WO2016143823A1 - Composé et matériau semi-conducteur organique contenant celui-ci - Google Patents

Composé et matériau semi-conducteur organique contenant celui-ci Download PDF

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WO2016143823A1
WO2016143823A1 PCT/JP2016/057383 JP2016057383W WO2016143823A1 WO 2016143823 A1 WO2016143823 A1 WO 2016143823A1 JP 2016057383 W JP2016057383 W JP 2016057383W WO 2016143823 A1 WO2016143823 A1 WO 2016143823A1
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compound
group
formula
aromatic ring
integer
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Japanese (ja)
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俊輔 丹波
家　裕隆
安蘇　芳雄
一剛 萩谷
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国立大学法人大阪大学
東洋紡株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets

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  • the present invention relates to a tetrazolopyridine compound.
  • a 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.
  • 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.
  • the effect of using the above compound as an organic semiconductor material has not been known.
  • the above compounds may not have sufficient thermal stability.
  • 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.
  • the compound of the present invention is represented by the 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
  • 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).
  • a 1 represents an optionally substituted aromatic ring or a halogen atom.
  • two or more A 1 are an aromatic ring substituted with a halogen atom or a halogen atom.
  • 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).
  • 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
  • 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.
  • 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
  • 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.
  • a 1 represents an optionally substituted aromatic ring or a halogen atom.
  • the present invention includes a compound represented by the following formula.
  • 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
  • r represents an integer of 1 or more. However, either n7 or r is 2 or more.
  • 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.
  • 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).
  • 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).
  • 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
  • n represents an integer of 2 to 4. However, m + n is 4. ]
  • 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.
  • R 1 and A 1 are as defined above.
  • 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.
  • 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)).
  • 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
  • n3 represents an integer of 1 to 3.
  • m + n1 and m + n2 + n3 are 4 or less.
  • the halogen atom of X 1 is the same as the halogen atom of A 1
  • 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.
  • two or more A 1 are preferably an aromatic ring substituted with a halogen atom or a halogen atom.
  • 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.
  • 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.
  • 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.
  • aliphatic hydrocarbon group for R 1 examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group.
  • 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.
  • alicyclic hydrocarbon group for R 1 examples 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.
  • R 1 is preferably a hydrogen atom or an aliphatic hydrocarbon group, and more preferably a hydrogen atom.
  • halogen atom for A 1 examples 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.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine 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.
  • alkyl group examples 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.
  • alkoxy group examples 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.
  • 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.
  • 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.
  • the aromatic ring represented by A 1 is preferably an aromatic ring represented by the following formula.
  • 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
  • p4 represents an integer of 0 to 4.
  • halogen atom for R 2 examples 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.
  • 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.
  • the formulas (Ar1) to (Ar8) are preferable, and the formulas (Ar1) to (Ar4) are respectively the following formulas (Ar1-1) to (Ar4-1) Is more preferable.
  • X 2 is preferably bonded to the 2-position, and in (Ar3-1), X 2 is bonded to the 4-position. It is preferable.
  • 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
  • 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
  • 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).
  • each formula number means a group represented by the following formula.
  • R 4 has the same meaning as above, and * represents a bond.
  • 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).
  • 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
  • n5 represents an integer of 1 to 3.
  • k1 represents an integer of 2 or 3.
  • 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).
  • 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),
  • R 1 , A x1 , X 1 , m, n4, and n5 have the same meanings as described above. ]
  • 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
  • the aromatic ring may be substituted with a halogen atom (halogenation step: step 9).
  • R 1 , A 3 , X 1 , m, n4 and n5 have the same meanings as described above. ]
  • the compound (2) can be obtained by reacting the compound (3) with an oxidizing agent.
  • an oxidizing agent for example, a compound represented by the following formula (3-I) is preferable.
  • a percarboxylic acid such as metachloroperbenzoic acid
  • 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).
  • halogen solvents such as dichloromethane, chloroform, dichloroethane, dichloropropane and the like are preferable.
  • 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)
  • the compound (2) which has an aromatic ring can be manufactured by making it react with the compound (henceforth "compound (4)") represented by these.
  • compound (4) represented by these.
  • a compound represented by the following formula (2-I) is preferable, and a compound (2A) is preferable.
  • each formula number has the same meaning as described above.
  • 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.
  • examples of * -M 1 (L 1 ) k1 include groups represented by the following formulae.
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (preferably a hydrogen atom). * Represents a bond.
  • examples of * -M 1 (L 1 ) k1 include groups represented by the following formulae. In the formula, * represents a bond.
  • 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).
  • a catalyst When reacting compound (2) and compound (4), a catalyst may coexist.
  • 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.
  • the palladium-based catalyst examples 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 (diphenyl
  • 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 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-methoxyphen
  • the molar ratio of the catalyst to the 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.
  • a base When reacting compound (2) and compound (4), a base may be allowed to coexist.
  • a base 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.
  • 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 is generally about 1: 1 to 1:10, and from the viewpoint of yield and reaction efficiency, 1: 1.5 to 1: 8
  • 1: 1.8 to 1: 6 is more preferable, and 1: 2 to 1: 5 is more preferable.
  • reaction solvent a solvent that does not affect the reaction
  • ether solvents aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents, amide solvents, and the like are used.
  • 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.
  • amide solvent examples 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • R 1 and R 2 are each preferably bonded to any of the 2 to 5 positions, and examples thereof include the following arrangements.
  • R 1 and A 1 are as defined above.
  • 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.
  • 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)).
  • 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).
  • R 3 has the same meaning as above, and * represents a bond.
  • each formula number has the same meaning as described above.
  • 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)
  • azide compounds examples 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.
  • 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.
  • a sulfonyl halide compound or a phosphoric acid halide compound coexist.
  • 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-ch
  • 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.
  • 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 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
  • 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.
  • reaction solvent it is preferable not to use a reaction solvent.
  • a reaction solvent it can be used as long as it does not affect the reaction.
  • an ether solvent examples 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.
  • amide solvent examples 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.
  • 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.
  • 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
  • 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.
  • aromatic solvents such as benzene solvents, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene.
  • 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. .
  • 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.
  • 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.
  • n7 is preferably 1 or 2.
  • r is preferably 1 or 2.
  • 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).
  • (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.
  • 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.
  • 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).
  • 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.
  • compound (IIB) can be produced by the following three routes.
  • 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).
  • 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).
  • each step will be described.
  • Aromatic ring addition step 2 (steps 12 and 14) In the aromatic ring addition step 2, compound (IIA3) and compound (IIA4)
  • compound (IIA2) can be reacted to produce compound (IIA2).
  • compound (IIA3) used in this step include compound (2E) having an aromatic ring substituted with a halogen atom among compounds (2) exemplified above.
  • compound (IIA) can be produced by reacting compound (IIA5) with compound (IIA4).
  • 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.
  • 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.
  • 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.
  • the reaction temperature in the aromatic ring addition step 2 is the same as that in the aromatic ring addition step 1.
  • 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)
  • 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.
  • (ArI-1) has the same meaning as above.
  • 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.
  • the bases exemplified in the aromatic ring addition step 1 may coexist on the same conditions.
  • 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.
  • 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.
  • 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.
  • the same conditions as in the cyclization step 1 can be employed for the reaction solvent and the reaction temperature.
  • Organometallic compound addition step (step 16) Compound (IID) can be obtained by reacting compound (IIC) with a base and a halogenated organometallic compound.
  • M 12 is preferably a tin atom.
  • (IIC) for example, a compound represented by the following formula is preferable.
  • (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.
  • alkyl lithium examples include n-butyl lithium, sec-butyl lithium, and tert-butyl lithium.
  • alkyl metal amide examples 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.
  • alkylmagnesium and the magnesium complex examples include tert-butylmagnesium chloride, ethylmagnesium chloride, 2,2,6,6-tetramethylpiperidinylmagnesium chloride, and lithium chloride complex.
  • alkali metal hydride examples include lithium hydride, sodium hydride, and potassium hydride.
  • 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 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.
  • 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.
  • halogenated cycloalkyl tin compound examples include tricyclohexyl tin chloride and tricyclohexyl tin bromide.
  • halogenated aryl tin compound examples include triphenyl tin chloride, tribenzyl tin chloride, triphenyl tin bromide, and tribenzyl tin bromide.
  • 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.
  • 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.
  • an ether solvent As the reaction solvent, an ether solvent, a hydrocarbon solvent, or the like can be used.
  • the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether, and dioxane.
  • 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.
  • Multimerization process 2 (process 17)
  • Compound (IIB) can be obtained by reacting compound (IID) with compound (IIE) in the presence of a metal catalyst.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • compound (IIB) can be obtained by reacting compound (IIC) with compound (IIF) in the presence of a base and a metal catalyst.
  • compound (IIF) a compound represented by the following formula is preferable.
  • (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).
  • the base 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.
  • 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.
  • a copper catalyst is preferable.
  • the copper-based catalyst examples 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.
  • 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.
  • reaction solvent and reaction temperature the same conditions as in the organometallic compound addition step can be employed.
  • 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.
  • the structural unit (I) derived from the compound (1) is also included in the technical scope of the present invention.
  • R 1 , A 20 , m, and n7 are as defined above.
  • R 1 , A 20 , m, and n7 are as defined above.
  • it Since it is electron accepting and can be expected to function as an acceptor unit in an extended ⁇ -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.
  • 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).
  • R 30 represents an aliphatic hydrocarbon group
  • 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.
  • R 1 , A x1 , X 1 , m, n4 and n5 have the same meanings as described above. ]
  • 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.
  • the same catalyst as that used in the aromatic ring addition step 1 can be used.
  • the palladium of the palladium-based catalyst may be zero-valent or divalent.
  • 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.
  • tris (dibenzylideneacetone) dipalladium (0) and tris (dibenzylideneacetone) dipalladium (0) chloroform adduct are particularly preferable.
  • the molar ratio of the compound (1) to the 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.
  • a specific ligand may be coordinated with the catalyst.
  • 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.
  • the molar ratio of the catalyst to the 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.
  • a solvent that does not affect the reaction can be used.
  • ether solvents aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents
  • An amide solvent or the like can be used.
  • 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.
  • ketone solvent examples include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro- (1H ) -Pyrimidinone.
  • nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethyl sulfoxide, and sulfone solvents such as sulfolane can be used.
  • 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 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.
  • 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.
  • Step 3 Synthesis of 2,5- (dithiophen-2-yl) pyridine-N-oxide
  • Step 9 Synthesis of 2,5-bis (5-bromothiophenyl) tetrazolopyridine (Compound (Tz-2))
  • Step 15 Synthesis of pyridine-N-oxide hexamer
  • Step 16 Synthesis of tetrazolopyridine hexamer (compound (Tz-4))
  • Step 4 Synthesis of 2,5-bis (4-methoxyphenyl) tetrazolopyridine (Compound (Tz-8))
  • Step 4 Synthesis of 2,5-bis (4-trifluoromethylphenyl) tetrazolopyridine (Compound (Tz-9))
  • Step 4 2,5-bis (piperidin-2-yl) tetrazolopyridine (compound (Tz-10))
  • Example 5 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%).
  • Step 4 Synthesis of 2,5-bis (piperidin-4-yl) tetrazolopyridine (Compound (Tz-11))
  • Step 3 Synthesis of 2- (piperidin-2-yl) -5- (piperidin-4-yl) pyridine-N-oxide
  • Step 4 Synthesis of 2- (piperidin-2-yl) -5- (piperidin-4-yl) tetrazolopyridine (Compound (Tz-12))
  • Step 3 Synthesis of 2- (piperidin-2-yl) -5- (piperidin-4-yl) pyridine-N-oxide
  • Step 4 Synthesis of 2- (piperidin-4-yl) -5- (piperidin-2-yl) tetrazolopyridine (Compound (Tz-13))
  • Step 4 Synthesis of 2- (piperidin-4-yl) -5- (piperidin-2-yl) tetrazolopyridine (Compound (Tz-14))
  • Step 4 Synthesis of 2- (piperidin-4-yl) -5- (piperidin-2-yl) tetrazolopyridine (Compound (Tz-15))
  • Step 4 Synthesis of 2- (thiophen-2-yl) -5- (5-hexylthiophen-2-yl) tetrazolopyridine (Compound (Tz-16))
  • Step 19 Synthesis of pyridine-N-oxide hexamer (compound (Tz-4))
  • Step 3 Synthesis of 2- (5-hexylthiophen-2-yl) -5- (thiophen-2-yl) tetrazolopyridine
  • Step 17 Synthesis of 2- (5-tributylstannylthiophen-2-yl) -5- (5-hexylthiophen-2-yl) tetrazolopyridine
  • Step 9 Synthesis of 2- (5-hexylthiophen-2-yl) -5- (5-bromothiophen-2-yl) tetrazolopyridine
  • Step 18 Synthesis of pyridine-N-oxide hexamer (compound (Tz-4))
  • thermogravimetric analysis measurement Thermogravimetric Analysis Measurement
  • TGA-50 thermogravimetric analyzer
  • 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.
  • 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'objectif de la présente invention est de fournir un composé tétrazolopyridine qui est utile en tant que matériau semi-conducteur organique, qui est également utile en tant qu'agent de génération de gaz grâce à son excellente stabilité thermique, et qui est en outre utile en tant que matière première pour divers composés. Le composé selon la présente invention est caractérisé en ce qu'il est représenté par la formule (1). (Dans la formule (1), R1 représente un atome d'hydrogène, un groupe hydrocarboné aliphatique, ou un groupe hydrocarboné alicyclique, A1 représente un cycle aromatique qui peut être substitué ou un atome d'halogène, m représente un nombre entier de 0 à 2, n représente un nombre entier de 2 à 4, m + n est 4.)
PCT/JP2016/057383 2015-03-10 2016-03-09 Composé et matériau semi-conducteur organique contenant celui-ci WO2016143823A1 (fr)

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WO2018051979A1 (fr) * 2016-09-14 2018-03-22 国立大学法人大阪大学 Composé polymère et matériau semi-conducteur organique en comprenant
WO2019078040A1 (fr) * 2017-10-18 2019-04-25 国立大学法人大阪大学 Composé, corps lié de celui-ci, et matériau semi-conducteur organique
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WO2019181645A1 (fr) * 2018-03-22 2019-09-26 国立大学法人大阪大学 Composé, précurseur de composé, matériau semi-conducteur organique comprenant le composé, et dispositif électronique organique comprenant le matériau semi-conducteur organique
WO2020195632A1 (fr) * 2019-03-27 2020-10-01 国立大学法人大阪大学 Composé et matériau semi-conducteur organique contenant ledit composé
WO2021024675A1 (fr) * 2019-08-05 2021-02-11 国立大学法人大阪大学 Composé et son procédé de fabrication

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Cited By (13)

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WO2017155030A1 (fr) * 2016-03-09 2017-09-14 国立大学法人大阪大学 Composé et matériau semi-conducteur organique contenant celui-ci
WO2018051979A1 (fr) * 2016-09-14 2018-03-22 国立大学法人大阪大学 Composé polymère et matériau semi-conducteur organique en comprenant
JPWO2019078040A1 (ja) * 2017-10-18 2021-01-21 国立大学法人大阪大学 化合物またはその結合物、及び有機半導体材料
WO2019078040A1 (fr) * 2017-10-18 2019-04-25 国立大学法人大阪大学 Composé, corps lié de celui-ci, et matériau semi-conducteur organique
JP7320784B2 (ja) 2017-10-18 2023-08-04 国立大学法人大阪大学 化合物の結合物、及び有機半導体材料
WO2019181646A1 (fr) * 2018-03-22 2019-09-26 国立大学法人大阪大学 Composé macromoléculaire, matériau semi-conducteur organique comprenant un composé macromoléculaire, et dispositif électronique organique comprenant un matériau semi-conducteur organique
JPWO2019181645A1 (ja) * 2018-03-22 2021-03-25 国立大学法人大阪大学 化合物、化合物の前駆体、化合物を含む有機半導体材料、および有機半導体材料を含む有機電子デバイス
JPWO2019181646A1 (ja) * 2018-03-22 2021-03-25 国立大学法人大阪大学 高分子化合物、高分子化合物を含む有機半導体材料、および有機半導体材料を含む有機電子デバイス
JP7194392B2 (ja) 2018-03-22 2022-12-22 国立大学法人大阪大学 高分子化合物、高分子化合物を含む有機半導体材料、および有機半導体材料を含む有機電子デバイス
JP7308489B2 (ja) 2018-03-22 2023-07-14 国立大学法人大阪大学 化合物、化合物の前駆体、化合物を含む有機半導体材料、および有機半導体材料を含む有機電子デバイス
WO2019181645A1 (fr) * 2018-03-22 2019-09-26 国立大学法人大阪大学 Composé, précurseur de composé, matériau semi-conducteur organique comprenant le composé, et dispositif électronique organique comprenant le matériau semi-conducteur organique
WO2020195632A1 (fr) * 2019-03-27 2020-10-01 国立大学法人大阪大学 Composé et matériau semi-conducteur organique contenant ledit composé
WO2021024675A1 (fr) * 2019-08-05 2021-02-11 国立大学法人大阪大学 Composé et son procédé de fabrication

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