, and 1,3-dimethyl-3,4,5,6-tetrahydro-(1H)-pyrimidine. Other examples of the solvent that can be used include nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethyl sulfoxide, and sulfone solvents such as sulfolane.

[0107] In order to increase the reaction efficiency, the reaction temperature in the cyclization step is preferably 0° C. or higher and 200° C. or lower, more preferably 30° C. or higher and 180° C. or lower, and even more preferably 40° C. or higher and 150° C. or lower. The reaction temperature may be adjusted using microwaves.

[0108] [Step E: Deprotection step] In step E, the protecting group in the compound (7) is deprotected to give the compound (1), as shown in the following formula.

[0109] [ka]

[0110] [In the formula, A 1 , n, R 1 , m, R 2 , R 6 are the same as above.]

[0111] The protecting group in the compound (7) can be removed by, for example, dissolving the compound (7) in a solvent and then adding an acid such as hydrochloric acid or acetic acid to adjust the pH, or by adding the compound (7) to a solution of dilute hydrochloric acid or acetic acid. Examples of the solvent that can be used include ether-based solvents such as diethyl ether and tetrahydrofuran; and nitrile-based solvents such as acetonitrile. The reaction temperature in the deprotection step is preferably, for example, 40° C. or higher and 90° C. or lower, and more preferably 50° C. or higher and 80° C. or lower.

[0112] 3. Method for producing condensation product The present invention also encompasses a method for producing a condensation product by condensing compound (1) with a first electron-withdrawing compound represented by the following formula (8a) or a second electron-withdrawing compound represented by the following formula (8b).

[0113] [ka]

[0114] [In the formula, R c represents an aromatic ring, E 1a each independently represents an electron-withdrawing group or a group represented by the following formula (X), 1b represents an electron-withdrawing group, an aromatic ring, or a group represented by the following formula (X), and p represents an integer of 1 to 3. 1a and E1b may be bonded to each other to form a heterocycle having a carbonyl group or a thiocarbonyl group as a ring member. 1a and E 1b is a group represented by the following formula (X), R 11 may be bonded together to form a ring. ·· indicates a carbon atom which forms a double bond by a condensation reaction.]

[0115] R c , E 1b Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring, with a benzene ring being preferred.

[0116] E 1a , E 1b Examples of the electron-withdrawing group include a halogen atom, a halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, a diarylphosphono group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, an acylthio group, a sulfamoyl group, a thiocyanate group, and a thiocarbonyl group, with a nitrile group being preferred.

[0117] [ka]

[0118] [In the formula, E 2 each independently represents an electron-withdrawing group; R 11 represents an organic group, and * represents a bond.

[0119] E 2 The electron-withdrawing group of E 1a , E 1b The electron-withdrawing groups are the same as those exemplified as the electron-withdrawing groups of the above.

[0120] R 11Examples of the organic group include an alkyl group, an alkoxy group, an alkylthiooxy group (an alkylthio group), an alkyloxycarbonyl group, an alkylsulfonyl group, an aryl group, an aralkyl group, an aryloxy group, an arylthiooxy group (an arylthio group), an aryloxycarbonyl group, an arylsulfonyl group, an arylsulfinyl group, an amide group (-NHCOR), a sulfonamide group (-NHSO 2 R), a carboxy group (a carboxylic acid group), a benzothiazole group, a halogenoalkyl group, a cyano group, etc. The number of carbon atoms in the organic group is, for example, about 1 to 30, preferably 1 to 10, and more preferably 1 to 3.

[0121] Since compound (1) contains an aldehyde group or a ketone group, the first electron-withdrawing compound represented by the above formula (8a) or the second electron-withdrawing compound represented by the above formula (8b) can be easily condensed with compound (1).

[0122] The compound of the above formula (8a) is preferably at least one selected from the following compound group (8A).

[0123] [ka]

[0124] [In the formula, Ar represents an aromatic ring; R 12 , R 13 , and R 14 Each of E independently represents a hydrogen atom or an organic group. 1a , and ·· are as defined above.]

[0125] Examples of the aromatic ring of Ar include an aromatic hydrocarbon ring and an aromatic heterocycle. 1 The aromatic hydrocarbon ring and aromatic heterocycle are the same as those described in the above. The aromatic hydrocarbon ring is preferably a benzene ring, and the aromatic heterocycle is preferably a thiophene ring. Ar is most preferably a benzene ring.

[0126] R12 , R 13 , and R 14 Examples of the organic group of R include an alkyl group, an alkoxy group, an alkylthiooxy group (alkylthio group), an alkyloxycarbonyl group, an alkylsulfonyl group, an aryl group, an aralkyl group, an aryloxy group, and a carboxy group (carboxylic acid group). 12 , R 13 , and R 14 The number of carbon atoms is, for example, about 1 to 30.

[0127] The compound (1) and the compound represented by the formula (8a) can be condensed to produce a condensate represented by the following formula (9a).

[0128] [ka]

[0129] [In the formula, A 1 , n, R 1 , m, R 2 , E 1a , E 1b are the same as above.]

[0130] In addition, by condensing the compound (1) with a compound represented by the formula (8b) in which p is 1, a condensation product represented by the following formula (9b) can be produced.

[0131] [ka]

[0132] [In the formula, A 1 , n, R 1 , m, R 2 , E 1a , R c are the same as above.]

[0133] As the compound represented by formula (8b) in which p is 1, the compound represented by the following formula is preferred.

[0134] [ka]

[0135] [In the formula, ·· has the same meaning as above. The benzene ring may be substituted with an alkyl group having 1 to 10 carbon atoms.]

[0136] This application claims the benefit of priority based on Japanese Patent Application No. 2019-143812, filed on August 5, 2019. The entire contents of the specification of Japanese Patent Application No. 2019-143812 are incorporated by reference into this application. EXAMPLES

[0137] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples, and can be modified within the scope of the above and below-mentioned aims, and all of these are included in the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0138] [Example] (Process A: Protection process)

[0139] [ka]

[0140] Pinacol (10.54g, 89.17mmol) and a catalytic amount of p-toluenesulfonic acid (500mg) were added to 2-thiophenecarbaldehyde (5.00g, 44.6mmol) and refluxed in benzene solvent (250mL). After the reaction, the mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate using a separatory funnel. The organic layer was dried over sodium sulfate, and the sodium sulfate was removed by natural filtration. After concentrating with an evaporator, the mixture was dried under reduced pressure and the compound was isolated and purified by alumina column chromatography (hexane / EtOAc=25 / 1) (7.38g, yield 78%). 1 H-NMR (CDCl 3 , 400 MHz): δ 7.31 (m, 1H), 7.16 (m, 1H), 6.98-6.95 (dd, J = 3.6, 3.6 Hz 1H), 6.21 (s, 1H), 1.34 (s, 6H), 1.30 (s, 1H).

[0141] (Step B: Trialkyltin Group Addition Step)

[0142] [ka]

[0143] The ketal molecule (4.03 mg, 18.96 mmol) obtained in the above reaction formula (a) was added dropwise to n-butyl lithium (13.2 mL, 1.57 M) in a THF (30 mL) solvent at -78 ° C., and stirred at -78 ° C. for 1 hour. Next, tributyltin (IV) chloride (6.79 g, 20.86 mmol) was added dropwise, and the mixture was returned to room temperature and stirred overnight. After the reaction, water was added, and the mixture was extracted with diethyl ether using a separatory funnel. The organic layer was dried with sodium sulfate, and the sodium sulfate was removed by natural filtration. After concentration with an evaporator, the mixture was dried under reduced pressure and purified by alumina column chromatography (hexane / EtOAc = 25 / 1) to isolate the tin compound (6.38 g, yield 67%). 1 H-NMR (CDCl 3 , 400 MHz): δ7.53(d, J = 3.2 Hz, 1H), 7.02 (d, J = 3.2 Hz, 1H), 6.24 (s, 1H), 12.9 (m, 6 H), 12.6 (m, 6 H).

[0144] (Step C': Oxidation step)

[0145] [ka]

[0146] 2,5-dibromopyridine (11.8 g, 50 mmol), mCPBA (18.5 g, 75 mmol), and anhydrous dichloromethane (100 mL) were placed in a 300 mL eggplant flask and stirred at room temperature for 2 days. After the reaction was completed, a saturated aqueous solution of sodium bicarbonate was added, and the organic layer was extracted with dichloromethane and dried using anhydrous sodium sulfate. After concentration, the mixture was purified using silica gel column chromatography (Hexane / AcOEt=5:1) to obtain 6.74 g of 2,5-dibromopyridine-N-oxide (white solid) (yield 53%). 1 H-NMR (400MHz, CDCl 3 ): δ=7.23(dd,J=2.1,8.7Hz,1H), 7.52(d,J=8.7Hz,1H), 8.50(d,J=2.1Hz,1H).

[0147] (Step C: Coupling Step)

[0148] [ka]

[0149] The ketal tin compound (1.03 g, 4.07 mmol) obtained in the above reaction formula (b) was dissolved in toluene (10.5 mL), and the 2,5-dibromopyridine-N-oxide (6.07 g, 12.11 mmol) obtained in the above reaction formula (c') and a catalytic amount of tetrakis(triphenylphosphine)palladium (469 mg, 0.41 mmol) were added and reacted at 180 ° C for 20 minutes under microwave irradiation conditions to perform a Stille coupling reaction. The tetrakis(triphenylphosphine)palladium was removed by filtration through Celite and collected as a chloroform solution. After concentrating with an evaporator, it was dried under reduced pressure and the coupling compound was isolated and purified by alumina column chromatography (hexane / EtOAc = 2 / 1) (1.46 g, yield 70%). 1 H-NMR (CDCl 3, 400 MHz):δ 8.52 (s, 1H), 7.88 (m, 1H), 7.72 (m, 1H), 7.45 (m, 1H), 7.13 (m, 1H), 6.24 (s, 1H), 6.16 (s, 1H), 1.57-1.24 (m, 24H).

[0150] (Step D: cyclization step)

[0151] [ka]

[0152] Diphenylphosphoryl azide (DPPA) (1.06 g, 3.85 mmol) and pyridine (1.15 g, 3.84 mmol) were added to the oligomer (396 mg, 0.77 mmol) obtained in the above reaction formula (c), and after replacing with nitrogen, the mixture was refluxed at 120°C overnight. After the reaction, the mixture was cooled to room temperature, washed with methanol, and the solid was collected by suction filtration. The solid was dissolved in a small amount of chloroform and sprinkled on the mixture, and the compound was isolated (126 mg, yield 30%) by alumina column chromatography (hexane / EtOAc = 3 / 1). 1 H-NMR (CDCl 3 , 400 MHz): δ 8.34-8.33 (d, J = 3.6 Hz, 1H), 8.29-8.28 (d, J = 4.0 Hz, 1H), 7.86-7.84 (d, J = 8.0 Hz, 1H), 7.52-7.50 (d, J = 7.6 Hz, 1H), 7.30-7.29 (d, J = 3.2 Hz, 1H), 7.24-7.23 (d, J = 4.4 Hz, 1H), 6.26-6.23(m, 2H), 1.36-1.34 (m, 12H).

[0153] (Step E: Deprotection step)

[0154] [ka]

[0155] 1N hydrochloric acid (16 mL) was added to the tetrazole (126 mg, 0.233 mmol) obtained in the above reaction formula (d) in tetrahydrofuran (THF) solvent (38 mL) and reacted at 60°C overnight. After the reaction, the mixture was cooled, neutralized with an aqueous ammonium chloride solution, and extracted with chloroform. After concentrating with an evaporator, the mixture was dried under reduced pressure, washed with methanol, hexane, and diethyl ether in that order, and the solid was collected by suction filtration (20 mg, yield 25%). 1 H-NMR (CDCl 3 , 400 MHz): δ 10.058 (s, 1H), 10.016 (s, 1H), 8.647-8.637 (d, J = 4.0 Hz, 1H), 8.552-8.542 (d, J = 4.0 Hz, 1H), 8.081-8.062 (d, J = 7.6 Hz, 1H), 7.945-7.935 (d, J = 4.0 Hz, 1H), 7.919-7.908 (d, J = 4.4 Hz, 1H), 7.759-7.740 (d, J = 7.6 Hz, 1H).

[0156] (Condensation Product Manufacturing Process)

[0157] [ka]

[0158] Toluene (6 mL), cyanoester (29 mg, 0.123 mmol), and a catalytic amount of piperidine (15 mg) were added to the aldehyde (20 mg, 0.059 mmol) obtained in the above reaction formula (e), and the mixture was refluxed overnight. The reaction solution was recovered with chloroform, concentrated with an evaporator, and then dried under reduced pressure. After drying, the mixture was purified by silica gel column chromatography and washed with methanol. 1 The structure was identified by H-NMR (35 mg, yield 93%). 1 H-NMR (CDCl 3, 400 MHz): δ 8.685-8.675 (d, J = 4.0 Hz, 1H), 8.576-8.566 (d, J= 4.0 Hz, 1H), 8.378 (s, 2H), 8.321-8.305 (d, J = 6.4 Hz, 1H), 8.095-8.075 (d, J = 8.0 Hz, 1H), 8.010-7.999 (d, J = 4.4 Hz, 1H), 7.921-7.911 (d, J = 4.0 Hz, 1H), 7.819 (m, 1 H), 7.770-7.749 (d, J = 8.4 Hz, 2H), 4 36-4.32 (m, 8H), 1.80 (m, 8H), 1.36 (m, 8H), 1.35 (m, 16H), 0.92 (m, 12H)。

Claims

1. A compound represented by formula (1). 【Chemistry 1】 [In formula (1), R 1 represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, m represents an integer of 0 to 2. R 1 When more than one is present, they may be different from each other. A 1 each independently represents an aromatic ring which may have a substituent, n represents an integer of 1 to 5; R 2 each independently represents a hydrogen atom or an alkyl group.

2. A carbonyl group of an aromatic carbonyl compound represented by the following formula (2) is protected, and the aromatic ring A of the formula (2) is 1 to produce a tin compound represented by the following formula (4): a step of reacting the tin compound represented by formula (4) with a pyridine-N-oxide compound represented by formula (5) below to produce a coupling compound represented by formula (6) below; A step of deprotecting the carbonyl group of the coupling compound of the following formula (6) and cyclizing the pyridine-N-oxide: A method for producing a compound represented by formula (1) according to claim 1, comprising: 【Chemistry 2】 [In the formula, A 1 , n, R 1 , m, R 2 are as defined in claim 1, R 6 , R 7 represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom.

3. A method for producing a condensation product, comprising condensing a compound represented by formula (1) according to claim 1 with a first electron-withdrawing compound represented by formula (8a) or a second electron-withdrawing compound represented by formula (8b). 【Chemistry 3】 [In the formula, R c represents an aromatic ring, E 1a each independently represents an electron-withdrawing group or a group represented by the following formula (X): E 1b represents an electron-withdrawing group, an aromatic ring, or a group represented by the following formula (X) (wherein E １ａ is a group represented by the following formula (X), E １ｂ is an aromatic ring), p represents an integer of 1 to 3. E in formula (8a) 1a and E. 1b is a group represented by the following formula (X), R 11 They may be bonded to each other to form a ring. ... represents a carbon atom that forms a double bond by a condensation reaction, and the carbon atom and the carbon atom in the carbonyl group represented by formula (1) form a C=C bond.] 【Chemistry 4】 [In the formula, E 2 each independently represents an electron-withdrawing group, R 11 represents an organic group, the organic group being an alkyl group, an alkoxy group, an alkylthiooxy group, an alkyloxycarbonyl group, an alkylsulfonyl group, an aryl group, an aralkyl group, an aryloxy group, an arylthiooxy group, an aryloxycarbonyl group, an arylsulfonyl group, an arylsulfinyl group, an amido group, a sulfonamide group, a carboxy group, a benzothiazole group, a halogenoalkyl group, or a cyano group; * represents a bond. E 1a , E 1b , E 2 In the above formula, the electron-withdrawing group is a halogen atom, a halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, a diarylphosphono group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, an acylthio group, a sulfamoyl group, a thiocyanate group, or a thiocarbonyl group.]

4. The method for producing a condensate according to claim 3, wherein the condensate of the compound represented by formula (1) and the compound represented by formula (8a) is represented by the following formula (9a): 【Chemistry 5】 [In the formula, A 1 , n, R 1 , m, and R2 are as defined in claim 1, E 1a and E 1b are as defined in claim 3.]

5. A method for producing a condensation product, comprising condensing a compound represented by formula (1) according to claim 1 with at least one compound selected from the following compound group (8A): 【Chemistry 6】 [In the formula, Ar represents an aromatic ring; R 12 represents a hydrogen atom or an organic group, and the organic group is an alkyl group, an alkoxy group, an alkylthiooxy group, an alkyloxycarbonyl group, an alkylsulfonyl group, an aryl group, an aralkyl group, an aryloxy group, or a carboxy group. E 1a , ... are as defined in claim 3.

6. The method for producing a condensate according to claim 3, wherein the condensate of the compound represented by formula (1) and the compound represented by formula (8b) in which p is 1 is represented by the following formula (9b). 【Chemistry 7】 [In the formula, A 1 , n, R 1 , m, and R2 are as defined in claim 1, E 1a and R c are as defined in claim 3.]

7. A compound represented by the following formula (9a): 【Chemistry 8】 [In the formula, A 1 , n, R 1 , m, and R2 are as defined in claim 1, E 1a and E 1b are as defined in claim 3.]

8. A compound represented by the following formula (9b): 【Chemistry 9】 [In the formula, A 1 , n, R 1 , m, and R2 are as defined in claim 1, E 1a and R c are as defined in claim 3.]

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