JP2021172623A - Nitrogen-containing condensed polycyclic aromatic compound and method for producing the same - Google Patents

Abstract

To provide a novel nitrogen-containing condensed polycyclic aromatic compound.SOLUTION: The present invention relates to a compound represented by formula (I) (where, R1-R10 are a hydrogen atom, or a substituent such as an alkyl group. Q is one of 5-7 membered ring structures. Z1 is a nitrogen atom, or a phosphorus atom, or (Z2)+Y- (where, (Z2)+ is a monovalent counter cation of an oxygen atom or a sulfur atom, Y-is a monovalent counter anion).SELECTED DRAWING: None

Description

The present invention relates to a novel nitrogen-containing condensed polycyclic aromatic compound and a method for producing the nitrogen-containing condensed polycyclic aromatic compound.

The condensed polycyclic aromatic hydrocarbon compound into which a nitrogen atom has been introduced is a nitrogen-containing graphite derivative, which is a negative electrode material for a lithium battery (for example, Patent Document 1) and a fuel cell catalyst instead of a platinum catalyst (for example, Patent Document 2). Various uses are being studied and developed.

Conventionally, a method of calcining a nitrogen-containing polymer such as a melamine resin or a urea resin has been used for producing a nitrogen-containing graphite derivative.
However, with this method, it is difficult to control the amount of nitrogen atoms introduced into the produced nitrogen-containing graphite derivative, it is also difficult to confirm the amount of nitrogen atoms introduced, and it is difficult to quantitatively evaluate the nitrogen content. there were.

By using a monomer compound having a small molecular weight instead of a polymer as the nitrogen atom-containing compound for introducing a nitrogen atom into a graphite derivative, it is considered that the amount of nitrogen atom introduced can be easily controlled and quantified.
However, since compounds having a small molecular weight generally have a low boiling point and are unstable at high temperatures, it has been considered difficult to use them for introducing nitrogen atoms into graphite derivatives exposed to high-temperature firing conditions.
However, in recent years, it has been reported that condensed polycyclic aromatic compounds having a nitrogen atom exhibit high thermal stability having a melting point of 250 ° C. or higher (for example, Non-Patent Document 1).

Based on such background technology, it is currently required to provide a new nitrogen-containing condensed polycyclic aromatic compound.

Japanese Unexamined Patent Publication No. 2001-80914 Japanese Unexamined Patent Publication No. 2016-102037

S. Ito, Y. Tokimaru, K.K. Nozaki Chem. Commun. , 2015, 51,221-224.

An object of the present invention is to provide a novel nitrogen-containing condensed polycyclic aromatic compound as a nitrogen atom-containing compound.

As a result of repeated studies to solve the above problems, the present inventor has succeeded in synthesizing a novel nitrogen-containing condensed polycyclic aromatic compound, and completed the present invention.
That is, the gist of the present invention is as follows.

[1] A nitrogen-containing condensed polycyclic aromatic compound represented by the following general formula (I).

(In the general formula (I), R ^{1 to} R ¹⁰ are independently hydrogen atoms, or alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, allyloxy groups, halogen elements, and amino groups. Represents a substituent selected from the group consisting of: Q is any of the 5-7 membered ring structures. Z ¹ is a nitrogen atom, or a phosphorus atom, or (Z ² ) ⁺ Y ⁻ (where, (where, Z ² ) ⁺ represents a monovalent counter cation of an oxygen atom or a sulfur atom, and Y ⁻ represents a monovalent counter anion.)

[2] The nitrogen-containing ring according to [1], wherein the ring structure Q in the general formula (I) is a substituted or unsubstituted benzene ring, pyridine ring, furan ring, thiophene ring, or pyrrole ring. Condensed polycyclic aromatic compound.

[3] The nitrogen-containing condensed polycyclic aromatic compound according to [2], wherein the ring structure Q in the general formula (I) is a substituted or unsubstituted benzene ring or pyridine ring.

[4] A step of reacting a substituted aromatic compound represented by the following general formula (II) with an isoquinolino [4,3,2-de] phenanthriginium compound represented by the following general formula (III). The method for producing a nitrogen-containing condensed polycyclic aromatic compound according to any one of [1] to [3].

(In the general formula (II), Q is synonymous with the above general formula (I), X is a halogen atom, W is a formyl group, a carboxyl group, a thioformyl group, a thiocarboxyl group, and 2 to 20 carbon atoms. Indicates a substituent selected from the group consisting of an acyl group, an ester group having 2 to 20 carbon atoms, a substituted ethynyl group having 2 to 20 carbon atoms, a phosphoethynyl group, and a cyano group.

(In the general formula (III), R ^{1 to} R ¹⁰ are synonymous with those in the general formula (I), and Y ⁻ represents a monovalent counter anion.)

[5] The nitrogen-containing ring according to [4], wherein the ring structure Q in the general formula (II) is a substituted or unsubstituted benzene ring, pyridine ring, furan ring, thiophene ring, or pyrrole ring. A method for producing a condensed polycyclic aromatic compound.

[6] The method for producing a nitrogen-containing condensed polycyclic aromatic compound according to [5], wherein the ring structure Q in the general formula (II) is a substituted or unsubstituted benzene ring or pyridine ring. ..

[7] The substituent W in the general formula (II) is selected from the group consisting of a formyl group, a carboxyl group, an ester group having 2 to 20 carbon atoms, a substituted ethynyl group having 2 to 20 carbon atoms, and a cyano group. The method for producing a nitrogen-containing condensed polycyclic aromatic compound according to any one of [4] to [6], which is a substituent.

[8] The inclusion according to [7], wherein the substituent W in the general formula (II) is a substituent selected from the group consisting of a formyl group, an ester group having 2 to 20 carbon atoms, and a cyano group. A method for producing a nitrogen-condensed polycyclic aromatic compound.

[9] The method for producing a nitrogen-containing condensed polycyclic aromatic compound according to [8], wherein the substituent W in the general formula (II) is a cyano group.

The nitrogen-containing condensed polycyclic aromatic compound of the present invention is a novel nitrogen-containing condensed polycyclic aromatic compound and can be produced by a simple reaction step. Therefore, it is a compound for introducing a nitrogen atom during production of a nitrogen-containing graphite derivative. It is useful as.
Moreover, since the nitrogen-containing condensed polycyclic aromatic compound of the present invention is not a high-molecular polymer such as a conventional nitrogen-containing polymer such as a melamine resin or a urea resin, this nitrogen-containing condensed polycyclic aromatic compound should be used. Therefore, it is possible to efficiently introduce nitrogen atoms after precisely controlling the amount of nitrogen introduced into the nitrogen-containing graphite derivative, and it is possible to easily control the structure of the obtained nitrogen-containing graphite derivative and quantify the amount of nitrogen atoms introduced. ..

Hereinafter, embodiments of the present invention will be described in detail.

[Nitrogen-containing condensed polycyclic aromatic compounds]
The nitrogen-containing condensed polycyclic aromatic compound of the present invention is represented by the following general formula (I).

(In the general formula (I), R ^{1 to} R ¹⁰ are independently hydrogen atoms, or alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, allyloxy groups, halogen elements, and amino groups. Represents a substituent selected from the group consisting of: Q is any of the 5-7 membered ring structures. Z ¹ is a nitrogen atom, or a phosphorus atom, or (Z ² ) ⁺ Y ⁻ (where, (where, Z ² ) ⁺ represents a monovalent counter cation of an oxygen atom or a sulfur atom, and Y ⁻ represents a monovalent counter anion.)

In the general formula (I), R ^{1 to} R ¹⁰ are independently hydrogen atoms or alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, allyloxy groups, halogen elements, and substituted or absent. Represents a substituent selected from the group consisting of substituted amino groups.

The ^{alkyl groups R 1 to} R ¹⁰ are preferably substituted or unsubstituted non-cyclic hydrocarbon groups having 1 to 20 carbon atoms, and may be substituted with an alkoxy group, an ester group, or a halogen atom. Specific examples of alkyl groups include methyl group, ethyl group, 1-propyl group, isopropyl group, 1-butyl group, isobutyl group, t-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1 -Octyl group, 1-nonyl group, 1-decyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1 -Diethylpropyl group, 1-phenyl-2-propyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl Group, 3-heptyl group, 4-heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, 1- (methoxymethyl) ethyl group, 1- (ethoxymethyl) ethyl group, 1- (methoxy) Ethyl) Ethyl group, 1- (ethoxyethyl) ethyl group, di (methoxymethyl) methyl group, di (ethoxymethyl) methyl group, di (phenoxymethyl) methyl group, 1- (methoxycarbonyl) methyl group, 2- ( Examples thereof include methoxycarbonyl) ethyl group, 1- (ethoxycarbonyl) methyl group, 2- (ethoxycarbonyl) ethyl group, monochloromethyl group, dichloromethyl group and trifluoromethyl group. Among these, preferred alkyl groups are methyl group, ethyl group, 1-propyl group, isopropyl group, 1-butyl group, isobutyl group, t-butyl group and trifluoromethyl group, and particularly preferable substituents are It is a methyl group, a t-butyl group, and a trifluoromethyl group.

The ^{cycloalkyl groups R 1 to} R ¹⁰ are preferably cycloalkyl groups having 3 to 20 carbon atoms and which may have an alkyl group as a substituent, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and the like. Methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo [2.2 .2] Examples include an octyl group, a decahydronaphthyl group, a mentyl group, a neomentyl group, and a 5-decyl group. Among these, a preferable cycloalkyl group is a cyclohexyl group and a methylcyclohexyl group, and a particularly preferable cycloalkyl group is a cyclohexyl group.

Examples of the alkenyl group having R ^{1 to R 10} include an alkenyl group having 2 to 20 carbon atoms, which may have an alkyl group as a substituent such as a vinyl group, an allyl group, a butenyl group, a cinnamyl group and a styryl group. Can be mentioned. A vinyl group, an allyl group, and a styryl group are preferable, and a vinyl group is particularly preferable.

Examples of the alkynyl group having R ^{1 to R 10} include an ethynyl group, an n-1-propynyl group, an n-2-propynyl group, an n-1-butynyl group, an n-2-butynyl group and an n-3-butynyl group. 1-Methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4-pentynyl group, 1-methyl-n-butynyl group, 2-methyl- n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, 2,2-dimethyl-1-propynyl group, n-1-hexynyl group, n-1-decynyl group, Examples thereof include an alkynyl group having 2 to 20 carbon atoms, which may have an alkyl group or an aryl group as a substituent such as an n-1-pentadecynyl group, an n-1-eicosynyl group, a 2-phenylethynyl group and the like. Among these, preferred alkynyl groups are ethynyl group, n-1-propynyl group, 1-methyl-2-propynyl group, n-1-pentynyl group, 2,2-dimethyl-1-propynyl group and 2-phenyl. It is an ethynyl group, and particularly preferably an ethynyl group, an n-1-propynyl group, or a 2-phenylethynyl group.

Examples of the aryl group having R ^{1 to R 10} include a phenyl group, a naphthyl group, an anthrasenyl group, and a fluorenyl group. Substituents may be present in the aromatic rings of these aryl groups. Examples of the substituents that can be present include an alkyl group, an aryl group, a phenylcyclohexyl group, a phenylbutenyl group, a trill group, a xsilyl group, a p-ethylphenyl group and the like. Among these, preferred aryl groups are a phenyl group and a substituted phenyl group, and preferred specific examples of the substituent of the substituted phenyl group are a methyl group, an ethyl group and a phenyl group, and a methyl group is particularly preferable. be.

Examples of the alkoxy group having R ^{1 to R 10} include an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group, a 1-propoxy group, a 1-butoxy group, and a t-butoxy group. .. Among these, a more preferable alkoxy group is a methoxy group, an ethoxy group or an isopropoxy group, and a methoxy group is particularly preferable.

The ^{allyloxy groups R 1 to} R ¹⁰ include a phenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 2,6-dimethylphenoxy group, a 3,5-di-t-butylphenoxy group and 2,6. Examples of the substituent such as the -di-t-butylphenoxy group include an aryloxy group which may have an alkyl group. Among these, the preferred allyloxy group is a phenoxy group, 3,5-di-t-butylphenoxy group or 2,6-dimethylphenoxy group, and particularly preferably a phenoxy group, 3,5-di-t-butyl. It is a phenoxy group.

The ^{halogen element of R 1 to} R ¹⁰ means a halogen element belonging to Group 17 of the periodic table, and specifically, it is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and preferably a fluorine atom or a chlorine atom. , Bromine atom, particularly preferably a fluorine atom and a chlorine atom.

Examples of the amino groups R ^{1 to R 10} include monomethylamino group, dimethylamino group, monoethylamino group, diethylamino group, monoisopropylamino group, diisopropylamino group, monophenylamino group, diphenylamino group and bis (trimethylsilyl). Examples thereof include a mono-substituted amino group substituted with an alkyl group such as an amino group and a morpholinyl group or an aryl group, and a di-substituted amino group. Among these, more preferable amino groups are dimethylamino group and diphenylamino group.

^{In the present invention, R 1 to} R ¹⁰ in the general formula (I) are preferably methyl group, t-butyl group, trifluoromethyl group, phenyl group and methoxy group from the viewpoint of availability of raw materials and compound stability. , Phenoxy group, 3,5-di-t-butylphenoxy group, fluorine atom, chlorine atom, dimethylamino group. Particularly preferred are a t-butyl group, a trifluoromethyl group, a fluorine atom and a chlorine atom.

Q has any of a 5- to 7-membered ring structure and may contain a heteroatom. Specific examples of a preferable ring structure are a benzene ring, a pyridine ring, a furan ring, a thiophene ring, or a pyrrole ring. Among these, a benzene ring, a pyridine ring, or a thiophene ring is more preferable, and a benzene ring or a pyridine ring is particularly preferable.

The ring structure formed by Q may have a substituent or may be unsubstituted. When it has a substituent, the substituent includes a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, and a substituted silyl group having 3 to 18 carbon atoms. , Or a halogen atom. Preferred specific examples of the substituent are methyl group, ethyl group, 1-propyl group, isopropyl group, 1-butyl group, isobutyl group, t-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1, 1-diethylpropyl group, 1-phenyl-2-propyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2- Heptyl group, 3-heptyl group, 4-heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, monochloromethyl group, dichloromethyl group, trifluoromethyl group, methoxy group, ethoxy group, isopropoxy Group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, (4-hydroxybutoxy) carbonyl group, (4-glycidylbutoxy) carbonyl group , Phenoxycarbonyl group, trimethylsilyl group, (dimethyl) (phenyl) silyl group, (diphenyl) (methyl) silyl group, triphenylsilyl group, fluorine atom, chlorine atom, bromine atom. Among these, more preferably, a methyl group, an isopropyl group, a t-butyl group, a trifluoromethyl group, a methoxy group, an isopropoxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a trimethylsilyl group, a fluorine atom and a chlorine atom. Particularly preferred are a methyl group, a t-butyl group, a trifluoromethyl group, and a fluorine atom.

^{Z 1} in the general formula (I) represents a nitrogen atom or a phosphorus atom. ^{In the present invention, Z 1 which} is particularly preferable from the viewpoint of availability of raw materials and compound stability is a nitrogen atom.

Further, Z ¹ may be an ion pair consisting of (Z ² ) ⁺ Y ^−. Here, (Z ² ) ⁺ is a monovalent counter cation of an oxygen atom or a sulfur atom, and preferred specific examples are oxonium or sulfonium, and more preferably oxonium.

Y ⁻ represents a monovalent counter anion. The ^{counter anion represented by Y −} may be any monovalent anion. Specific examples of Y ⁻ include halide ions such as fluoride ion (F ⁻ ), chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), and iodide ion (I ⁻ ); tetrafluoroborate (BF _4). ^-), bromo trifluoroborate (BBrF ₃ ^-), chloro trifluoroborate (BCLF ₃ ^-), trifluoromethoxy borate ^{_{(BF 3 (OCH 3) -}} ), trifluoroethoxy borate _{(BF 3 (OC 2 H 5} ) ^-), trifluoroacetic Ali Loki Chevrolet preparative _{(BF 3 (OC 3 H 5} ) -), tetraphenylborate _{(B (C 6 H 5)} 4 -), tetrakis (3,5-bis (trifluoromethyl) phenyl) borate ( _{B (3,5- (CF 3) 2} C 6 H 3) 4 - = BArF 4 -), bromo triphenyl borate _{(BBr (C 6 H 5)} 3 -), chlorotrifluoroethylene tetraphenylborate _{(BCl (C} 6 H _{5) 3} ^-), methoxy triphenyl borate _{(B (OCH 3) (C} 6 H 5) 3 -), ethoxy triphenyl borate _{(B (OC 2 H 5)} (C 6 H 5) 3 -), aryloxy triphenyl borate _{(B (OC 3 H 5)} (C 6 H 5) 3 -), tetrakis (pentafluorophenyl) borate _{(B (C 6 F 5)} 4 -), bromotris (pentafluorophenyl) borate (BBr ( ^{_{C 6 F 5) 3 -)}} , chlorotris (pentafluorophenyl) borate _{(BCl (C 6 F 5)} 3 -), methoxy tris (pentafluorophenyl) borate _{(B (OCH 3) (C} 6 F 5) 3 - ), ethoxy tris (pentafluorophenyl) borate _{(B (OC 2 H 5)} (C 6 F 5) 3 -), Arirokishitorisu (pentafluorophenyl) borate _{(B (OC 3 H 5)} (C 6 F 5 ^-) ₃₎ borate ions and the like; methanesulfonate _(CH 3 SO ₃ ^-), trifluoromethanesulfonate _(CF 3 SO ₃ ^-), nonafluorobutanesulfonate ^{_{(C 4 F 9 SO 3 -}} ), benzenesulfonate _(C 6 H ₅ SO ₃ ^-), p- toluenesulfonate _{(p-CH 3 -C 6 H} 4 Ssulfonate ions such as SO ₃ ⁻ ); acetate ion (CH ₃ CO ₂ ⁻ ), trifluoroacetate ion (CF ₃ CO ₂ ⁻ ), trichloroacetate ion (CCl ₃ CO ₂ ⁻ ), propionate ion (C ₂ H _{5 −)} Carboxylate ions such as CO ₂ ⁻ ) and benzoate ion (C ₆ H ₅ CO ₂ ⁻ ); Phosphate ions such as hexafluorophosphate (PF ₆ ⁻ ); Arsenate such as hexafluoroarsenate ion (AsF ₆ ^{−) -} ion, hexafluoroantimonate (SbF ₆₎ antimonate ions such; hexafluorosilicate (SiF ₆ ^-) silicate ions and the like; sulfate ion _(SO ^{4 2-),} nitrate ion (NO ₃ ^-), carbonate ions ( CO ₃ ^2-), perchlorate ion (ClO ₄ ^-, etc.). In the present invention, from the viewpoint of availability of raw materials and compound stability, Y ⁻ is preferably F ⁻ , Cl ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , or BF ₄ ⁻ . Particularly preferably Cl ^-, or BF ₄ ^- is.

Specific examples of the nitrogen-containing condensed polycyclic aromatic compound of the present invention include the following compounds. These are examples, and it is self-evident that they are not limited to these.

[Method for producing nitrogen-containing condensed polycyclic aromatic compounds]
The method for producing a nitrogen-containing condensed polycyclic aromatic compound of the present invention includes a substituted aromatic compound represented by the following general formula (II) (hereinafter, may be referred to as “compound (II)”) and a general formula. It is characterized by having a step of reacting with an isoquinolino [4,3,2-de] phenanthriginium compound represented by (III) (hereinafter, may be referred to as "compound (III)"). .. More specifically, a compound added by reacting compound (II) with compound (III) (hereinafter, may be referred to as a "ring-opening body") is produced (hereinafter, this step is "added". (Sometimes referred to as "step"), the ring-opened compound is cyclized in the molecule (hereinafter, this step may be referred to as "ring-closing step"), and the book represented by the general formula (I). The nitrogen-containing condensed polycyclic aromatic compound of the present invention is produced.

(In the general formula (II), Q is synonymous with the above general formula (I), X is a halogen atom, W is a formyl group, a carboxyl group, a thioformyl group, a thiocarboxyl group, and 2 to 20 carbon atoms. Indicates a substituent selected from the group consisting of an acyl group, an ester group having 2 to 20 carbon atoms, a substituted ethynyl group having 2 to 20 carbon atoms, a phosphoethynyl group, and a cyano group.

(In the general formula (III), R ^{1 to} R ¹⁰ are synonymous with those in the general formula (I), and Y ⁻ represents a monovalent counter anion.)

The compound (II) may be any compound capable of producing a ring-opened compound, that is, a compound (II) capable of producing a nitrogen-containing condensed polycyclic aromatic compound of the present invention through a ring-closing step, particularly. There is no limit.

X in the general formula (II) means a halogen element belonging to Group 17 of the periodic table, specifically, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom and a bromine atom. Particularly preferably, it is a chlorine atom.

W in the general formula (II) is a formyl group, a carboxyl group, a thioformyl group, a thiocarboxyl group, an acyl group having 2 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a substituted ethynyl group having 2 to 20 carbon atoms, The substituent selected from the group consisting of a phosphaethynyl group and a cyano group is shown. It is preferably a substituent selected from the group consisting of a formyl group, a carboxyl group, an ester group having 2 to 10 carbon atoms, a substituted ethynyl group having 2 to 10 carbon atoms, and a cyano group, and particularly preferably a formyl group and a carbon number of carbon atoms. It is a substituent selected from the group consisting of 2 to 10 ester groups and a cyano group, and is most preferably a cyano group.

The acyl group having 2 to 10 carbon atoms, which is W in the general formula (II), is preferably an acyl group having 2 to 8 carbon atoms. Preferred specific examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group and a benzoyl group. Among these, more preferable acyl groups are acetyl groups, pivaloyl groups and benzoyl groups, and particularly preferably acetyl groups and benzoyl groups.

The ester group having 2 to 10 carbon atoms, which is W in the general formula (II), is preferably an ester group having 2 to 8 carbon atoms, and preferred specific examples are a methoxycarbonyl group, an ethoxycarbonyl group, and an n-propoxycarbonyl group. , Isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, (4-hydroxybutoxy) carbonyl group, (4-glycidylbutoxy) carbonyl group, phenoxycarbonyl group, succinic anhydride group, succinateimide group Can be mentioned. Among these, more preferable ester groups are a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a t-butoxycarbonyl group, and a methoxycarbonyl group is particularly preferable.

The substituted ethynyl group having 2 to 10 carbon atoms, which is W in the general formula (II), is preferably a substituted ethynyl group having 2 to 8 carbon atoms, and preferred specific examples are a phenylethynyl group and (4-methyl) phenylethynyl. Group, (3,5-dimethyl) phenylethynyl group, (4-hydroxy) phenylethynyl group, (3,5-dihydroxy) phenylethynyl group, (4-methoxy) phenylethynyl group, (3,5-dimethoxy) phenyl Ethynyl group, (4-acetyl) phenylethynyl group, (4-dimethylamino) phenylethynyl group, (4-amino) phenylethynyl group, (4-nitro) phenylethynyl group, (4-chloro) phenylethynyl group, ( A 4-bromo) phenylethynyl group can be mentioned. Among these, the more preferable substituted ethynyl group is a phenylethynyl group, a (4-acetyl) phenylethynyl group, a (4-dimethylamino) phenylethynyl group, and particularly preferably a phenylethynyl group.

Among the preferable specific examples of W in the general formula (II), further preferable substituents include an acetyl group, a benzoyl group, a methoxycarbonyl group, a phenylethynyl group and a cyano group, and particularly preferably an acetyl group and a cyano group. Yes, most preferably a cyano group.

The compound (III) may be any compound capable of producing an adduct, that is, a compound capable of producing the nitrogen-containing condensed polycyclic aromatic compound of the present invention through the addition step, and is particularly limited. There is no.

<Additional process>
The addition step is carried out by heating compound (II) and compound (III) in a solvent in the presence of a catalyst or pH adjuster, if necessary.

The amount of each compound added may be a reaction equivalent, but in general, compound (II) is added in an amount of 5.0 to 1.0 equivalent, particularly 3.0 to 1.0, based on compound (III). It is preferable to use an excess amount of the equivalent amount.

The reaction solvent may be any one that dissolves the reaction substrate and is not particularly limited. For example, a hydrocarbon solvent such as n-hexane, n-heptane, toluene, xylene, cyclohexane, or methylcyclohexane, or diethyl ether. , Ethylglycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, chloroform, dichloromethane, acetonitrile, methanol, ethanol, isopropyl alcohol, ethylene glycol, etc. Solvents can be mentioned. Only one of these solvents may be used, or two or more of these solvents may be mixed and used.

If the concentration of the compound represented by compound (II) and the concentration of compound (III) in the reaction solution are excessively low, it causes a decrease in yield due to a decrease in reactivity, and if it is excessively high, a side reaction occurs. The total concentration of the reaction substrates is preferably 0.05 to 0.50 mmol / L, particularly preferably about 0.10 to 0.20 mmol / L.

Examples of catalysts include cesium fluoride, potassium fluoride, tetrabutylammonium fluoride (TBAF), tetramethylammonium fluoride (TMAF), tetrabutylammonium triphenyldifluorosilicate (TBAT), and tris difluorotrimethylsilicate (dimethylamino). Examples thereof include sulfonium (TASF), cesium carbonate, cesium chloride, and cesium acetate, and cesium fluoride, cesium carbonate, cesium chloride, and cesium acetate are particularly preferable. Only one kind of these may be used, or two or more kinds thereof may be mixed and used. The catalyst is preferably used in the range of 0.0001 to 0.1000 equivalents relative to compound (II).

If the reaction temperature is excessively low, the addition cyclization reaction does not proceed sufficiently, and if it is excessively high, side reactions occur, so that the reaction temperature is preferably in the range of 50 to 250 ° C., particularly 100 to 200 ° C. ..

The reaction time varies depending on the reactivity of the compound (II) and the compound (III) used and the reaction temperature, but is usually about 0.5 to 12 hours.

The addition reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen from the viewpoint of suppressing by-products due to the oxidation reaction, but may be carried out in an air atmosphere.

After the addition reaction is completed, the generated ring-opened body can be used as it is in the ring-closing step.

The ring-opened body obtained by such an addition step can be identified by NMR, mass spectrometry and the like.

<Ring closure process>
The ring closure reaction of the ring-opening body can be carried out by dissolving the obtained ring-opening body in a solvent and heating in the presence of an additive such as a catalyst used as needed.

The solvent used in the ring closing step may be any solvent that dissolves the reaction substrate, and is not particularly limited. For example, a hydrocarbon solvent such as n-hexane, n-heptane, toluene, xylene, cyclohexane, or methylcyclohexane. Diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, chloroform, dichloromethane, acetonitrile, methanol, ethanol, isopropyl alcohol, ethylene glycol Such as polar solvents can be mentioned. Only one of these solvents may be used, or two or more of these solvents may be mixed and used.

If the concentration of the ring-opening substance in the reaction solution during the ring-closing reaction is excessively low, it causes a decrease in yield due to a decrease in reactivity, and if it is excessively high, a side reaction occurs. It is preferably used so as to be 0.01 to 0.30 mmol / L, particularly 0.02 to 0.10 mmol / L.

When the compound (II) used has a halogen atom as an active point of the ring closure reaction, such as 2-chlorobenzonitrile, di-tert-butyl (methyl) phosphonium tetrafluoro is used to enhance the ring closure reaction activity. It is preferable to use one kind or two or more kinds such as borate, and it is preferable to use 0.5 to 2.0 equivalents with respect to the ring-opened body.

In the ring closing step, as catalysts, tris (dibenzylideneacetone) dipalladium, (1,5-cyclooctadiene) (methyl) palladium chloride, palladium chloride, palladium acetate, bis (acetohydrate) dichloropalladium, bis (benzonitrile) ) Dichloropalladium, (N, N, N', N'-tetramethylethylenediamine) dichloropalladium, (N, N, N', N'-tetramethylethylenediamine) dimethylpalladium, bis (acetylacetonato) palladium, trifluoromethane It is preferable to use one or more kinds of palladium sulfonate, tetracarbonyl nickel, bis (1,5-cyclooctadien) nickel and the like, and the catalyst is used in an amount of 0.10 to 0.80 equivalent with respect to the ring-opened body. Is preferable.

The ring closure reaction is carried out by adding a required amount of a ring-opening agent, a dehalogenating agent, a catalyst, or the like to the above reaction solvent and heating the reaction solvent.

If the reaction temperature of the ring closure reaction is excessively low, the reaction will not proceed sufficiently, and if it is excessively high, side reactions of the raw materials will occur, so the reaction temperature should be in the range of 50 to 250 ° C, especially 100 to 200 ° C. Is preferable.

The reaction time varies depending on the reactivity of the active site of the ring closure reaction of the ring-opening body used and the reaction temperature, but is usually about 0.5 to 24 hours.

The ring closure reaction may be carried out in an atmosphere of an inert gas such as nitrogen, or may be carried out in an atmospheric atmosphere.

After completion of the ring closure reaction, the nitrogen-containing condensed polycyclic aromatic compound of the present invention, which is a ring-closed product produced, can be purified by silica gel chromatography, recrystallization method or the like.

Specific reaction examples of the method for producing a nitrogen-containing condensed polycyclic aromatic compound of the present invention are shown below, but the method for producing a nitrogen-containing condensed polycyclic aromatic compound of the present invention is limited to the following reaction examples. It's not a thing.

Hereinafter, the present invention will be described in more detail with reference to examples.

The raw material 2-t-butyl-8-hydroisoquinolino [4,3,2-de] phenanthridinium (Compound 1) was prepared by the method described in the following literature.
S. Ito, Y. Tokimaru, K.K. Nozaki Chem. Commun. , 2015, 51,221-224.

[Example 1] Synthesis of 9- (t-butyl) -dibenzo [b, mn] benzo [7,8] indridino [2,3,4,5,6-defg] acridine (4a)

<Additional process>

2-t-Butyl-8-hydroisoquinolino chloride [4,5,2-de] phenanthridinium (Compound 1) (36 mg, 0.10 mmol), 2-chlorobenzonitrile (Compound 1) under a nitrogen atmosphere. 2a) Diisopropylethylamine (0.070 mL, 0.40 mmol) was added to a DMSO solution (3.0 mL) of (41 mg, 0.30 mmol) and cesium fluoride (61 mg, 0.40 mmol) at room temperature, and 12 at 160 ° C. Stirred for hours. After cooling to room temperature, the reaction solution was diluted with toluene (50 mL), washed with water (15 mL) and saturated aqueous sodium chloride solution (15 mL), and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was dissolved in methylene chloride (5 mL) to add 2,3-dichloro-5,6-dicyano-p-benzoquinone (23 mg, 0.10 mmol). Added. The solution was stirred at room temperature for 20 minutes. After diluting with methylene chloride (50 mL), the mixture was washed twice with saturated aqueous sodium hydrogen carbonate solution (15 mL) and saturated aqueous sodium chloride solution (15 mL) and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was purified by silica gel column chromatography to obtain compound 3a. 24 mg, yield 52%.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 8.80-8.70 (m, 1H), 8.52-8.45 (m, 2H), 8.43 (s, 1H), 8.38 (d, J = 8.0 Hz, 1H), 7.74 ( dd, J = 5.6, 3.6 Hz, 1H), 7.70-7.63 (m, 2H), 7.62 (dd, J = 5.6, 4.0 Hz, 1H), 7.56 (d, J = 8.0 Hz, 1H), 7.53-7.44 (m, 3H), 7.35 (t, J = 7.5 Hz, 1H), 1.58 (s, 9H);
¹³ C NMR (100 MHz, CDCl ₃ , 300 K) δ 147.9, 137.2, 135.4, 135.1, 134.5, 133.0, 129.9, 129.9, 128.7, 128.6, 128.5, 128.0, 127.2, 127.1, 126.6, 126.4, 125.4, 124.2, 123.9, 123.8, 123.0, 122.8, 122.8, 121.9, 120.8, 118.2, 118.0, 35.5, 31.8 (3C).

<Ring closure process>

Under a nitrogen atmosphere, compound 3a (27.5 mg, 0.06 mmol), palladium (II) acetate (8.1 mg, 0.036 mmol), di-tert-butylmethylphosphonium tetrafluoroborate (45 mg, 0.18 mmol). ) To the mixture was added dimethylformamide (2.0 mL) and diazabicycloundecene (0.5 mL) at room temperature, and the mixture was stirred at 160 ° C. overnight. After cooling to room temperature, the reaction solution was diluted with toluene, washed 4 times with water and 1 time with saturated aqueous sodium chloride solution, and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was purified by silica gel column chromatography to obtain compound 4a. 10.8 mg, yield 43%.

¹ H NMR (400 MHz, CD ₂ Cl ₂ / CS ₂ , 300 K) δ 8.79-8.74 (m, 1H), 8.66 (d, J = 8.4 Hz, 2H), 8.56 (d, J = 8.4 Hz, 1H) ), 8.55-8.49 (m, 1H), 8.47 (d, J = 2.8 Hz, 2H), 8.32 (d, J = 8.0 Hz, 1H), 7.81 (t, J = 7.6 Hz, 1H), 7.78-7.69 (m, 3H), 7.61 (t, J = 7.8 Hz, 1H), 1.64 (s, 9H);
¹³ C NMR (100 MHz, CD ₂ Cl ₂ / CS ₂ , 300 K) δ 148.9, 139.2, 132.9, 130.0, 129.6, 129.2, 129.2, 128.9, 128.7, 128.0, 126.8, 126.7, 126.2, 125.5, 125.0, 124.7 , 124.2, 123.7, 123.2, 122.8, 122.3, 121.5, 121.4, 120.2, 120.1, 119.4, 119.1, 36.0, 32.1 (3C).

[Example 2] 9- (t-butyl) -3-fluoro-14,15-dibenzo [b, mn] benzo [7,8] indridino [2,3,4,5,6-defg] acridine (4b) ) Synthesis

<Additional process>

2-t-Butyl-8-hydroisoquinolino chloride [4,5,2-de] phenanthridinium (Compound 1) (54 mg, 0.15 mmol), 2-chloro-4-fluoro under a nitrogen atmosphere. -DMSO (3.0 mL) was added to a mixture of benzonitrile (Compound 2b) (233 mg, 1.50 mmol) and cesium carbonate (98 mg, 0.30 mmol) at room temperature, and the mixture was stirred at 160 ° C. for 12 hours. After cooling to room temperature, the reaction solution was diluted with toluene (50 mL), washed with water (15 mL) and saturated aqueous sodium chloride solution (15 mL), and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was dissolved in methylene chloride (5 mL) to add 2,3-dichloro-5,6-dicyano-p-benzoquinone (23 mg, 0.10 mmol). Added. The solution was stirred at room temperature for 20 minutes. After diluting with methylene chloride (50 mL), the mixture was washed twice with saturated aqueous sodium hydrogen carbonate solution (15 mL) and saturated aqueous sodium chloride solution (15 mL) and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was purified by silica gel column chromatography to obtain compound 3b. 28.7 mg, yield 40%.

IR (neat); cm ^-1 3071, 2951, 2905, 2867, 1606, 1572, 1530, 1468, 1442, 1414, 1388, 1362, 1257, 1216, 1121, 1038, 965, 895, 863, 821, 783, 759, 729, 698, 687;
¹ H NMR (400 MHz, CDCl ₃ , 300 K) δ 8.77 (br s, 1H), 8.54-8.46 (m, 2H), 8.44 (s, 1H), 8.40 (d, J = 8.0 Hz, 1H), 7.78-7.63 (m, 3H), 7.56-7.48 (m, 2H), 7.42-7.34 (m, 2H), 7.20 (t, J = 6.8 Hz, 1H), 1.59 (s, 9H);
¹³ C NMR (126 MHz, CDCl ₃ , 300 K) δ 163.8, 161.8, 148.2, 137.1, 136.1, 136.0 (d, J = 10 Hz), 134.1 (d, J = 8.6 Hz), 128.8, 128.7, 128.1, 127.4, 126.7, 126.2, 125.1, 124.3, 123.7, 123.6, 123.2, 123.1, 122.9, 122.8, 122.0, 120.9, 118.3, 118.2, 117.3 (d, J = 24 Hz), 114.6 (d, J = 21 Hz), 35.5, 31.8 (3C);
HRMS (ESI) m / z calcd for C ₃₁ H ₂₃ ClFN ₂ [M ⁺ H] ⁺ 477.1534, found 477.1542.

<Ring closure process>

In a nitrogen atmosphere, to a mixture of compound 3b (50 mg, 0.10 mmol), palladium (II) acetate (14 mg, 0.06 mmol), di-tert-butylmethylphosphonium tetrafluoroborate (45 mg, 0.18 mmol). , Dimethylformamide (2.0 mL) and diazabicycloundecene (0.5 mL) were added at room temperature, and the mixture was stirred at 160 ° C. overnight. After cooling to room temperature, the reaction solution was diluted with toluene, washed 4 times with water and 1 time with saturated aqueous sodium chloride solution, and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was purified by silica gel column chromatography to obtain compound 4b. 18 mg, yield 41%.

IR (neat); cm ^-1 3067, 2950, 2905, 2868, 2216, 1671, 1601, 1576, 1549, 1527, 1478, 1450, 1417, 1393, 1374, 1324, 1240, 1199, 1181, 1146, 1122, 1043, 969, 941, 876, 851, 821, 800, 759, 694, 656;
^{1 1} H NMR (400 MHz, CDCl ₃ , 300 K) δ 8.78-8.71 (m, 1H), 8.62 (dd, J = 8.4, 6.0 Hz, 1H), 8.51-8.45 (m, 1H), 8.43 (s, 1H), 8.40 (s, 1H), 8.34 (d, J = 8.0 Hz, 1H), 8.24 (d, J = 7.6 Hz, 1H), 8.17 (dd, J = 10.8, 2.0 Hz, 1H), 7.77- 7.68 (m, 3H), 7.39 (dt, J = 8.3, 1.7 Hz, 1H), 1.63 (s, 9H);
¹³ C NMR (100 MHz, CDCl ₃ , 300 K) δ 148.4, 138.9, 132.3, 130.6 (d, J = 7.6 Hz), 129.5, 128.9, 128.8, 127.5, 127.5, 126.2, 126.1, 125.8, 124.9, 124.6, 124.5 (d, J = 9.0 Hz), 124.2, 123.7, 123.2, 122.4, 121.9, 120.1, 119.6, 119.1, 118.6, 115.8 (d, J = 23 Hz), 110.1 (d, J = 23 Hz), 35.7, 32.0 (3C);
HRMS (ESI) m / z calcd for C ₃₁ H ₂₂ FN ₂ [M + H] + 491.1767, found 441.1761.

[Example 3] 9- (t-butyl) -2- (trifluoromethyl) dibenzo [b, mn] benzo [7,8] indridino [2,3,4,5,6-defg] acridine (4c) Synthesis of

<Additional process>

2-t-Butyl-8-hydroisoquinolino chloride [4,5,2-de] phenanthridinium (Compound 1) (54 mg, 0.15 mmol), 2-chloro-5-tri, under a nitrogen atmosphere. DMSO (3.0 mL) was added to a mixture of fluoromethyl-benzonitrile (Compound 2c) (308 mg, 1.50 mmol) and cesium carbonate (98 mg, 0.30 mmol) at room temperature, and the mixture was stirred at 160 ° C. for 12 hours. After cooling to room temperature, the reaction solution was diluted with toluene (50 mL), washed with water (15 mL) and saturated aqueous sodium chloride solution (15 mL), and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was dissolved in methylene chloride (5 mL) to add 2,3-dichloro-5,6-dicyano-p-benzoquinone (23 mg, 0.10 mmol). Added. The solution was stirred at room temperature for 20 minutes. After diluting with methylene chloride (50 mL), the mixture was washed twice with saturated aqueous sodium hydrogen carbonate solution (15 mL) and saturated aqueous sodium chloride solution (15 mL) and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was purified by silica gel column chromatography to obtain compound 3c. 50 mg, yield 63%.

IR (neat); cm ^-1 3032, 2959, 2913, 2870, 1614, 1573, 1527, 1478, 1444, 1409, 1377, 1339, 1318, 1292, 1265, 1168, 1114, 1084, 1071, 1041, 973, 940, 905, 866, 845, 825, 783, 729, 696;
^{1 1} H NMR (400 MHz, CDCl ₃ , 300 K) δ 8.76-8.68 (m, 1H), 8.53-8.46 (m, 2H), 8.45 (s, 1H), 8.40 (d, J = 8.0 Hz, 1H) , 8.01 (s, 1H), 7.78-7.64 (m, 4H), 7.56-7.46 (m, 2H), 7.39 (t, J = 7.6 Hz, 1H), 1.59 (s, 9H);
¹³ C NMR (100 MHz, CDCl _3, 300 K) δ 148.2, 138.9, 137.5, 136.3, 132.7, 130.5, 130.2, 130.1 (q, J = 3.6 Hz), 129.7 (q, J = 33 Hz), 128.8, 128.7, 128.7, 128.1, 127.5, 126.8, 126.6 (q, J = 3.5 Hz), 126.2, 125.1, 124.9, 124.2, 123.8, 123.6, 123.2, 122.9, 122.7, 122.4, 122.0, 121.2, 118.4, 118.2, 35.5, 31.8 (3C);
HRMS (ESI) m / z calcd for C ₃₂ H ₂₃ ClF ₃ N ₂ [M ⁺ H] ⁺ 527.1502, found 527.1509.

<Ring closure process>

In a nitrogen atmosphere, to a mixture of compound 3c (46 mg, 0.090 mmol), palladium (II) acetate (12 mg, 0.054 mmol), di-tert-butylmethylphosphonium tetrafluoroborate (40 mg, 0.16 mmol). , Dimethylformamide (2.0 mL) and diazabicycloundecene (0.5 mL) were added at room temperature, and the mixture was stirred at 160 ° C. overnight. After cooling to room temperature, the reaction solution was diluted with toluene, washed 4 times with water and 1 time with saturated aqueous sodium chloride solution, and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was purified by silica gel column chromatography to obtain compound 4c. 21 mg, yield 48%.

IR (neat); cm ^-1 3067, 2964, 2909, 2873, 2237, 1671, 1600, 1572, 1523, 1471, 1457, 1428, 1394, 1360, 1319, 1299, 1270, 1243, 1214, 1166, 1141, 1112, 1074, 1064, 1018, 987, 954, 904, 868, 845, 832, 808, 780, 750, 735, 712, 691, 653;
¹ H NMR (400 MHz, THF-d8, 300 K) δ 8.77 (s, 1H), 8.72 (d, J = 8.4 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8,52- 8.43 (m, 3H), 8.41 (s, 1H), 8.19 (d, J = 7.6 Hz, 1H), 7.72 (t, J = 8.4 Hz, 1H), 7.68-7.64 (m, 2H), 7.61 (t) , J = 8.0 Hz, 1H), 1.65 (s, 9H);
¹³ C NMR (100 MHz, THF-d8, 300 K) δ 146.6, 137.1, 129.9, 129.4, 127.7, 127.0, 126.7, 126.6 (q, J = 32 Hz), 126.3, 125.2, 124.6, 124.3, 124.0, 123.8 , 123.6, 122.4, 122.2, 122.0, 121.6, 121.0, 120.8, 119.9, 118.8, 118.5 (q, J = 2 Hz), 117.9, 117.7 (q, J = 3 Hz), 117.2, 117.0, 33.6, 29.4 (3C) );
HRMS (ESI) m / z calcd for C ₃₂ H ₂₂ F ₃ N ₂ [M ⁺ H] ⁺ 491.1735, found 491.1733.

[Example 4] Synthesis of 9- (t-butyl) -3,14b1,15-triazadibenzo [fg, ij] cyclopentane [rst] pentaphen (4d)

<Additional process>

2-t-Butyl-8-hydroisoquinolino chloride [4,5,2-de] phenanthridinium (Compound 1) (54 mg, 0.15 mmol), 3-chloro-4-cyano under a nitrogen atmosphere DMSO (3.0 mL) was added to a mixture of pyridine (Compound 2d) (208 mg, 1.50 mmol) and cesium carbonate (98 mg, 0.30 mmol) at room temperature, and the mixture was stirred at 160 ° C. for 12 hours. After cooling to room temperature, the reaction solution was diluted with toluene (50 mL), washed with water (15 mL) and saturated aqueous sodium chloride solution (15 mL), and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was dissolved in methylene chloride (5 mL) to add 2,3-dichloro-5,6-dicyano-p-benzoquinone (23 mg, 0.10 mmol). Added. The solution was stirred at room temperature for 20 minutes. After diluting with methylene chloride (50 mL), the mixture was washed twice with saturated aqueous sodium hydrogen carbonate solution (15 mL) and saturated aqueous sodium chloride solution (15 mL) and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was purified by silica gel column chromatography to obtain compound 3d. 30 mg, yield 43%.

IR (neat); cm ^-1 3356, 3071, 2959, 2909, 2861, 2226, 1954, 1732, 1588, 1573, 1532, 1492, 1460, 1442, 1413, 1398, 1362, 1338, 1271, 1250, 1205, 1169, 1153, 1133, 1122, 1102, 1090, 1033, 967, 921, 864, 842, 784, 761, 729, 699, 680, 655;
^{1 1} H NMR (400 MHz, CDCl ₃ , 300 K) δ 8.84 (s, 1H), 8.75-8.67 (m, 2H), 8.55-8.48 (m, 2H), 8.46 (s, 1H), 8.42 (d, J = 8.0 Hz, 1H), 7.76-7.65 (m, 3H), 7.59-7.51 (m, 2H), 7.42 (t, J = 7.2 Hz, 1H), 1.60 (s, 9H);
¹³ C NMR (100 MHz, CDCl ₃ , 300 K) δ 150.1, 148.3, 148.0, 143.4, 143.4, 137.8, 132.5, 131.4, 128.9, 128.7, 128.2, 127.8, 127.1, 126.9, 126.1, 124.7, 124.2, 124.0, 123.6, 123.2, 122.9, 122.7, 122.0, 121.4, 118.4, 118.2, 35.6, 31.8 (3C);
HRMS (ESI) m / z calcd for C ₃₀ H ₂₃ ClN ₃ [M ⁺ H] ⁺ 460.1581, found 460.1584.

<Ring closure process>

Under a nitrogen atmosphere, compound 3d (30 mg, 0.065 mmol), palladium (II) acetate (8.8 mg, 0.039 mmol), di-tert-butylmethylphosphonium tetrafluoroborate (30 mg, 0.12 mmol). To the mixture was added dimethylformamide (2.0 mL) and diazabicycloundecene (0.5 mL) at room temperature and stirred at 160 ° C. overnight. After cooling to room temperature, the reaction solution was diluted with toluene, washed 4 times with water and 1 time with saturated aqueous sodium chloride solution, and dried over sodium sulfate. After removing the desiccant by filtration, the crude product obtained by concentration was purified by silica gel column chromatography to obtain compound 4d. 24 mg, yield 87%.

IR (neat); cm ^-1 3201, 3056, 2959, 2904, 2488, 2171, 1667, 1611, 1586, 1523, 1477, 1449, 1422, 1394, 1394, 1372, 1336, 1302, 1287, 1244, 1214, 1171, 1147, 1122, 1056, 1017, 974, 935, 870, 831, 816, 767, 696, 687, 679, 656;
¹ H NMR (400 MHz, CDCl ₃ , 300 K) δ 10.0 (s, 1H), 8.95-8.68 (m, 2H), 8.71 (d, J = 8.0 Hz, 1H), 8.58-8.48 (m, 4H) , 8.40 (d, J = 7.6 Hz, 1H), 7.93 (t, J = 7.8 Hz, 1H), 7.83-7.75 (m, 2H), 1.67 (s, 9H);
¹³ C NMR (100 MHz, CDCl ₃ , 300 K) 148.9, 140.1, 139.7, 130.7, 129.8, 129.5, 129.1, 127.4, 126.2, 126.1, 126.0, 124.9, 124.1, 124.1, 123.9, 123.2, 122.1, 121.9, 121.8 , 120.7, 120.4, 119.9, 119.2, 119.0, 117.1, 116.4, 35.8, 32.0 (3C);
HRMS (ESI) m / z calcd for C ₃₀ H ₂₂ N ₃ [M ⁺ H] ⁺ 424.1814, found 424.1818.

Claims (9)

A nitrogen-containing condensed polycyclic aromatic compound represented by the following general formula (I).

(In the general formula (I), R ^{1 to} R ¹⁰ are independently hydrogen atoms, or alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, allyloxy groups, halogen elements, and amino groups. Represents a substituent selected from the group consisting of: Q is any of the 5-7 membered ring structures. Z ¹ is a nitrogen atom, or a phosphorus atom, or (Z ² ) ⁺ Y ⁻ (where, (where, Z ² ) ⁺ represents a monovalent counter cation of an oxygen atom or a sulfur atom, and Y ⁻ represents a monovalent counter anion.) The nitrogen-containing condensed polycycle according to claim 1, wherein the ring structure Q in the general formula (I) is a substituted or unsubstituted benzene ring, pyridine ring, furan ring, thiophene ring, or pyrrole ring. Aromatic compounds. The nitrogen-containing condensed polycyclic aromatic compound according to claim 2, wherein the ring structure of Q in the general formula (I) is a substituted or unsubstituted benzene ring or pyridine ring. Claimed to have a step of reacting a substituted aromatic compound represented by the following general formula (II) with an isoquinolino [4,5,2-de] phenanthriginium compound represented by the following general formula (III). Item 3. The method for producing a nitrogen-containing condensed polycyclic aromatic compound according to any one of Items 1 to 3.

(In the general formula (II), Q is synonymous with the above general formula (I), X is a halogen atom, W is a formyl group, a carboxyl group, a thioformyl group, a thiocarboxyl group, and 2 to 20 carbon atoms. Indicates a substituent selected from the group consisting of an acyl group, an ester group having 2 to 20 carbon atoms, a substituted ethynyl group having 2 to 20 carbon atoms, a phosphoethynyl group, and a cyano group.

(In the general formula (III), R ^{1 to} R ¹⁰ are synonymous with those in the general formula (I), and Y ⁻ represents a monovalent counter anion.) The nitrogen-containing condensed polycycle according to claim 4, wherein the ring structure Q in the general formula (II) is a substituted or unsubstituted benzene ring, pyridine ring, furan ring, thiophene ring, or pyrrole ring. A method for producing an aromatic compound. The method for producing a nitrogen-containing condensed polycyclic aromatic compound according to claim 5, wherein the ring structure Q in the general formula (II) is a substituted or unsubstituted benzene ring or pyridine ring. The substituent W in the general formula (II) is selected from the group consisting of a formyl group, a carboxyl group, an ester group having 2 to 20 carbon atoms, a substituted ethynyl group having 2 to 20 carbon atoms, and a cyano group. The method for producing a nitrogen-containing condensed polycyclic aromatic compound according to any one of claims 4 to 6. The nitrogen-containing condensed poly according to claim 7, wherein the substituent W in the general formula (II) is a substituent selected from the group consisting of a formyl group, an ester group having 2 to 20 carbon atoms, and a cyano group. A method for producing a ring aromatic compound. The method for producing a nitrogen-containing condensed polycyclic aromatic compound according to claim 8, wherein the substituent W in the general formula (II) is a cyano group.