Method for producing condensed polycyclic aromatic heterocyclic compound and condensed polycyclic aromatic heterocyclic compound

Abstract

To provide a method for producing a novel condensed polycyclic aromatic heterocyclic compound having a basic framework suitable for devices, using a general-use condensed ring compound as a starting raw material, and also to provide a condensed polycyclic aromatic heterocyclic compound having a small full width at half maximum of the fluorescence spectral peak.SOLUTION: In the coexistence of a trivalent iron compound, a trivalent phosphorus compound, and trialkylaluminum, a coupling reaction is induced between an oxime ether and an acetylene derivative, to produce a condensed polycyclic aromatic heterocyclic compound having an extended ring structure.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a fused polycyclic aromatic heterocyclic compound using an iron catalyst. The present invention also relates to a fused polycyclic aromatic heterocyclic compound having a maximum peak in a fluorescence spectrum with a narrow half-width. [Background technology]

[0002] Organic semiconductor materials are used in devices such as PLED, OLED, OFET, OPV, PSC, pe-LED, and CMOS. Organic hole transport materials, electron transport materials, and host materials require new polycyclic aromatic hydrocarbon ring groups and polycyclic aromatic heterocyclic groups as their basic skeletons. However, due to the complexity of synthesis and reduced solubility, the polycyclic aromatic heterocyclic skeletons suitable for the above devices have been limited.

[0003] For example, in the method for producing a polycyclic aromatic heterocyclic compound, organic pigments such as quinacridone and acridone are known as basic skeletons (starting materials), but these are planar polycyclic aromatic heterocyclic compounds, and it has been difficult to use these as starting materials to derive various polycyclic aromatic heterocyclic compounds for the above-mentioned purpose due to their very low solubility. For this reason, a quinacridone skeleton that ensures solubility by introducing an alkyl group into the NH group of quinacridone is sometimes used, but it has been difficult to synthesize a polycyclic aromatic heterocyclic compound with a further expanded ring structure (see Non-Patent Document 1). [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] “Physical Sciences Reviews”, Vol. 7, No. 2, June 30, 2021 Internet (URL: https: / / doi.org / 10.1515 / psr-2020-0195) Summary of the Invention [Problem to be solved by the invention]

[0005] As described above, in the conventional methods, it was difficult to synthesize polycyclic aromatic heterocyclic compounds by using quinacridone, acridone, or the like as starting materials and expanding the ring structure of these compounds, and it was also difficult to produce new fused polycyclic aromatic heterocyclic compounds having a basic skeleton suitable for devices, including solubility.

[0006] An object of the present invention is to solve the above-mentioned problems of the conventional art and to provide a method for producing a novel fused polycyclic aromatic heterocyclic compound having a basic skeleton suitable for devices, using a general-purpose fused ring compound as a starting material.

[0007] In particular, the object of the present invention is to obtain a fused polycyclic aromatic heterocyclic compound having an expanded ring structure by converting a carbonyl group of a starting skeleton such as quinacridone, acridone, 2,3-dehydro-4(1H)-quinolinone, 4(1H)-quinolinone, thiochromanone, 1-thiochromone, chromanone, chromone, 1-tetralone, 1(4H)-naphthalenone, 1-indanone, or 1H-indenone-1-one, which forms a fused ring, into an oxime ether, and then reacting the obtained oxime ether with an acetylene derivative in the presence of an iron catalyst. Another object of the present invention is to provide a fused polycyclic aromatic heterocyclic compound having a maximum peak in a fluorescence spectrum with a narrow half-width. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems, and as a result have found that a fused polycyclic aromatic heterocyclic compound having an extended ring structure can be produced by carrying out a coupling reaction between an oxime ether and an acetylene derivative in the coexistence of a trivalent iron compound, a trivalent phosphorus compound, and a trialkylaluminum, and that this fused polycyclic aromatic heterocyclic compound has a small half-width of the maximum peak in the fluorescence spectrum. That is, the gist of the present invention lies in the following.

[0009] [1] A method for producing a fused polycyclic aromatic heterocyclic compound represented by the following general formula (I) by reacting an oxime ether with an acetylene derivative, the method comprising the steps of:

[0010] [ka]

[0011] (In the above formula (I), Y I , Y II each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or a divalent aliphatic hydrocarbon group which may have a substituent. R I ~R V each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, a silyl group which may have a substituent, or a hydrogen atom. Z I ~Z III each independently represents an element of Group 14, 15 or 16 of the periodic table which may have a substituent, or a hydrogen atom. In formula (I), Z I and Y I , Z II and Y II may be bonded directly or via a linking group to form a ring. A I ~A IX each independently has an optional substituent. m represents an integer.)

[0012] [2] A method for producing a fused polycyclic aromatic heterocyclic compound represented by the following formula (II), (III), (IV), or (V) by reacting an oxime ether with an acetylene derivative, in which the reaction is carried out in the presence of a trivalent iron compound, a trivalent phosphorus compound, and a trialkylaluminum.

[0013] [ka]

[0014] (In the above formulas (II), (III), (IV), and (V), R 1 ~R 12 each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, a silyl group which may have a substituent, or a hydrogen atom. Z 1 ~Z 12 Z each independently represents an element of Group 14, 15, or 16 of the periodic table which may have a substituent, or a hydrogen atom. 1 and Z 2 , Z 3 and Z 4 , Z 5 and Z 6 , Z 7 and Z 8 , Z 9 and Z 10 , Z 11 and Z 12 may be bonded directly or via a linking group, or may form a ring. A 1 ~A 12 , B 1 ~B 10 and C 1 ~C 6 each independently represents an arbitrary substituent. The dotted line in formula (II) represents an ethylene group which may have a substituent, or an ethynylene group which may have a substituent.

[0015] [3] The method for producing a fused polycyclic aromatic heterocyclic compound according to [1] or [2], wherein the trivalent phosphorus compound includes a compound represented by the following formula (VI):

[0016] [ka]

[0017] (In the above formula (VI), R 13 , R 14 each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aliphatic hydrocarbon group which may have a substituent. X represents a nitrogen atom, an oxygen atom, or a sulfur atom, each of which may have a substituent.

[0018] [4] The method for producing a fused polycyclic aromatic heterocyclic compound according to any one of [1] to [3], wherein the reaction is further carried out in the presence of one or more of a bidentate ligand capable of forming a 6-membered or 5-membered ring complex with aluminum, catechol, 1,8-dihydroxynaphthalene, and derivatives thereof.

[0019] [5] The method for producing a fused polycyclic aromatic heterocyclic compound according to any one of [1] to [4], wherein the reaction is carried out in the presence of one or more reaction solvents selected from the group consisting of ether solvents, aromatic solvents, and halogenated solvents.

[0020] [6] A condensed polycyclic aromatic heterocyclic compound represented by the following formula (I):

[0021] [ka]

[0022] (In the above formula (I), Y I , Y II each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or a divalent aliphatic hydrocarbon group which may have a substituent. R I ~R V each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, a silyl group which may have a substituent, or a hydrogen atom. Z I ~Z III each independently represents an element of Group 14, 15 or 16 of the periodic table which may have a substituent, or a hydrogen atom. In formula (I), Z I and Y I , Z II and Y II may be bonded directly or via a linking group to form a ring. A I ~A IX each independently has an optional substituent. m represents an integer.)

[0023] [7] A fused polycyclic aromatic heterocyclic compound represented by the following formula (II), (III), (IV) or (V):

[0024] [ka]

[0025] (In the above formulas (II), (III), (IV), and (V), R 1 ~R 12 each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, a silyl group which may have a substituent, or a hydrogen atom. Z 1 ~Z 12 Z each independently represents an element of Group 14, 15, or 16 of the periodic table which may have a substituent, or a hydrogen atom. 1 and Z 2 , Z 3 and Z 4 , Z 5 and Z 6 , Z7 and Z 8 , Z 9 and Z 10 , Z 11 and Z 12 may be bonded directly or via a linking group, or may form a ring. A 1 ~A 12 , B 1 ~B 10 and C 1 ~C 6 each independently represents an arbitrary substituent. The dotted line in formula (II) represents an ethylene group which may have a substituent, or an ethynylene group which may have a substituent.

[0026] [8] The fused polycyclic aromatic heterocyclic compound according to [6] or [7], wherein the half-value width of the maximum peak of the fluorescence spectrum is 25 nm or less. Effect of the Invention

[0027] According to the present invention, a fused polycyclic aromatic heterocyclic compound having an expanded ring structure can be produced by carrying out a coupling reaction between an oxime ether and an acetylene derivative in the presence of a specific catalyst. Furthermore, according to the present invention, it is possible to provide a fused polycyclic aromatic heterocyclic compound having a maximum peak in a fluorescence spectrum with a narrow half-width. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] The following is a detailed description of the embodiments of the present invention. The following description of the components is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to these contents as long as it does not deviate from the gist of the present invention.

[0029] [Functional Groups According to the Invention] Prior to a detailed description of the method for producing the fused polycyclic aromatic heterocyclic compound of the present invention and the compound, each functional group according to the present invention will be described.

[0030] The functional groups described in the formulas (I) to (V) and the formulas (VI), (VII) and (VIIa), (VIII) and (VIIIa), (IX) and (IXa), and (X) in the present invention include those described in "Guide to Naming Organic Compounds" (1990) published by Kagaku Dojin, and specifically, are as follows:

[0031] In the present invention, those not specifically labeled "divalent" represent "monovalent" functional groups.

[0032] <Aromatic hydrocarbon group> Examples of the aromatic hydrocarbon group include aryl groups having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, an anthranyl group, a fluorenyl group, a phenanthrenyl group, and an azulenyl group. Examples of the divalent aromatic hydrocarbon group include arylene groups having 6 to 20 carbon atoms, such as a phenylene group, a naphthylene group, an anthranylene group, a fluorenylene group, a phenanthrenylene group, and an azulenylene group.

[0033] <Aromatic heterocyclic group> Examples of the aromatic heterocyclic group include heteroaryl groups having 2 to 18 carbon atoms, such as a thienyl group, an imidazolyl group, a pyrazolyl group, and a thiazolyl group. Examples of the divalent aromatic heterocyclic group include heteroarylene groups having 2 to 18 carbon atoms, such as a thienylene group, an imidazolylene group, a pyrazolylene group, and a thiazolylene group.

[0034] <Aliphatic hydrocarbon group> Examples of the aliphatic hydrocarbon group include saturated aliphatic hydrocarbon groups such as alkyl groups, unsaturated aliphatic hydrocarbon groups having a carbon-carbon double bond such as alkenyl groups, and unsaturated aliphatic hydrocarbon groups having a carbon-carbon triple bond such as alkynyl groups. The unsaturated aliphatic hydrocarbon group may have a plurality of carbon-carbon double bonds and / or carbon-carbon triple bonds. The aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms (2 or more carbon atoms in the case of an unsaturated aliphatic hydrocarbon group), particularly preferably 1 to 10 carbon atoms (2 or more carbon atoms in the case of an unsaturated aliphatic hydrocarbon group).

[0035] Examples of the divalent aliphatic hydrocarbon group include divalent saturated aliphatic hydrocarbon groups such as alkylene groups, divalent unsaturated aliphatic hydrocarbon groups having a carbon-carbon double bond such as alkenylene groups, divalent unsaturated aliphatic hydrocarbon groups having a carbon-carbon triple bond such as alkynylene groups, etc. The divalent unsaturated aliphatic hydrocarbon group may have a plurality of carbon-carbon double bonds and / or carbon-carbon triple bonds. The divalent aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms (2 or more carbon atoms in the case of an unsaturated aliphatic hydrocarbon group), particularly preferably 1 to 10 carbon atoms (2 or more carbon atoms in the case of an unsaturated aliphatic hydrocarbon group).

[0036] <Substituent> When the above aromatic hydrocarbon group, aromatic heterocyclic group, aliphatic hydrocarbon group, silyl group, element of Groups 14 to 16 of the periodic table, or nitrogen atom has a substituent, it may have only one substituent, or may have two or more substituents within the range of the allowable substitution positions. The two or more substituents may be the same or different.

[0037] Examples of the substituents which these groups may have include those described in "Guide to Naming Organic Compounds" (1990) published by Kagaku Dojin. Examples of such an alkyl group include a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, an amino group, an acyl group, an aminoacyl group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a sulfamoylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a heteroarylsulfonyl group, an imido group, and a silyl group.

[0038] Specifically, the following applies: Halogen atoms: fluorine, chlorine, bromine, and iodine; Alkyl groups having 1 to 15 carbon atoms, such as methyl and ethyl groups; Alkenyl groups having about 2 to 10 carbon atoms, such as ethynyl and propylenyl groups; Alkynyl groups with 2 to 10 carbon atoms, such as acetylenyl groups; Aryl groups having about 6 to 20 carbon atoms, such as phenyl and naphthyl groups; Heteroaryl groups having about 3 to 20 carbon atoms, such as thienyl, furyl, and pyridyl groups; Alkoxy groups having about 1 to 15 carbon atoms, such as a methoxy group, an ethoxy group, or a propoxy group; Aryloxy groups having about 6 to 20 carbon atoms, such as phenoxy and naphthoxy groups; Heteroaryloxy groups having about 3 to 20 carbon atoms, such as a pyridyloxy group and a thienyloxy group; Alkylthio groups having about 1 to 15 carbon atoms, such as methylthio and ethylthio groups; Arylthio groups having about 6 to 20 carbon atoms, such as a phenylthio group and a naphthylthio group; Heteroarylthio groups having about 3 to 20 carbon atoms, such as a pyridylthio group and a thienylthio group; an amino group having about 1 to 20 carbon atoms, such as a dimethylamino group or a diphenylamino group, which may have a substituent; Acyl groups having about 2 to 20 carbon atoms, such as acetyl and pivaloyl groups; Acylamino groups having about 2 to 20 carbon atoms, such as acetylamino and propionylamino groups; Ureido groups with 2 to 20 carbon atoms, such as 3-methylureido groups; Sulfonamide groups having about 1 to 20 carbon atoms, such as methanesulfonamide groups and benzenesulfonamide groups; Carbamoyl groups having about 1 to 20 carbon atoms, such as a dimethylcarbamoyl group and an ethylcarbamoyl group; Sulfamoyl groups having about 1 to 20 carbon atoms, such as ethylsulfamoyl groups; Sulfamoylamino groups having about 1 to 20 carbon atoms, such as dimethylsulfamoylamino groups; Alkoxycarbonyl groups having about 2 to 6 carbon atoms, such as a methoxycarbonyl group or an ethoxycarbonyl group; Aromatic hydrocarbon oxycarbonyl groups having about 7 to 20 carbon atoms, such as phenoxycarbonyl and naphthoxycarbonyl groups; Aromatic heterocyclic hydrocarbon oxycarbonyl groups having about 6 to 20 carbon atoms, such as pyridyloxycarbonyl groups; Alkylsulfonyl groups having about 1 to 6 carbon atoms, such as a methanesulfonyl group, an ethanesulfonyl group, or a trifluoromethanesulfonyl group; Arylsulfonyl groups having about 6 to 20 carbon atoms, such as benzenesulfonyl groups and monofluorobenzenesulfonyl groups; Heteroaryloxysulfonyl groups having about 3 to 20 carbon atoms, such as thienylsulfonyl groups; Imide groups with 4 to 20 carbon atoms, such as phthalimide; A silyl group trisubstituted with a substituent selected from the group consisting of an alkyl group and an aryl group:

[0039] <Optional Substituents> The optional substituents include the above-mentioned substituents and a hydrogen atom.

[0040] [Fused polycyclic aromatic heterocyclic compounds] The method for producing a fused polycyclic aromatic heterocyclic compound of the present invention is a method for producing a fused polycyclic aromatic heterocyclic compound represented by the following general formula (I) (hereinafter, sometimes referred to as "fused polycyclic aromatic heterocyclic compound (1)" or "compound (1)") by reacting an oxime ether with an acetylene derivative, and is characterized in that the reaction is carried out in the presence of a trivalent iron compound, a trivalent phosphorus compound, and a trialkylaluminum.

[0041] [ka]

[0042] (In the above formula (I), Y I , Y II each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or a divalent aliphatic hydrocarbon group which may have a substituent. RI ~R V each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, a silyl group which may have a substituent, or a hydrogen atom. Z I ~Z III each independently represents an element of Group 14, 15 or 16 of the periodic table which may have a substituent, or a hydrogen atom. In formula (I), Z I and Y I , Z II and Y II may be bonded directly or via a linking group to form a ring. A I ~A IX each independently has an optional substituent. m represents an integer.)

[0043] The method for producing a fused polycyclic aromatic heterocyclic compound of the present invention is also a method for producing a fused polycyclic aromatic heterocyclic compound represented by the following formula (II), the following formula (III), the following formula (IV), or the following formula (V) by reacting an oxime ether with an acetylene derivative (hereinafter, each of these may be referred to as "fused polycyclic aromatic heterocyclic compound (II)" or "compound (II)", "fused polycyclic aromatic heterocyclic compound (III)" or "compound (III)", "fused polycyclic aromatic heterocyclic compound (IV)" or "compound (IV)", "fused polycyclic aromatic heterocyclic compound (V)" or "compound (V)", respectively), characterized in that the reaction is carried out in the coexistence of a trivalent iron compound, a trivalent phosphorus compound, and a trialkylaluminum.

[0044] [ka]

[0045] (In the above formulas (II), (III), (IV), and (V), R 1 ~R 12each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, a silyl group which may have a substituent, or a hydrogen atom. Z 1 ~Z 12 Z each independently represents an element of Group 14, 15, or 16 of the periodic table which may have a substituent, or a hydrogen atom. 1 and Z 2 , Z 3 and Z 4 , Z 5 and Z 6 , Z 7 and Z 8 , Z 9 and Z 10 , Z 11 and Z 12 may be bonded directly or via a linking group, or may form a ring. A 1 ~A 12 , B 1 ~B 10 and C 1 ~C 6 each independently represents an arbitrary substituent. The dotted line in formula (II) represents an ethylene group which may have a substituent, or an ethynylene group which may have a substituent.

[0046] Hereinafter, the reaction for producing the fused polycyclic aromatic heterocyclic compounds (I) to (V) from an oxime ether and an acetylene derivative may be referred to as the "reaction of the present invention."

[0047] <Fused polycyclic aromatic heterocyclic compounds (I)> In the formula (I) representing the condensed polycyclic aromatic heterocyclic compound (I), Y I , Y II each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or a divalent aliphatic hydrocarbon group which may have a substituent. The divalent aromatic hydrocarbon group, aromatic heterocyclic group, and aliphatic hydrocarbon group are as described above. YI , Y II The aromatic hydrocarbon group and aromatic heterocyclic group are preferably, independently, a monocyclic or bicondensed ring arylene group or a monocyclic heteroarylene group having 12 or less carbon atoms, and more preferably a monocyclic aryl group or heteroarylene group having 6 or less carbon atoms, specifically a phenylene group or a thienylene group. Y I , Y II When the divalent aliphatic hydrocarbon group has a carbon-carbon double bond, the number of carbon-carbon double bonds is preferably 1 to 5 from the viewpoint of light resistance. When the divalent aliphatic hydrocarbon group has a carbon-carbon triple bond, the number of carbon-carbon triple bonds is preferably 1 to 3 from the viewpoint of effective conjugation. I , Y II When the divalent aliphatic hydrocarbon group has a carbon-carbon single bond, preferred examples include a methyl group, a monoalkylmethyl group, and a dialkylmethyl group having 1 to 15 carbon atoms.

[0048] In formula (I), R I ~R V each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, a silyl group which may have a substituent, or a hydrogen atom. Of these functional groups, the aromatic hydrocarbon group and the aromatic heterocyclic group are I , Y II Examples of the monovalent aromatic hydrocarbon group and aromatic heterocyclic group are the same as those listed under 1.

[0049] R I ~R V Examples of the aliphatic hydrocarbon group are each independently a straight-chain, branched-chain or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a 2-methylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a cyclohexylmethyl group, a neopentyl group, a 2-ethylbutyl group, an isopropyl group, a 2-butyl group, a cyclohexyl group, a 3-pentyl group, a tert-butyl group, a 1,1-dimethylpropyl group, a 2-ethylhexyl group, a 2-butyloctyl group, etc. Among these, preferred are alkyl groups having 20 or less carbon atoms.

[0050] As the silyl group which may have a substituent, those having an alkyl group having 6 or less carbon atoms as a substituent, such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group, are preferable. Of these, R I ~R V As the silyl group, a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tri-t-butyldisilyl group are preferable.

[0051] In formula (I), Z I ~Z III are each independently an element of Group 14, 15, or 16 of the periodic table which may have a substituent, or a hydrogen atom. Preferred examples of elements of Groups 14 to 16 of the periodic table include carbon atoms, nitrogen atoms, oxygen atoms, silicon atoms, phosphorus atoms, sulfur atoms, germanium atoms, and selenium atoms. When these atoms have a substituent, preferred examples of the substituent include an alkyl group, an alkoxy group, an aromatic hydrocarbon group, and an aromatic heterocyclic group, among the above-mentioned exemplary substituents. Also, Z I and Y I , Z II and Y II may each independently be bonded via a linking group or directly to form a ring. Z I and Y I , Z II and Y II The ring formed by bonding is preferably a 5-, 6-, 7-, or 8-membered ring from the viewpoint of suppressing vibration of the ring.

[0052] In formula (I), A I ~A XI is an arbitrary substituent, but preferably, Y 1 , Y 2 The substituents are the same as those of the groups which may have the substituents listed in 1. Furthermore, an alkyl group, an alkoxy group, or a hydrogen atom is preferable in terms of solubility, and a halogen atom such as a bromine atom or an iodine atom is preferable in terms of further functionalization.

[0053] m represents an integer, and is preferably an integer of 0 to 5 from the viewpoint of solubility.

[0054] <Fused polycyclic aromatic heterocyclic compounds (II)-(V)> In the formulas (II) to (V) representing the condensed polycyclic aromatic heterocyclic compounds (II) to (V), R 1 ~R 12 The aromatic hydrocarbon group which may have a substituent, the aromatic heterocyclic group which may have a substituent, the aliphatic hydrocarbon group which may have a substituent, and the silyl group which may have a substituent include R I ~R V The same applies to preferred examples. In formulas (II) to (V), Z 1 ~Z 12 As the group, Z in the formula (I) I ~Z III The same applies to preferred examples. Also, Z 1 and Z 2 , Z 3 and Z 4 , Z 5 and Z 6 , Z 7 and Z 8 , Z 9 and Z 10 , Z 11 and Z 12 Examples of the ring formed by bonding these groups directly or via a linking group include a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring. A 1 ~A 12 , B 1 ~B 10 and C 1 ~C 6 each independently represents an arbitrary substituent. This arbitrary substituent is as described above, but is preferably a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.

[0055] The dotted line in formula (II) represents an ethylene group which may have a substituent, or an ethynylene group which may have a substituent, and is preferably an ethylene group in order not to break conjugation.

[0056] [Method for producing a fused polycyclic aromatic heterocyclic compound according to one embodiment] The method for producing the fused polycyclic aromatic heterocyclic compounds of the present invention represented by the above formulas (I) to (V) (hereinafter, sometimes referred to as "compounds (I) to (V)" or "target compounds") will be described below by reacting oxime ethers represented by the following formulas (VIIa) to (IXa) (hereinafter, sometimes referred to as "oxime ethers (VIIa) to (IXa)") with an acetylene derivative represented by the following formula (X) (hereinafter, sometimes referred to as "acetylene derivative (X)"), which has a preferred fused ring skeleton among the compounds (I) to (V). The method for producing the fused polycyclic aromatic heterocyclic compounds of the present invention represented by the following formulas (VII) to (IX) (hereinafter, sometimes referred to as "compounds (VII) to (IX)") will be described below. Compounds (I) to (V) can also be produced in the same manner as described below.

[0057] [ka]

[0058] (Among (VIIa) to (IXa) above, X 1 , X 2 R each independently represents an element of Group 14, 15, or 16 of the periodic table which may have a substituent. The aromatic rings in formulae (VIIa) to (IXa) may have any substituent. a , R b each independently represents an alkyl group such as a methyl group.

[0059] [ka]

[0060] (In the above formula (X), R 15 , R 16each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, or a silyl group which may have a substituent.

[0061] [ka]

[0062] (In the above formulas (VII) to (IX), X 1 , X 2 , R 15 , R 16 have the same meanings as in formulae (VIIa) to (IXa) and (X), respectively.)

[0063] The compounds (VII) to (IX) can be produced by reacting the oxime ethers (VIIa) to (IXa) with the acetylene derivative (X) in the presence of a trivalent iron compound, a trivalent phosphorus compound, and trialkylammonium.

[0064] <Oxime ethers (VIIa) to (IXa)> The oxime ethers (VIIa) to (IXa) serving as raw material compounds can be produced by using the corresponding carbonyl compounds as starting materials and modifying the carbonyl group of the carbonyl compound to an oxime ether group. Specific examples of the carbonyl compound as the starting material will be described later. The carbonyl group can be converted into an oxime ether group by a known method, for example, the method described in "The Chemistry of Hydroamines, Oximes and Hydroxamic Acids" by Rappoport (published by John Wiley & Sons in 2009).

[0065] In the formulae (VIIa) to (IXa) representing the oxime ethers (VIIa) to (IXa), X 1 , X 2is as described above, but is preferably a nitrogen atom, an oxygen atom or a sulfur atom which may have a substituent, and more preferably a nitrogen atom which has a substituent.

[0066] <Acetylene derivatives (X)> In the formula (X) representing the acetylene derivative (X), R 15 , R 16 are each independently as defined above, but are preferably a methyl group, an ethyl group, an isopropyl group, a phenyl group, a tosyl group, a mesityl group, or a silyl group having a substituent thereof, and are more preferably a phenyl group or a trimethylsilyl group. Specific examples of the acetylene derivative (X) include those described in "Modern Acetylene Chemistry" edited by P. Stang, published by Wiley-VCH in 2008, "Acetylene Chemistry: Chemistry, Biology, and Material Science" edited by F. Diederich, published by Wiley-VCH in 2005, and "Synthesis of Acetylenes, Allenes, and Cumulenes" edited by B. Lambert, published by Elsevier in 2004, and examples thereof include the structures shown below. In the following, "Me" represents a methyl group, "Et" represents an ethyl group, "Pr" represents a propyl group, and "TMS" represents a trimethylsilyl group.

[0067] [ka]

[0068] [ka]

[0069] <Compounds (VII)~(IX)> In the present invention, preferred compounds (VII) to (IX) are produced by reacting the above-mentioned suitable oxime ethers (VIIa) to (IXa) with a suitable acetylene derivative (X).

[0070] Therefore, in the formulas (VII) to (IX) representing the compounds (VII) to (IX), R 15 , R 16 are preferably each independently a methyl group, an ethyl group, an isopropyl group, a phenyl group, a tosyl group, a mesityl group, or a silyl group having any of these substituents; 1 , X 2 is preferably a nitrogen atom, an oxygen atom or a sulfur atom, each of which may independently have a substituent.

[0071] Specific examples of the compounds (1) to (V) of the present invention, including these compounds (VII) to (IX), will be described later.

[0072] <Trivalent iron compounds> In the present invention, the trivalent iron compound coexisting in the reaction system means that the iron in the compound is trivalent. The trivalent iron compound is specifically FeCl 3 , FeBr 3 , FeI 3 , Fe(OAc) 3 , Fe(acac) 3 Here, "OAc" is an acetoxy group, and "acac" is an acetylacetonato group.

[0073] The amount of the trivalent iron compound to be coexisted in the reaction system is not particularly limited, but the amount of the trivalent iron compound to be coexisted with respect to the target compound is preferably within the range of 1 to 30 mol %, and more preferably within the range of 5 to 20 mol %. If the amount of the trivalent iron compound to be coexisted is not less than the above lower limit, it is preferable from the viewpoint of yield, and if it is not more than the above upper limit, it is preferable from the viewpoint of not decreasing the stirring efficiency in the reaction system and from the viewpoint of ease of removal after the reaction.

[0074] <Trivalent phosphorus compounds> In the present invention, the trivalent phosphorus compound coexisting in the reaction system means that phosphorus in the compound is trivalent.

[0075] As the trivalent phosphorus compound, a compound having an aromatic heterocycle-phosphorus bond represented by the following formula (VI) is preferred from the viewpoint of improving the yield of the product.

[0076] [ka]

[0077] (In the above formula (VI), R 13 , R 14 each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aliphatic hydrocarbon group which may have a substituent. X represents a nitrogen atom, an oxygen atom, or a sulfur atom, each of which may have a substituent.

[0078] In the above formula (VI), R 13 , R 14 is preferably an aromatic hydrocarbon group which may have a substituent for ease of handling, and particularly preferably an aromatic hydrocarbon group having a monocyclic aromatic ring, such as a phenyl group. From the viewpoint of reactivity, X is preferably an oxygen atom or a sulfur atom. As the trivalent phosphorus compound, specifically, the following compounds are particularly preferred. In the following, "Ph" represents a phenyl group, and "Tol" represents a tolyl group.

[0079] [ka]

[0080] The trivalent phosphorus compound also functions as a ligand for the above-mentioned trivalent iron compound, and its amount present in the reaction system is preferably 1 to 3 mol, and more preferably 1.1 to 2.0 mol, per mol of the trivalent iron compound. When the amount of the trivalent phosphorus compound present is equal to or more than the lower limit, the initiation of the reaction is remarkable, whereas when the amount is equal to or less than the upper limit, the trivalent phosphorus compound is unlikely to remain after purification, which is preferable.

[0081] <Trialkylaluminum> The alkyl group of the trialkylaluminum to be present in the reaction system of the present invention is generally a methyl group, an ethyl group, an isobutyl group, etc., but in the reaction of the present invention, an alkyl group having an isopropyl group or an isobutyl group, which are highly sterically hindered, is preferred from the viewpoint of the yield of the product.

[0082] The amount of trialkylaluminum coexisting in the reaction system is preferably 0.1 to 0.5 mol, particularly preferably 0.1 to 0.3 mol, per mol of the trivalent iron compound. When the amount of trialkylaluminum coexisting is equal to or greater than the above lower limit, the initiation of the reaction is remarkable, whereas when the amount is equal to or less than the above upper limit, the operation of deactivating the trialkylaluminum after the reaction is easy.

[0083] <Bidentate ligand capable of forming a complex with aluminum and a six- or five-membered ring, catechol, 1,8-dihydroxynaphthalene> In the reaction of the present invention, additives other than the above-mentioned trivalent iron compound, the above-mentioned trivalent phosphorus compound and the above-mentioned trialkylaluminum can be present in the reaction system. In particular, the coexistence of a bidentate ligand capable of forming a 6- or 5-membered ring complex with aluminum is preferable because it accelerates the reaction. Also, the coexistence of catechol, 1,8-dihydroxynaphthalene, or a derivative thereof is preferable because it accelerates the reaction by forming a 5- or 6-membered ring complex between two adjacent hydroxyl groups and trialkylaluminum.

[0084] When a bidentate ligand capable of forming a 6-membered or 5-membered ring complex with aluminum, such as catechol or 1,8-dihydroxynaphthalene, or a derivative thereof is used, the amount of such a ligand coexisting in the reaction system is preferably 0.01 to 0.5 mol, particularly preferably 0.1 to 0.3 mol, per mol of the trivalent iron compound. When the amount of the bidentate ligand capable of forming a 6-membered or 5-membered ring complex with aluminum, catechol, 1,8-dihydroxynaphthalene, or a derivative thereof is equal to or greater than the above-mentioned lower limit, the addition of these coexisting compounds has an excellent effect of accelerating the reaction, whereas when the amount is equal to or less than the above-mentioned upper limit, the removal of these coexisting compounds during purification is easy.

[0085] (solvent) The reaction of the present invention is usually carried out in a solvent. The solvent used in this case is preferably selected from ether solvents such as tetrahydrofuran (THF), cyclopentyl methyl ether (CPME), 2-methyltetrahydrofuran (MTHF), and methyl tert-butyl ether (MTBE); aromatic solvents such as xylene and toluene; and halogen solvents such as dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene.

[0086] These solvents may be used alone or in combination of two or more. For example, when a solvent having low solubility for a substrate is used, the reaction results are improved by combining it with a halogen-based solvent or an ether-based solvent. Also, when a high-boiling point solvent is used to increase the reaction temperature, the reaction results are improved by preferably combining it with an aromatic solvent.

[0087] <Reaction conditions> The reaction of the present invention is usually carried out at a reaction temperature in the range of -5°C or higher, preferably 0°C or higher, more preferably 10°C or higher, and particularly preferably 25°C or higher to the boiling point of the solvent used. The reaction temperature can be set arbitrarily within the range up to the reflux temperature of the solvent used, depending on the reaction rate. In particular, the reaction is preferably carried out at a reaction temperature of 100 to 150°C, since the yield of the target compound is high. When the yield of the target compound is poor, it is preferable to irradiate the reaction solution with ultrasonic waves or microwaves, or to autoclave the reaction solution.

[0088] The reaction time is usually from 30 minutes to 48 hours, but may be set arbitrarily since it depends on the type of solvent used and other reaction conditions. The progress of the reaction can be confirmed by high performance liquid chromatography (HPLC).

[0089] After completion of the reaction, the target compound can be obtained using known isolation and purification methods. In order to remove trivalent iron compounds, it is preferable to further carry out extraction with a dilute aqueous hydrochloric acid solution.

[0090] <Starting materials> Specific examples (skeleton examples) of carbonyl compounds as starting materials for obtaining the above-mentioned oxime ethers (VIa) to (IXa) to be subjected to the reaction of the present invention are shown below. However, the starting materials in the present invention are not limited to these.

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] In the above exemplary compounds, R represents, by way of example, a methyl group, an ethyl group, a propyl group, or a butyl group, but is not limited thereto. The aromatic ring of the above exemplary compounds may have any substituent.

[0095] [Specific examples of condensed polycyclic aromatic heterocyclic compounds] Specific examples of the fused polycyclic aromatic heterocyclic compounds of the present invention represented by the formulas (I) to (V), including the compounds represented by the formulas (VII) to (IX), are shown below, although the present invention is not limited thereto. In the following, "Me" stands for methyl group, "Bu" stands for butyl group, "TMS" stands for trimethylsilyl group, and "Ph" stands for phenyl group. The same applies to the examples shown later.

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] [Full width at half maximum of the maximum peak in the fluorescence spectrum] The compounds of the present invention represented by the formulas (I) to (V) preferably have a half-width of the maximum peak of the fluorescence spectrum of 25 nm or less, more preferably 23 nm or less. The half-width here refers to the full width at half maximum (FMHM). The half width of the fluorescence spectrum is determined by first measuring the maximum excitation wavelength, obtaining the fluorescence spectrum at the maximum excitation wavelength, and measuring the full width at half maximum. In the present invention, three or more condensed rings are used as the starting material, and aromatic rings are expanded on the starting material, so that the structure becomes so-called "hard" and vibration is reduced, resulting in a narrow half-width. This tendency is considered to occur significantly when three or more condensed rings containing a nitrogen atom are used as the starting material. If the half-width of the maximum peak of the fluorescence spectrum is 25 nm or less, the color purity is high when used as a light-emitting material. The smaller this value, the higher the color purity, which is preferable, but in the case of ordinary organic materials, the lower limit is about 15 nm. The half-value width of the maximum peak in the fluorescence spectrum of the compound is measured by the method described in the Examples section below. EXAMPLES

[0104] The following provides a more detailed explanation of the embodiments of the present invention by way of examples. However, the present invention is not limited to the following examples as long as it does not depart from the gist of the present invention.

[0105] In the following, the half-value width of the maximum peak in the fluorescence spectrum of the produced compound was measured by the following method. <Method for measuring the half-width of the maximum peak of a fluorescence spectrum> Absorption spectrum (in dichloromethane, approximately 1.0×10 -5 The fluorescence spectrum (in dichloromethane, approximately 1.0 × 10 -6 M or approx. 1.0 x 10 -7 M) was measured using a JASCO FP-8500 spectrometer. The absolute luminescence quantum yields were measured with a Hamamatsu Photonics C9920-02 spectrometer equipped with an integrating sphere. Dichloromethane for spectroscopic analysis (Fujifilm Wako Pure Chemical Industries, Ltd.) was used as received.

[0106] [Experimental Examples 1 to 15: Production of oxime ether compounds] In an oven-dried Schlenk flask, the carbonyl compound (2.0 mmol), O-methylhydroxylamine hydrochloride (0.86 g, 10 mmol), pyridine (2.5 mL), and ethanol (10 mL) were mixed. The reaction solution was stirred at 80°C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting crude product was purified using silica gel chromatography (developing solvent: hexane / ethyl acetate) to obtain the oxime ether compounds shown in the following Experimental Examples 1 to 15. The structural formula, yield, and NMR measurement results of each oxime ether compound are shown below.

[0107] (Experimental Example 1) [ka]

[0108] 0.45g, 95% 1 H NMR (500 MHz, CDCl 3 ):δ8.65(dd,J=8.1,1.8Hz,1H),8.00(dd,J=7.5,1.2Hz,1H),7.39-7.45(m ,2H),7.13(d,J=8.6Hz,1H),7.03-7.09(m,3H),4.06(s,3H),3.55(s,3H).

[0109] (Experimental Example 2) [ka]

[0110] 0.56g, 94% 1 H NMR (500 MHz, CDCl 3): δ 8.86 (dd, J = 8.1, 1.8 Hz, 1H), 8.15 (dd, J = 8.0, 1.7 Hz, 1H), 7.63 - 7.66 (m, 2H), 7.54 - 7.57 (m, 1H), 7.29 - 7.31 (m, 2H), 7.14 - 7.20 (m, 2H), 7.00 - 7.04 (m, 2H), 6.44 (dd, J = 8.6, 1.2 Hz, 1H), 6.38 (m, 1H), 4.11 (s, 3H).

[0111] (Experimental Example 3)

Chemical Structure

[0112] 0.39 g, 86% 1 H NMR (500 MHz, CDCl 3 ): δ 8.84 (dd, J = 8.0, 1.2 Hz, 1H), 8.08 (dd, J = 8.1, 1.8 Hz, 1H), 7.41 - 7.47 (m, 1H), 7.38 - 7.40 (m, 1H), 7.24 (d, J = 1.8 Hz, 1H), 7.14 - 7.20 (m, 3H).

[0113] (Experimental Example 4)

Chemical Structure

[0114] 0.40 g, 84% 1 H NMR (500 MHz, CDCl 3 ): δ 8.29 (dd, J = 8.1, 1.8 Hz, 1H), 7.87 - 7.89 (m, 1H), 7.47 - 7.49 (m, 1H), 7.39 - 7.41 (m, 1H), 7.29 - 7.36 (m, 4H), 4.01 (s, 3H).

[0115] (Experimental Example 5)

Chemical Structure

[0116] 0.42 g, 84% 1 1H NMR (500 MHz, CDCl 3 ): δ 8.34 (dd, J = 8.0, 1.7 Hz, 1H), 7.86 (dd, J = 7.5, 1.4 Hz, 1H), 7.62 (dd, J = 8.0, 1.2 Hz, 1H), 7.55 (dd, J = 8.1, 1.2 Hz, 1H), 7.36 - 7.41 (m, 2H), 7.28 - 7.33 (m, 2H), 4.10 (s, 3H), 1.64 (s, 6H).

[0117] (Experimental Example 6)

Chemical Structure

[0118] 0.43 g, 92% 1 1H NMR (500 MHz, CDCl 3 ): δ 7.58 - 7.42 (m, 2H), 7.25 - 7.44 (m, 6H), 6.90 (s, 2H), 3.94 (d, J = 1.7 Hz, 3H).

[0119] (Experimental Example 7)

Chemical Structure

[0120] 0.39 g, 93% 1 1H NMR (500 MHz, CDCl 3 ): δ 8.26 - 8.28 (m, 1H), 7.76 - 7.77 (m, 1H), 7.65 (dd, J = 7.5, 1.2 Hz, 1H), 7.61 - 7.62 (m, 1H), 7.41 - 7.44 (m, 1H), 7.37 - 7.39 (m, 1H), 7.26 - 7.32 (m, 2H), 4.22 (s, 3H).

[0121] (Experimental Example 8)

Chemical Structure

[0122] 0.34 g, 81% 1 H NMR (500 MHz, CDCl 3 ): δ 8.41 (d, J = 7.4 Hz, 1H), 7.81 (d, J = 8.0 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 7.51 (t, J = 7.8 Hz, 1H), 7.38 (t, J = 7.5 Hz, 1H), 7.33 (d, J = 6.3 Hz, 1H), 7.15 - 7.21 (m, 1H), 7.03 - 7.07 (m, 1H), 4.10 (s, 3H)

[0123] (Experimental Example 9)

Chemical Structure

[0124] 0.70 g, 94% 1 H NMR (500 MHz, CDCl 3 ): δ 8.61 (d, J = 8.0 Hz, 1H), 8.07 (d, J = 8.1 Hz, 1H), 7.79 (d, J = 7.5 Hz, 2H), 7.36 (t, J = 7.4 Hz, 2H), 7.27 - 7.31 (m, 2H), 7.19 (t, J = 7.4 Hz, 2H), 7.05 - 7.11 (m, 4H), 6.63 (d, J = 8.1 Hz, 1H), 6.54 (d, J = 7.5 Hz, 1H), 4.23 (s, 3H).

[0125] (Experimental Example 10)

Chemical Structure

[0126] 0.41 g, 94% 1 H NMR (500 MHz, CDCl 3 ): δ 8.02 (d, J = 8.1 Hz, 1H), 7.87 - 7.89 (m, 2H), 7.41 - 7.48 (m, 4H), 7.29 (d, J = 8.6 Hz, 1H), 7.20 - 7.23 (m, 1H), 7.06 (d, J = 1.2 Hz, 1H), 4.03 (d, J = 1.2 Hz, 3H).

[0127] (Experimental Example 11)

Chem.

[0128] 0.48 g, 80% 1 H NMR (500 MHz, CDCl 3 ): δ 8.45 - 8.47 (m, 1H), 8.00 - 8.04 (m, 3H), 7.86 - 7.88 (m, 1H), 7.66 (d, J = 9.2 Hz, 1H), 7.58 - 7.65 (m, 2H), 7.49 - 7.54 (m, 3H), 7.20 (s, 1H), 4.06 (s, 3H).

[0129] (Experimental Example 12)

Chem.

[0130] 0.75 g, 95% 1 H NMR (500 MHz, CDCl 3 ): δ 8.73 (dd, J = 8.0, 1.2 Hz, 1H), 8.06, (dd, J = 8.0, 1.7 Hz, 1H), 7.38 - 7.44 (m, 2H), 7.14 (d, J = 8.6 Hz, 1H), 7.09 (d, J = 8.0 Hz, 1H), 7.01 - 7.06 (m, 2H), 4.04 (s, 3H), 3.99 (t, J = 8.3 Hz, 2H), 1.84 - 1.87 (m, 2H), 1.26 - 1.49 (m, 18H), 0.87 - 0.90 (m, 3H).

[0131] (Experimental Example 13)

Chem.

[0132] 0.67 g, 91% 1 H NMR (500 MHz, CDCl 3): δ 9.00 (s, 0.9H), 8.99 (s, 1.1H), 8.46 (s, 0.9H), 8.41 (s, 1H), 7.92 - 7.94 (m, 4H), 7.49 - 7.58 (m, 4H), 4.22 (s, 3.3H), 4.21 (s, 2.7H),

[0133] (Experimental Example 14) [Chemical Formula]

[0134] 0.58 g, 78% 1 H NMR (500 MHz, CDCl 3 ): δ 8.40 (dd, J = 8.0, 1.7 Hz, 2H), 7.43 - 7.46 (m, 2H), 7.30 (d, J = 1.2 Hz, 2H), 7.28 (s, 2H), 7.22 - 7.24 (m, 2H), 4.03 (s, 6H).

[0135] (Experimental Example 15) [Chemical Formula]

[0136] 0.62 g, 82% 1 H NMR (500 MHz, CDCl 3 ): δ 8.68 - 8.70 (m, 1.3H), 8.57 (s, 0.2H), 8.55 (s, 0.5H), 8.02 - 8.03 (m, 0.7H), 7.80 (s, 0.5H), 7.77 (s, 0.8H), 7.40 - 7.46 (m, 2H), 7.14 - 7.16 (1.3H), 7.10 (d, J = 8.6 Hz, 0.7H), 7.00 - 7.06 (m, 2H), 4.11 (s, 2.1H; s, 1.6H), 4.10 (s, 2.3H), 3.65 (s, 2.3H), 3.64 (s, 1.6H), 3.59 (s, 1.4H), 3.58 (s, 0.7H).

[0137] [Examples 1 - 40: Production of Condensed Polycyclic Aromatic Heterocyclic Compounds] In an oven-dried Schlenk flask, add oxime ether (0.20 mmol), alkyne (0.30 mmol), catechol (44 mg, 0.40 mmol), phosphorus ligand (benzofuryl-TP, 15 mg, 0.022 mmol), Fe(acac) 3 (7.0 mg, 0.020 mmol), and xylene (0.40 mL) were mixed. 3 A toluene solution (1.0 mol / L, 0.40 mL, 0.40 mmol) of was added. The reaction solution was stirred at room temperature for 5 minutes, and then stirred at 140°C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, diluted with dichloromethane (2 mL), and carefully quenched with methanol (0.1 mL). The solvent was then removed under reduced pressure, and the resulting crude product was purified by silica gel chromatography (developing solvent: hexane / dichloromethane) to obtain the target compound. According to the above synthesis method, the fused polycyclic aromatic heterocyclic compounds described in the following Examples 1 to 40 were produced. The structural formulas, yields and NMR measurement results of the produced fused polycyclic aromatic heterocyclic compounds are shown below.

[0138] Example 1 [ka]

[0139] Yield: 99% 1 H NMR (500 MHz, CDCl 3 ):δ8.86(dd,J=8.0,1.7Hz,1H),7.46-7.51(m,4H),7.35-7.38(m,2H),7.25-7.32(m ,4H),7.17-7.21(m,4H),6.93(d,J=7.5Hz,1H),6.78(d,J=8.1Hz,1H),3.63(s,3H).

[0140] Example 2 [ka]

[0141] Yield: 99% 1 H NMR (500 MHz, CDCl 3 ): δ8.84(dd,J=8.0Hz,1H),7,70-7.74(m,2H),7.59-7.63(m,1H),7.48-7.50(m,2H),7.35-7.40(m,4H),7.29-7.3 2(m,1H),7.20-7.27(m,7H),7.10-7.14(m,1H),6.87-6.90(m,1H),6.44(d,J=8.6Hz,1H),6.06(dd,J=8.0Hz,1H).

[0142] (Example 3)

change

[0143] Yield: 99% 1 H NMR (500 MHz, CDCl 3 ): δ8.61-8.63(m,1H),7.53(t,J=8.0Hz,1H),7.45-7.50(m,3H),7.33-7.3 9(m,3H),7.20-7.28(m,7H),7.17(d,J=8.6Hz,1H),7.14(d,J=8.6Hz,1H).

[0144] (Example 4)

change

[0145] Yield: 99% 1 H NMR (500 MHz, CDCl 3 ): δ8.97(dd,J=8.0,2.3Hz,1H),7.45-7.47(m,2H),7.32-7.40(m,7H),7.27-7.7.30(m,2H),7.21-7.26(m,5H).

[0146] (Example 5)

change

[0147] Yield: 98% 1 H NMR (500 MHz, CDCl 3 ): δ9.00(dd,J=8.0,1.7Hz,1H),7.68-7.73(m,2H),7.64(t,J=7.7Hz,1H),7.48-7 .55(m,4H),7.35-7.44(m,4H),7.28-7.30(m,2H),7.21-7.25(m,3H),1.81(s,6H).

[0148] (Example 6)

change

[0149] Yield: 86% 1 H NMR (500 MHz, CDCl 3 ): δ8.51(dd,J=8.0,1.2Hz,1H),7.49-7.52(m,3H),7.41-7.47(m,2H),7.32-7.40(m,5 H),7.25-7.28(m,3H),7.17-7.24(m,3H),6.74(d,J=12.0Hz,1H),6.68(d,J=12Hz,1H).

[0150] (Example 7)

change

[0151] Yield: 68% 1 H NMR (500 MHz, CDCl 3 ): δ7.91(m,2H),7.48-7.53(m,4H),7.27-7.36(m,5H),7.16-7.23(m,6H),7.11(d,J=8.6Hz,1H),7.06(s,1H).

[0152] (Example 8)

change

[0153] Yield: 71% 1 H NMR (500 MHz, CDCl 3 ): δ8.48-8.50(m,1H),8.04-8.06(m,2H),7.79(dd,J=6.3,2.3Hz,1H),7.51-7.5 9(m,6H),7.36-7.41(m,5H),7.29-7.34(m,2H),7.24(s,1H),7.17-7.22(m,3H).

[0154] (Example 9)

change

[0155] Yield: 65% 1 H NMR (500 MHz, CDCl 3 ): δ8.38-8.44(m,2H),8.36(d,J=6.9Hz,1H),8.27(d,J=7.4Hz,1H),8.19(d,J=9.2Hz,1H),8.09( t,J=7.5Hz,1H),7.92(d,J=9.2Hz,1H),7.48-7.50(m,2H),7.33-7.43(m,5H),7.25-7.30(m,3H).

[0156] (Example 10)

change

[0157] Yield: 97% 1 H NMR (500 MHz, CDCl 3 ): δ8.19(d,J=8.6Hz,1H),7.82-7.84(m,2H),7.73(d,J=8.0Hz,1H),7.4 9-7.62(m,5H),7.36-7.44(m,5H),7.30-7.31(m,2H),7.16-7.19(m,3H).

[0158] (Example 11)

change

[0159] Yield: 98% 1 H NMR (500 MHz, CDCl 3 ): δ8.72(dd,J=8.1,1.8Hz,1H),7.56(t,J=8.3Hz,1H),7.43-7.47(m,1H),7.21(d,J=8.6 Hz,1H),7.14-7.16(m,2H),6.69(d,J=8.0Hz,1H),3.57(s,3H),2.70(s,3H),2.41(s,3H).

[0160] (Example 12)

change

[0161] Yield: 99% 1 H NMR (500 MHz, CDCl 3 ): δ8.76(dd,J=8.0,1.7Hz,1H),7.53(t,J=8.0Hz,1H),7.41-7.45(m,1H),7.17-7.20(m, 2H),7.12-7.15(m,1H),2.90-2.99(m,4H),1.41(t,J=7.5Hz,3H),1.25(t,J=7.8Hz,3H).

[0162] (Example 13)

change

[0163] Yield: 99% 1 H NMR (500 MHz, CDCl 3): δ8.74(dd,J=8.0,1.7Hz,1H),7.51(t,J=8.1Hz,1H),7.40-7.44(m,1H),7.11-7.25(m,3H),6.65(d,J =8.1Hz,1H),3.53(s,3H),2.84-2.92(m,4H),1.87-1.92(m,2H),1.62-1.67(m,2H),1.05-1.09(m,6H).

[0164] (Example 14)

change

[0165] Yield: 98% 1 H NMR (500 MHz, CDCl 3 ): δ8.74(dd,J=8.0,1.7Hz,1H),7.52(t,J=8.1Hz,1H),7.12-7.18(m,3H),6.66(d,J=8.0Hz,1H),3.54(s,3H),2.93(t ,J=7.7Hz,2H),2.88(t,J=8.3Hz,2H),1.81-1.87(m,2H),1.58-1.62(m,2H),1.47-1.54(m,4H),1.00(t,J=7.4Hz,6H)

[0166] (Example 15)

change

[0167] Yield: 98% 1 H NMR (500 MHz, CDCl 3 ): δ8.87(dd,J=7.5,1.2Hz,1H),7.44-7.49(m,2H),7.36-7.41(m,4H),7.24(d,J=8.0Hz,1H),7.14 -7.20(m,5H),6.98(d,J=8.0Hz,1H),6.75(d,J=8.0Hz,1H),3.61(s,3H),1.35(s,9H),1.27(s,9H). 13CNMR (125MHz, CDCl 3 ):δ151.2,149.6,149.0,14

[0168] (Example 16)

change

[0169] Yield: 89% 1 H NMR (500 MHz, CDCl 3 ): δ8.74(dd,J=8.0Hz,1H),7.60-7.63(m,3H),7.40-7.49(m,4H),7.28(d,J=8.6Hz,1H),7.22(d,J=7.5Hz,1H),7.09-7.12(m,1 H),6.79(d,J=7.4Hz,1HHH),3.60(s,3H),2.86-2.89(m,2H),1.62-1.65(m,2H),1.32-1.36(m,2H),0.85-0.87(t,J=7.5Hz,3H).

[0170] (Example 17)

change

[0171] Yield: 96% 1 H NMR (500 MHz, CDCl 3 ): δ8.76(dd,J=8.1,1.8Hz),7.64-7.66(m,2H),7.59(t,J=8.0Hz,1H),7.41-7.49(m,5H),7. 23(d,J=8.6Hz,1H),7.13(t,J=7.2Hz,1H),6.80(d,J=8.0Hz,1H),3.61(s,3H),0.11(s,9H).

[0172] (Example 18)

change

[0173] Yield: 99% 1 H NMR (500 MHz, CDCl 3 ): δ8.86(dd,J=8.0,1.8Hz,1H),7.45-7.50(m,2H),7.38-7.40(m,2H),7.2 4(d,J=4.6Hz,1H),7.14-7.18(m,5H),7.00(d,J=8.6Hz,2H),6.96(d,J=7.5 Hz,1H),6.75(d,J=7.5Hz,1H),3.60(s,3H),2.65(t,J=7.5Hz,2H),2.55,( t,J=7.7Hz,2H),1.56-1.65(m,4H),1.28-1.36(m,12H),0.87-0.93(m,6H).

[0174] (Example 19)

change

[0175] Yield: 92% 1 H NMR (500 MHz, CDCl 3 ): δ8.78(d,J=7.5Hz,2H),7.39-7.46(m,3H),7.08-7.26(m,5H),6.77-6.91(m ,4H),6.73(d,J=8.0Hz,1H),6.66(d,J=8.1Hz,1H),3.59(s,6H),3.51(s,3H).

[0176] (Example 20)

change

[0177] Yield: 98% 1 H NMR (500 MHz, CDCl 3): δ8.85(d,J=7.5Hz,1H),7.44-7.49(m,2H),7.24-7.31(m,2H),7.14-7.18(m,3H),7.06(s,1H),6.96(d,J =8.0Hz,1H),6.86-6.89(m,2H),6.80(s,1H),6.76(d,J=8.0Hz,2H),3.72(s,3H),3.64(s,3H),3.60(s,3H).

[0178] (Example 21)

change

[0179] Yield: 62% 1 H NMR (500 MHz, CDCl 3 ): δ8.19(d,J=8.1Hz,1H),7.79-7.80(m,2H),7.67(d,J=8.6Hz,1H),7.61-7.64(m ,1H),7.51-7.58(m,6H),7.34-7.36(m,2H),7.28-7.30(m,2H),7.16-7.19(m,2H).

[0180] (Example 22)

change

[0181] Yield: 77% 1 H NMR (500 MHz, CDCl 3 ): δ8.23(d,J=8.6Hz,1H),7.80-7.82(m,2H),7.70(d,J=8.0Hz,2H),7.51-7.67(m,8H),7.44-7.48(m,4H).

[0182] (Example 23)

change

[0183] Yield: 77% 1 H NMR (500 MHz, CDCl 3 ): δ8.23(d,J=8.6Hz,1H),7.80-7.82(m,2H),7.70(d,J=8.0Hz,2H),7.51-7.67(m,8H),7.44-7.48(m,4H).

[0184] (Example 24)

change

[0185] Yield: 92% 1 H NMR (500 MHz, CDCl 3 ): δ8.16(d,J=8.1Hz,1H),7.81-7.83(m,2H),7.74(d,J=8.1Hz,1H),7.53-7.60(m,3H),7.47-7.51(m,2H ),7.38-7.41(m,2H),7.20-7.23(m,2H),6.94-6.97(m,2H),6.73-6.76(m,2H),3.88(s,3H),3.76(s,3H).

[0186] (Example 25)

change

[0187] Yield: 89% 1 H NMR (500 MHz, DMSO-d 6 ): δ8.23(d,J=8.0Hz,1H),7.82-7.84(m,3H),7.74-7.78(m,3H),7.75-7.68(m,1H), 7.52-7.63(m,5H),7.26-7.44(m,7H),7.22(d,J=7.5Hz,2H),7.10(t,J=7.5Hz,1H).

[0188] (Example 26)

change

[0189] Yield: 47% 1 H NMR (500MHz, CD 2 Cl 2 / CS 2 ): δ9.20(s,2H),8.59(d,J=8.6Hz,2H),8.08(d,J=8.1Hz,2H),7.63-7.70(m,4H),3.39(t,J=8.3 Hz,4H),3.21(t,J=7.7Hz,4H),2.08-2.17(m,8H),1.36(t,J=7.2Hz,6H),1.25(t,J=7.5Hz,6H).

[0190] (Example 27)

change

[0191] Yield: 73% 1 H NMR (500MHz, CD 2 Cl 2 / CS 2 ): δ9.7(s,2H),8.50(dd,J=5.8,3.5Hz,2H),8.21(dd,J=6.3,3.2Hz,2H),7.68(dd,J=6.3,3.5Hz,2H),7.60(dd,J=6.3,3.4Hz,2H) ,3.50(t,J=8.0Hz,4H),3.30(t,J=7.7Hz,4H),2.19-2.26(m,4H),1.99-2.07(m,4H),1.27(t,J=7.2Hz,6H),1.19(t,J=7.4Hz,6H).

[0192] (Example 28)

change

[0193] Yield: 64% 1 H NMR (500 MHz, CDCl 3): δ 10.0 (s, 2H), 8.30 (dd, J = 6.3, 3.4 Hz, 2H), 7.95 (s, 2H), 7.65 (dd, J = 6.3, 2.3 Hz, 6H), 7.27 (t, J = 7.4 Hz, 4H), 6.98 (d, J = 8.6 Hz, 4H), 6.90 (d, J = 8.6 Hz, 4H), 3.89 (s, 6H), 3.87 (s, 6H).

[0194] (Example 29) [Chemical formula]

[0195] Yield: 69% 1 1H NMR (500 MHz, CDCl 3 ): δ 9.43 (dd, J = 6.3, 3.5 Hz, 2H), 7.85 (dd, J = 5.8, 3.4 Hz, 2H), 7.68 (dd, J = 6.9, 3.4 Hz, 2H), 7.28 - 7.42 (m, 4H), 7.23 - 7.26 (m, 4H), 7.01 (dd, J = 6.9, 3.5 Hz, 2H), 6.92 - 6.94 (m, 4H), 6.84 - 6.86 (m, 4H), 3.88 (s, 6H), 3.85 (s, 6H).

[0196] (Example 30) [Chemical formula]

[0197] Yield: 73% 1 1H NMR (500 MHz, C 2 D 2 Cl 4 , 120 °C): δ 9.88 (s, 2H), 8.28 (dd, J = 6.3, 3.4 Hz, 2H), 7.65 (dd, J = 6.3, 3.5 Hz, 4H), 7.45 (d, J = 8.6 Hz, 4H), 7.24 (d, J = 8.6 H, 4H), 7.03 (dd, J = 6.9, 3.5 Hz, 2H), 6.94 (d, J = 8.6 Hz, 4H), 6.89 (d, J = 9.2 Hz, 4H), 3.88 (s, 6H), 3.87 (s, 6H).

[0198] (Example 31)

change

[0199] Yield: 84% 1 H NMR (500 MHz, CDCl 3 ): δ9.91(s,2H),8.24(dd,J=6.3,2.9Hz,2H),7.61-7.65(m,4H),7.48-7.50(m,4H),7.32-7.37(m,16H),6.98(dd,J=6.9,3.4Hz,2H).

[0200] (Example 32)

change

[0201] Yield: 82% 1 H NMR (500 MHz, CDCl 3 ): δ9.21(s,1H),9.20(d,J=7.5Hz,1H),8.61(d,J=8.0Hz,1H),8.12(dd,J=8.0,1.7Hz,1H),7.89-7.91(m,1H),7.75-7.79(m,1H),7.62-7.68( m,2H),3.32-3.35(m,2H),3.13-3.16(m,2H),3.03-3.07(m,4H),1.99- 2.06(m,6H),1.73-1.76(m,2H),1.24-1.27(m,4H),1.12-1.16(m,8H).

[0202] (Example 33)

change

[0203] Yield: 66% 1 H NMR (500 MHz, CDCl 3): δ9.90(s,2H),8.31(s,2H),8.27(dd,J=6.3,2.9Hz,2H),7.62(dd,J=6.3,3.4Hz .2H)3.25-3.30(m,8H),2.12-2.17(m,4H),1.79-1.84(m,4H),1.16-1.21(m,12H).

[0204] (Example 34)

change

[0205] Yield: 67% 1 H NMR (500 MHz, CDCl 3 ): δ9.45(dd,J=6.3,3.5Hz,2H),8.34(s,2H),7.84-7.86(m,2H),3.25-3.30(m,8H),2.09-2.17(m,4H),1.78-1.83(m,4H),1.15-1.18(m,12H).

[0206] (Example 35)

change

[0207] Yield: 78% 1 H NMR (500 MHz, CDCl 3 ): δ8.88(d,J=8.0Hz,2H),7.92(d,J=8.6Hz,2H),7.73-7.76(m,2H),2.99 -3.05(m,8H),1.93-1.98(m,4H),1.69-1.75(m,4H),1.09-1.14(m,12H).

[0208] (Example 36)

change

[0209] Yield: 76% 1H NMR (500MHz, CD 2 Cl 2 / CS 2 ): δ8.66(s,2H),7.38-7.42(m,6H),7.25-7.30(m,6H),7.14-7.18(m,10H),6.79(d,J=8.0Hz,2H),6.74(d,J=8.1Hz,2H),3.69(s,6H).

[0210] (Example 37)

change

[0211] Yield: 74% 1 H NMR (500MHz, CD 2 Cl 2 / CS 2 ): δ8.49(s,2H),7.45(t,J=8.0Hz,2H),6.99(d,J=8.0Hz,2H),6.61(d,J=8.1Hz,2H),4.09(s,br,4H),2.63(s,6H) ,2.35(s,6H),1.86-1.91(m,4H),1.58-1.63(m,4H),1.49-1.55(m,4H),1.22-1.40(m,36H),0.83(t,J=6.9Hz,6H)

[0212] (Example 38)

change

[0213] Yield: 82% 1 H NMR (500MHz, CD 2 Cl 2 / CS 2 ): δ8.66(s,2H)7.64-7.66(m,4H),7.61(t,J=8.0Hz,2H),7.48-7.49(m,6H ),7.40(d,J=8.6Hz,2H),6.86(d,J=7.4Hz,2H),3.76(s,6H),0.15(s,18H).

[0214] (Example 39)

change

[0215] Yield: 59% 1 H NMR (500 MHz, C 2 D 2 Cl 4 ,120℃): δ7.60(t,J=8.0Hz,2H),7.46(s,2H),7.40-7.43(m,4H),7.36-7.38(m,4H),7 .32(d,J=8.0Hz,4H),7.22-7.24(m,6H),7.04(t,J=7.5Hz,2H),6.97(t,J=7.4Hz,4H)

[0216] (Example 40)

change

[0217] Yield: 72% 1 H NMR (500 MHz, CDCl 3 ): δ8.32(d,J=8.6Hz,1H),8.04(s,1H),7.81-7.83(m,2H),7.68(dd,J=9.2,1.8Hz,1H) ,7.53-7.59(m,3H),7.41-7.43(m,5H),7.28-7.30(m,2H),7.20(dd,J=5.2,1.7Hz,3H).

Claims

1. A method for producing a fused polycyclic aromatic heterocyclic compound represented by the following general formula (I) by reacting an oxime ether with an acetylene derivative, the method comprising carrying out the reaction in the presence of a trivalent iron compound, a trivalent phosphorus compound, and a trialkylaluminum: 【Chemistry 1】 (In the above formula (I), Y Ｉ , Y ＩＩ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or a divalent aliphatic hydrocarbon group which may have a substituent. R Ｉ ~R Ｖ each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, a silyl group which may have a substituent, or a hydrogen atom. Z Ｉ ~Z ＩＩＩ each independently represents an element of Group 14, 15 or 16 of the periodic table which may have a substituent, or a hydrogen atom. In formula (I), Z Ｉ and Y Ｉ , Z ＩＩ and Y ＩＩ may be bonded directly or via a linking group to form a ring. A Ｉ ~A ＩＸ each independently has an optional substituent. m represents an integer.

2. A method for producing a fused polycyclic aromatic heterocyclic compound represented by the following formula (II), (III), (IV), or (V) by reacting an oxime ether with an acetylene derivative, the method comprising the steps of: 【Chemistry 2】 (In the above formulas (II), (III), (IV), and (V), R １ ~R １２ each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, a silyl group which may have a substituent, or a hydrogen atom. Z １ ~Z １２ each independently represents an element of Group 14, 15, or 16 of the periodic table which may have a substituent, or a hydrogen atom. １ and Z ２ , Z ３ and Z ４ , Z ５ and Z ６ , Z ７ and Z ８ , Z ９ and Z １０ , Z １１ and Z １２ may be bonded directly or via a linking group, or may form a ring. A １ ~A １２ , B １ ~B １０ and C １ ~C ６ each independently represents an arbitrary substituent. The dotted line in formula (II) represents an ethylene group which may have a substituent, or an ethynylene group which may have a substituent.

3. The method for producing a fused polycyclic aromatic heterocyclic compound according to claim 1 or 2, wherein the trivalent phosphorus compound includes a compound represented by the following formula (VI): 【Chemistry 3】 (In the above formula (VI), R １３ , R １４ each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aliphatic hydrocarbon group which may have a substituent. X represents a nitrogen atom, an oxygen atom, or a sulfur atom which may have a substituent.

4. The method for producing a fused polycyclic aromatic heterocyclic compound according to claim 1 or 2, wherein the reaction is further carried out in the presence of at least one of a bidentate ligand capable of forming a 6-membered or 5-membered ring complex with aluminum, catechol, 1,8-dihydroxynaphthalene, and derivatives thereof.

5. The method for producing a fused polycyclic aromatic heterocyclic compound according to claim 1 or 2, wherein the reaction is carried out in the presence of one or more reaction solvents selected from the group consisting of ether solvents, aromatic solvents, and halogenated solvents.

6. A condensed polycyclic aromatic heterocyclic compound represented by the following formula (I): 【Chemistry 4】 (In the above formula (I), Y Ｉ , Y ＩＩ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or a divalent aliphatic hydrocarbon group which may have a substituent. R Ｉ ~R Ｖ each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, a silyl group which may have a substituent, or a hydrogen atom. Z Ｉ ~Z ＩＩＩ each independently represents an element of Group 14, 15 or 16 of the periodic table which may have a substituent, or a hydrogen atom. In formula (I), Z Ｉ and Y Ｉ , Z ＩＩ and Y ＩＩ may be bonded directly or via a linking group to form a ring. A Ｉ ~A ＩＸ each independently has an optional substituent. m represents an integer.

7. A condensed polycyclic aromatic heterocyclic compound represented by the following formula (II), (III), (IV) or (V): 【Chemistry 5】 (In the above formulas (II), (III), (IV), and (V), R １ ~R １２ each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, a silyl group which may have a substituent, or a hydrogen atom. Z １ ~Z １２ each independently represents an element of Group 14, 15, or 16 of the periodic table which may have a substituent, or a hydrogen atom. １ and Z ２ , Z ３ and Z ４ , Z ５ and Z ６ , Z ７ and Z ８ , Z ９ and Z １０ , Z １１ and Z １２ may be bonded directly or via a linking group, or may form a ring. A １ ~A １２ , B １ ~B １０ and C １ ~C ６ each independently represents an arbitrary substituent. The dotted line in formula (II) represents an ethylene group which may have a substituent, or an ethynylene group which may have a substituent.

8. 8. The fused polycyclic aromatic heterocyclic compound according to claim 6, wherein the half-value width of the maximum peak of the fluorescence spectrum is 25 nm or less.

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