JPWO2017209297A1 - Triarylene compound and method for producing the same - Google Patents

Abstract

In the presence of a palladium catalyst and a base, a compound of the general formula (2): wherein R 1 and R 2 are as defined above. X represents a halogen atom. The triarylene compound can be synthesized under mild conditions using a readily available compound by reacting the compound represented by the formula].

Description

  The present invention relates to a triarylene compound and a method for producing the same.

  Benzyne from which two hydrogen atoms located at the ortho position are removed from benzene has a highly distorted triple bond and exhibits high reactivity. For this reason, it has been used for various organic syntheses as a reaction intermediate, for example, Dictyodendrin A having telomerase inhibitory activity isolated from sponge, Chelidonine which is an active ingredient of anticancer drug Ukrain, etc., triarylene compounds etc. It is also used in the synthesis of Among them, triarylene compounds (in particular, triphenylene compounds) are useful compounds which are also used as organic EL materials, liquid crystal materials and the like.

  Thus, although benzine is a useful chemical species that has been widely used in synthetic organic chemistry, benZane is an unstable compound and must be generated in situ. In addition, it is necessary to use a strong base, an oxidizing agent or the like for the generation of benzine or to prepare a precursor in advance. For this reason, there has been a problem that the applicable substrate is limited, or the number of steps is increased due to precursor preparation.

  For this reason, in the synthesis of the above-described triarylene compounds, how to generate benzyne, which is a reaction intermediate, is a key.

  For example, it is known that halogen is eliminated and a strong base is added by causing a strong base to act on a halogenated aryl compound. In this reaction, it is known that strong bases generate benzine by deprotonating a hydrogen atom at the ortho position of a halogen atom (see, for example, Non-Patent Document 1). It is also known that benzyne is also generated by the action of tetrabutylammonium fluoride (TBAF) on an aryl triflate having a silyl group at the ortho position (see, for example, Non-Patent Document 2). In this reaction, silyl group is eliminated by acting TBAF on aryl triflate to generate carbanion in the ortho position of triflate group.

J. Am. Chem. Soc. 1953, 75, 3290 Chem. Lett. 1983, 1211

  However, since the use of a strong base is indispensable in the method of Non-Patent Document 1, the functional group tolerance of the substrate is low, and the range of application of the substrate is greatly limited. On the other hand, in the method of Non-Patent Document 2, the silyl group is eliminated by acting TBAF on the aryl triflate to generate carbanion at the ortho position of the triflate group, and a strong base is not necessary, and it is carried out at room temperature. Although the reaction can be mild because it can be carried out, the preparation of the aryl triflate which is a substrate is complicated, and an increase in the number of steps is inevitable. For this reason, there is no method for generating benzine under mild conditions using readily available compounds. Of course, there is also no known method for synthesizing triarylene compounds under mild conditions using readily available compounds.

  From the above, it is an object of the present invention to synthesize triarylene compounds under mild conditions using easily available compounds.

  As a result of intensive studies to solve the above problems, the present inventors have found that by reacting desired substrate compounds with each other in the presence of a palladium catalyst and a base, a mild base is obtained without using a strong base. It has been found that triarylene compounds can be synthesized under the conditions. The substrate compound which can be used at this time is a compound which is easy to obtain. Based on such findings, the present inventors have further studied and completed the present invention. That is, the present invention includes the following configurations.

  Item 1. General formula (1):

[Wherein, R ¹ and R ^{1 ′} represent a hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ³ represents a hydrogen atom. R ′ represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. R ¹ and R ³ may combine to form a ring. R ^{1 ′} and R ³ may combine to form a ring. R ² and R ′ may combine to form a ring. ]
A process for producing a polycyclic aromatic compound represented by
In the presence of a palladium catalyst and a base
General formula (2):

[Wherein, R ¹ and R ² are as defined above. X represents a halogen atom. ]
A production method comprising a reaction step of reacting a compound represented by

Item 2. The production method according to Item 1, wherein R ¹ is a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzothienyl group.

Item 3. The production method according to Item 1 or 2, wherein R ² is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzothienyl group.

  Item 4. The method according to any one of Items 1 to 3, wherein R 'is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted benzothiophene ring.

  Item 5. Item 5. The production method according to any one of Items 1 to 4, wherein a ligand compound is added in the reaction step.

  Item 6. Item 6. The production method according to Item 5, wherein the ligand compound is a phosphine compound.

  Item 7. 7. The method according to any one of Items 1 to 6, wherein the base is an alkali metal carbonate or an alkali metal fluoride salt.

  Item 8. Item 8. The method according to any one of Items 1 to 7, wherein a carboxylic acid is added in the reaction step.

  Item 9. Item 9. The method according to any one of Items 1 to 8, further comprising the step of causing an intramolecular cyclization reaction in the presence of an oxidizing agent after the reaction step.

  Item 10. General formula (1A1):

[Wherein, R ¹ and R ^{1 ′} represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ′ represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. Provided that R ¹ , R ^{1 ′} and R ² are all unsubstituted phenyl groups, R ′ is 4- (9,12-diphenyltriphenyl) -2,5-dimethylphenyl group, 4- (2,9) , 12-triphenyltriphenyl) -2,5-dimethylphenyl group, or compounds which are benzene substituted with triphenylphenyl group. ]
, General formula (1A2):

[Wherein, R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ′ represents a substituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. However, when R ² is a substituted phenyl group and R ′ is a substituted benzene ring, 1,5-bis [3- (9,9-dimethyl-9H-fluoren-3-yl) phenyltriphenylene, 7,7 '-(1,5-triphenylenediyl) -bisbenzoxazole, 1,12-bis ([1,1': 3 ', 1-terphenyl] -3-yl) triphenylene, 3,3'-(1- 12-triphenylenediyl) bis [9-phenyl-9H-carbazole] ,, 3 '-(1-12-triphenylenediyl) bisdibenzothiophene, 1- [3- (bromomethyl) -5-methylphenyl] -12- 3,5-Dimethylphenyl) -triphenylene, 1- [3- (bromomethyl) -5-methylphenyl] -12-phenyltriphenylene, 1-phenyl-12- (2,4,6-trimethylphenyl) -triphenylene, 1 -(4-Methylphenyl) -12-phenyl-triphenylene, 1- (3,5-dimethylphenyl) -12-phenyltriphenylene, 1,12-bis (3,5-dimethylphenyl) -triphenylene, 8,9- The Enirujibenzo except [f, j] picene, 2-iodo-1,12-diphenyl triphenylene, and 1,12 diphenyl triphenylene. When R ′ is a non-substituted benzene ring, R ² is a substituted or non-substituted phenyl group, a substituted naphthyl group, a substituted pyridyl group, a substituted pyrazyl, a substituted or non-substituted dibenzofuran group, or a substituted or non-substituted dibenzothiophene group Excluding substituted or unsubstituted carbazole group, substituted or unsubstituted benzotriazole group, substituted or unsubstituted quinoline group, triphenylene group, phenanthrene group, indandione group, and flowene group. ]
A triarylene compound represented by

Item 11. Item 11. The triarylene compound according to item 10, wherein R ¹ and R ^{1 ′} are a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzothienyl group.

Item 12. Item 12. The triarylene compound according to item 10 or 11, wherein R ² is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzothienyl group.

  Item 13. Item 13. The triarylene compound according to any of items 10 to 12, wherein R ′ is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted benzothiophene ring.

  Item 14. General formula (1B):

Polycyclic aromatic compound represented by

  According to the present invention, by reacting desired substrate compounds with each other in the presence of a palladium catalyst and a base, a triarylene compound can be obtained by a mild condition reaction in only one step. In addition, the substrate compound which can be used is an easily available compound.

7 is a structure of compound 2b obtained in Example 2 by thermal ellipsometry drawing software (ORTEP). It is the structure by thermal oscillation ellipsoid drawing software (ORTEP) of the compound 2p obtained in Examples 2 and 5. 7 is a structure of compound 2p ′ obtained in Example 5 by thermal ellipsometry drawing software (ORTEP). (A) Raman spectra of flakes of compound 3c and simulated spectra calculated using B3LYP / 6-31G (d) level theory scaled with a factor of 0.9613. (B, C) The expanded spectrum of A is shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (broken line) of compound 2b are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (broken line) of compound 2p are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (broken line) of compound 2p 'are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (broken line) of compound 2d are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (dotted line) of compound 2l are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (broken line) of compound 2m are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (broken line) of compound 2n are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (dotted line) of compound 2g are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (broken line) of compound 2e are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (broken line) of compound 2f are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (broken line) of compound 2k are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (broken line) of compound 2c are shown. The UV-Vis absorption spectrum (solid line) and the fluorescence spectrum (broken line) of compound 3a are shown.

  The process for producing a polycyclic aromatic compound of the present invention comprises the general formula (1):

[Wherein, R ¹ and R ^{1 ′} represent a hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ³ represents a hydrogen atom. R ′ represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. R ¹ and R ³ may combine to form a ring. R ^{1 ′} and R ³ may combine to form a ring. R ² and R ′ may combine to form a ring. ]
A method for producing a polycyclic aromatic compound (hereinafter sometimes referred to as "polycyclic aromatic compound (1)")
In the presence of a palladium catalyst and a base
General formula (2):

[Wherein, R ¹ and R ² are as defined above. X represents a halogen atom. ]
And a reaction step of reacting the compound represented by

  In this reaction step, compounds represented by the general formula (2) as a substrate (hereinafter sometimes referred to as “compound (2)”) are reacted with each other in the presence of a palladium catalyst and a base to form a polycyclic ring. An aromatic compound (1) can be obtained. At this time, as the compound (2) to be reacted, it is preferable to make the same kind of compound (2) react with each other. In this reaction step, as the compound (2) as a substrate, compounds having various substituents can also be used, so that various polycyclic aromatic compounds can be synthesized.

In the general formulas (1) and (2), examples of the aryl group represented by R ¹ and R ^{1 ′} include, for example, phenyl group, pentalenyl group, indenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, benzoanthracenyl group And pyrenyl group, perylenyl group, triphenylenyl group, azulenyl group, heptalenyl group, indasenyl group, acenaphthyl group, acenaphthyl group, fluorenyl group, phenalenyl group, fluoranthenyl group, colonenyl group and the like.

Moreover, as a substituent which the aryl group shown by R ¹ and R ^{1 ′} may have, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a cyano group, an alkyl group ( C1-6 alkyl group such as methyl group, tert-butyl group etc., alkoxy group (C1-6 alkoxy group such as methoxy group etc.), the above aryl group, heteroaryl group described later, alkoxycarbonyl group (methoxycarbonyl group etc.) C2-7 alkoxycarbonyl group of 1), a thioalkyl group (a C1-6 thioalkyl group such as a thiomethyl group etc.) and the like. The alkyl group, alkoxy group, aryl group and heteroaryl group as a substituent may be substituted by the above-mentioned substituent. The number of substituents in the case of having a substituent is preferably 1 to 6, and more preferably 1 to 3.

Examples of the heteroaryl group represented by R ¹ and R ^{1 ′} in the general formulas (1) and (2) include imidazolyl group, pyrazolyl group, pyrazyl group, pyrimidyl group, pyridazyl group, oxazolyl group, isoxazolyl group, thiazolyl group. Groups, isothiazolyl groups, indolyl groups, quinolyl groups, isoquinolyl groups, benzimidazolyl groups, quinazolyl groups, phthalazyl groups, pteridyl groups, benzofuranyl groups, coumaryl groups, benzothienyl groups and the like.

Moreover, as a substituent which the heteroaryl group shown by R ¹ and R ^{1 ′} may have, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc.), a cyano group, an alkyl group (C1-6 alkyl group such as methyl group), alkoxy group (C1-6 alkoxy group such as methoxy group), the above aryl group, the above heteroaryl group, alkoxycarbonyl group (C2-7 alkoxy such as methoxycarbonyl group) Examples thereof include a carbonyl group etc., a thioalkyl group (C1-6 thioalkyl group such as a thiomethyl group etc.) and the like. The alkyl group, alkoxy group, aryl group and heteroaryl group as a substituent may be substituted by the above-mentioned substituent. The number of substituents in the case of having a substituent is preferably 1 to 6, and more preferably 1 to 3.

Among them, as R ¹ and R ^{1 ′} , a hydrogen atom, a phenyl group, a naphthyl group, a benzothienyl group and the like are preferable, and these are a cyano group, the above alkyl group, the above alkoxy group, the above aryl group, the above alkoxycarbonyl group And may be substituted with the above-mentioned thioalkyl group or the like. However, since a heteroaryl group tends to have low stability and low yield, a hydrogen atom or an aryl group is preferable as R ¹ .

In the general formulas (1) and (2), as the aryl group and heteroaryl group represented by R ² , those described above can be adopted. The types and numbers of substituents are also the same. Among them, as R ² , a phenyl group, a naphthyl group, a benzothienyl group and the like are preferable, and these are substituted with a cyano group, the above alkyl group, the above alkoxy group, the above aryl group, the above aryl group, the above alkoxycarbonyl group, the above thioalkyl group etc. It may be done. However, since a heteroaryl group tends to have low stability and low yield, a hydrogen atom or an aryl group is preferable as R ¹ .

In the general formula (1), R ′ represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. When R ² of compound (2) used as a substrate is a substituted or unsubstituted aryl group, R ′ is a substituted or unsubstituted aromatic hydrocarbon ring derived from the substituted or unsubstituted aryl group and used as a substrate When R ² of the compound (2) is a substituted or unsubstituted heteroaryl group, R ′ is a substituted or unsubstituted heteroaromatic ring derived from the substituted or unsubstituted heteroaryl group.

  From this viewpoint, examples of the aromatic hydrocarbon ring represented by R ′ include benzene ring, pentalene ring, indene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, phenanthrene ring, benzoanthracene ring, pyrene ring, Perylene ring, triphenylene ring, azulene ring, heptalene ring, indacene ring, acenaphthalene ring, a fluorene ring, phenalene ring, fluoranthene ring, coronene ring etc. are mentioned, and the above-mentioned halogen atom, cyano group, the above alkyl group, the above alkoxy group, It may be substituted by 1 to 6 (particularly 1 to 3) such as the above aryl group, the above heteroaryl group, the above alkoxycarbonyl group, the above thioalkyl group and the like.

  Moreover, as the heteroaromatic ring represented by R ′, for example, pyrrole ring, pyrrolidine ring, piperidine ring, imidazole ring, pyrazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, piperazine ring, triazine ring, oxazole ring, isoxazole Ring, morpholine ring, thiazole ring, isothiazole ring, indole ring, quinoline ring, isoquinoline ring, benzimidazole ring, quinazoline ring, phthalazine ring, purine ring, pteridine ring, benzofuran ring, coumarin ring, benzothiophene ring, etc. Substituted by 1 to 6 (particularly 1 to 3) such as the above halogen atom, cyano group, the above alkyl group, the above alkoxy group, the above aryl group, the above heteroaryl group, the above alkoxycarbonyl group, the above thioalkyl group, etc. May be

Among them, as R ^′ , a benzene ring, a naphthalene ring, a benzothiophene ring and the like are preferable, and these are substituted by a cyano group, the above alkyl group, the above alkoxy group, the above aryl group, the above alkoxycarbonyl group, the above thioalkyl group and the like It may be done. However, an aromatic hydrocarbon ring is preferable as R ^′ because a heteroaromatic ring tends to have low stability and a low yield.

In the general formula (1), R ¹ and R ³ may combine to form a ring. As a ring which may be formed, the above-mentioned aromatic hydrocarbon ring is mentioned.

In the general formula (1), R ^{1 ′} and R ³ may combine to form a ring. As a ring which may be formed, the above-mentioned aromatic hydrocarbon ring is mentioned.

In the general formula (1), R ² and R ′ may combine to form a ring. As a ring which may be formed, the above-mentioned aromatic hydrocarbon ring is mentioned.

  In the general formula (2), examples of the halogen atom represented by X include a fluorine atom, chlorine atom, bromine atom, iodine atom and the like, and from the viewpoint of yield etc., fluorine atom, chlorine atom and the like are preferable. The chlorine atom is more preferred.

  From the above viewpoints, as the compound (2) used as a substrate, for example,

[Wherein, t-Bu represents a tert-butyl group. Ph represents a phenyl group. The same applies to the following. ]
Etc.

By using a palladium catalyst, triarylene compounds can be obtained by the production method of the present invention. When the palladium catalyst is not used, the reaction of the present invention does not proceed. The palladium catalyst is not particularly limited, and examples thereof include metallic palladium and palladium compounds known as catalysts for synthesis of organic compounds (including polymer compounds). As the palladium catalyst, any of a compound containing zero-valent palladium and a compound containing II-valent palladium can be employed. When a compound containing zero-valent palladium is used, the zero-valent palladium is oxidized in the system to become II-valent palladium. Specific examples of palladium compounds that can be used include tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ) , Bis (dibenzylideneacetone) palladium (0), bis (tritert-butylphosphino) palladium (0), palladium acetate (Pd (OAc) ₂ (Ac is an acetyl group; the same applies hereinafter)), palladium halide (PdCl ₂ , PdBr ₂ , PdI ₂ ), Pd (PPh ₃ ) ₂ Cl ₂ (Ph is a phenyl group; the same shall apply hereinafter), Pd (OTf) ₂ (Tf is a trifluoromethylsulfonyl group), and the like. In the present invention, from the viewpoint of reaction yield and the like, palladium halides are preferred, and PdCl ₂ is more preferred. These palladium catalysts can be used alone or in combination of two or more.

  The amount of the palladium catalyst to be used can be appropriately selected depending on the type of the substrate, and for example, usually 0.01 to 1 mol is preferable, and 0.02 to 0.5 per 1 mol of the total amount of the compound (2) which is the substrate. The mole is more preferable, and 0.03 to 0.3 mole is more preferable.

  In the present invention, a ligand compound which can be coordinated to a palladium atom can be used together with the above-mentioned palladium catalyst. Although the reaction can be allowed to proceed without using a ligand compound, it is also possible to further improve the reaction yield by using a ligand compound.

Such ligand compounds are preferably phosphine compounds, and examples thereof include triphenylphosphine, trimethoxyphosphine, triethylphosphine, triisopropylphosphine, tri (tert-butyl) phosphine, tri (n-butyl) phosphine and triisopropoxy. Phosphine, tricyclopentyl phosphine, trimesityl phosphine, triphenoxy phosphine, di (tert-butyl) methyl phosphine, methyl diphenyl phosphine, dimethyl phenyl phosphine, n-butyl diadamantyl phosphine (Pn-Bu (Ad) ₂ ), 1, 1 '-Bis (diphenylphosphino) ferrocene, 1,1'-bis (tert-butyl) ferrocene, diphenylphosphinomethane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) Propane, 1,5-bis (diphenylphosphino) pentane, 1, 2-Bis (dipentafluorophenylphosphino) ethane, 1,2-bis (dicyclohexylphosphino) ethane, 1,3- (dicyclohexylphosphino) propane, 1,2-bis (di-tert-butylphosphino) Ethane, 1,3-bis (di-tert-butylphosphino) propane, 1,2-bis (diphenylphosphino) benzene and the like can be mentioned. These ligand compounds may be solvates. These can be used alone or in combination of two or more. Among them, n-butyl diadamantyl phosphine (Pn-Bu (Ad) ₂ ) is preferable from the viewpoint of reaction yield and the like.

  The amount of the ligand compound used is preferably 0.1 to 20 moles, more preferably 0.5 to 10 moles, and still more preferably 1 to 5 moles with respect to 1 mole of the palladium catalyst, from the viewpoint of reaction yield and the like.

  As a base used in the present invention, from the viewpoint of facilitating the reaction of the present invention more efficiently by generating benzine in the system by acting on the benzene ring of the compound (2) to deprotonate. , Alkali metal carbonates, alkali metal fluorides, alkali metal phosphates and the like are preferable. The reaction of the present invention can be advanced by using a weak base instead of a strong base as these bases. As such bases, for example, alkali metal phosphates such as lithium phosphate, sodium phosphate and potassium phosphate; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; sodium fluoride, Examples thereof include alkali metal fluoride salts such as potassium fluoride and cesium fluoride. These can be used alone or in combination of two or more. Among them, in the present step, an alkali metal carbonate or an alkali metal fluoride salt is preferable from the viewpoint of selectivity, yield and safety.

  In the present invention, from the viewpoint of selectivity and yield, the amount of the base used is usually preferably 0.5 to 10 moles, more preferably 1 to 8 moles, per mole of the total amount of the compound (2) as a substrate. preferable. When an alkali metal carbonate, alkali metal phosphate or the like is used as the base, 2 to 4 moles is particularly preferable to 1 mole of the total amount of the compound (2) as a substrate, and an alkali metal fluoride salt is used. When used, 4 to 6 moles are particularly preferable to 1 mole of the total amount of the compound (2) which is a substrate.

  In the present invention, carboxylic acids can also be used as additives. It is also possible to obtain the triarylene compound of the present invention in higher yield by using a carboxylic acid. When X is chlorine, when a carboxylic acid is used, side reactions are more likely to occur than when it is not used, isolation is required, and the yield of the desired product itself is the carboxylic acid. From the viewpoint of the balance between the yield and the side reaction suppression, it is preferable not to use a carboxylic acid because it is higher when not used. On the other hand, when X is bromine, it is preferable to use a carboxylic acid because the yield of the desired product itself can be improved by using a carboxylic acid.

  Examples of the carboxylic acid include pivalic acid, 1-methylcyclopropanecarboxylic acid, isobutyric acid, 2,2-dimethylbutyric acid, 2-methylmalonic acid, cyclohexanecarboxylic acid, 1-methyl-1-cyclohexanecarboxylic acid, 1- Examples thereof include branched carboxylic acids such as adamantane carboxylic acid; aromatic carboxylic acids such as 2,4,6-trimethylbenzoic acid and benzoic acid; acetic acid and the like. These carboxylic acids can be used alone or in combination of two or more. Among them, branched carboxylic acids are preferred from the viewpoint of yield and suppression of side reactions, and pivalic acid, 1-methylcyclopropanecarboxylic acid, isobutyric acid, 2-methylmalonic acid, cyclohexanecarboxylic acid, 1-methyl-1-cyclohexane Carboxylic acids and the like are more preferable, and 1-methylcyclopropanecarboxylic acid is more preferable.

  The amount used in the case of using a carboxylic acid can be appropriately selected according to the type of substrate, and, for example, usually 0.01 to 5 mol is preferable per 1 mol of the total amount of the compound (2) which is a substrate 0.05-2 mol is more preferable, and 0.1-1 mol is further more preferable. In addition, when using several carboxylic acid, it is preferable to adjust so that the total usage-amount may become in the said range.

  In the present invention, in addition to the above components, additives can be appropriately used as long as the effects of the present invention are not impaired. The amount of additive used in this case is preferably in a range that does not impair the effects of the present invention.

  The reaction of the present invention is preferably carried out in a solvent. Examples of the solvent include aliphatic hydrocarbons such as heptane and cyclohexane; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride; and aromatic carbonization such as benzene, toluene, xylene, mesitylene, pentamethylbenzene and the like Hydrogen; linear ethers such as diisopropyl ether, dibutyl ether, dimethoxyethane, cyclopentyl methyl ether (CPME), tert-butyl methyl ether; cyclic ethers such as tetrahydrofuran and dioxane; ethyl acetate, butyl acetate (AcOn-Bu), propionic acid Esters such as ethyl; alcohols such as 2-methyl-2-butanol (tert-amyl alcohol) and the like. These can be used alone or in combination of two or more. Among these, in the present invention, a chain ether is preferable from the viewpoint of reaction yield and the like, and cyclopentyl methyl ether (CPME) is more preferable.

  The production method of the present invention is preferably carried out under an inert gas atmosphere (nitrogen gas, argon gas, etc.), and the reaction temperature is usually preferably 100 to 200 ° C., more preferably 110 to 180 ° C., 120 to 170 ° C is more preferred. The reaction time can be a time for the reaction to proceed sufficiently, and is preferably 10 minutes to 48 hours, and more preferably 1 to 36 hours.

  After completion of the reaction, the desired compound can be obtained, if necessary, through the usual isolation and purification steps.

  Thus, as one type of polycyclic aromatic compound of the present invention, a compound represented by the general formula (1A):

[Wherein, R ¹ and R ^{1 ′} represent a hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ′ represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. ]
The triarylene compound represented by these can be obtained.

  In the present invention, after obtaining a triarylene compound in this manner, an intramolecular cyclization reaction is caused in the presence of an oxidizing agent to obtain a compound represented by general formula (1B):

[Wherein, R ¹ and R ^{1 ′} represent a hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R ³ represents a hydrogen atom. R ′ represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. R ¹ and R ³ may combine to form a ring. R ^{1 ′} and R ³ may combine to form a ring. ]
It is also possible to obtain a polycyclic aromatic compound represented by The triarylene compound represented by the general formula (1A) and the aromatic compound represented by the general formula (1B) can be collectively described as an aromatic compound represented by the general formula (1) .

The oxidizing agent is not particularly limited, and is not particularly limited as long as it can cause an intramolecular cyclization reaction (Scholl reaction etc.), and FeCl ₃ , 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ) and the like can be mentioned. These oxidizing agents can be used alone or in combination of two or more.

  The amount of the oxidizing agent used is preferably adjusted appropriately depending on the substrate, but is preferably in excess with respect to the substrate triarylene compound (1A). Specifically, 1.0 to 30.0 mol is preferable, and 2.0 to 20.0 mol is more preferable, with respect to 1 mol of the triarylene compound (1A). In addition, when using several oxidizing agent, it is preferable to adjust so that the total usage-amount may become in the said range.

  The intramolecular cyclization reaction is preferably carried out in a solvent. Examples of the solvent include aliphatic hydrocarbons such as heptane and cyclohexane; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride; and aromatic carbonization such as benzene, toluene, xylene, mesitylene, pentamethylbenzene and the like Hydrogen; linear ethers such as diisopropyl ether, dibutyl ether, dimethoxyethane, cyclopentyl methyl ether (CPME), tert-butyl methyl ether; cyclic ethers such as tetrahydrofuran and dioxane; ethyl acetate, butyl acetate (AcOn-Bu), propionic acid Esters such as ethyl; alcohols such as 2-methyl-2-butanol (tert-amyl alcohol) and the like. These can be used alone or in combination of two or more. Among these, in the present invention, from the viewpoint of reaction yield and the like, aliphatic halogenated hydrocarbons are preferable, and dichloromethane is more preferable.

  The above-mentioned intramolecular cyclization reaction is preferably carried out under an inert gas atmosphere (nitrogen gas, argon gas or the like), and the reaction temperature is usually preferably −50 to 100 ° C., more preferably −20 to 50 ° C. The reaction time can be a time for the reaction to proceed sufficiently, and usually 10 minutes to 72 hours is preferable, and 1 to 48 hours is more preferable.

  After completion of the reaction, the desired compound can be obtained, if necessary, through the usual isolation and purification steps.

  The thus-obtained polycyclic aromatic compound of the present invention has the general formula (1):

[Wherein, R ¹ , R ² and R ′ are as defined above. ]
And a compound represented by the general formula (1A1):

[Wherein, R ¹ and R ^{1 ′} represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ′ represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. Provided that R ¹ , R ^{1 ′} and R ² are all unsubstituted phenyl groups, R ′ is 4- (9,12-diphenyltriphenyl) -2,5-dimethylphenyl group, 4- (2,9) , 12-triphenyltriphenyl) -2,5-dimethylphenyl group, or compounds which are benzene substituted with triphenylphenyl group. ]
, General formula (1A2):

[Wherein, R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ′ represents a substituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. However, when R ² is a substituted phenyl group and R ′ is a substituted benzene ring, 1,5-bis [3- (9,9-dimethyl-9H-fluoren-3-yl) phenyltriphenylene, 7,7 '-(1,5-triphenylenediyl) -bisbenzoxazole, 1,12-bis ([1,1': 3 ', 1-terphenyl] -3-yl) triphenylene, 3,3'-(1- 12-triphenylenediyl) bis [9-phenyl-9H-carbazole] ,, 3 '-(1-12-triphenylenediyl) bisdibenzothiophene, 1- [3- (bromomethyl) -5-methylphenyl] -12- 3,5-Dimethylphenyl) -triphenylene, 1- [3- (bromomethyl) -5-methylphenyl] -12-phenyltriphenylene, 1-phenyl-12- (2,4,6-trimethylphenyl) -triphenylene, 1 -(4-Methylphenyl) -12-phenyl-triphenylene, 1- (3,5-dimethylphenyl) -12-phenyltriphenylene, 1,12-bis (3,5-dimethylphenyl) -triphenylene, 8,9- The Enirujibenzo except [f, j] picene, 2-iodo-1,12-diphenyl triphenylene, and 1,12 diphenyl triphenylene. When R ′ is a non-substituted benzene ring, R ² is a substituted or non-substituted phenyl group, a substituted naphthyl group, a substituted pyridyl group, a substituted pyrazyl, a substituted or non-substituted dibenzofuran group, or a substituted or non-substituted dibenzothiophene group Excluding substituted or unsubstituted carbazole group, substituted or unsubstituted benzotriazole group, substituted or unsubstituted quinoline group, triphenylene group, phenanthrene group, indandione group, and flowene group. ]
Or general formula (1B):

The compounds represented by are novel compounds not described in the literature.

  As such a triarylene compound of the present invention, for example,

Etc.

  The reaction mechanism in the above-mentioned production method of the present invention is not necessarily clear, but when a carboxylic acid is used, the following reaction formula 1:

[Wherein, R ¹ , R ² , R ′ and X are as defined above. R represents a substituent. ]
It is assumed that the reaction proceeds according to

  First, the compound (2) undergoes oxidative addition to zero-valent palladium to form a compound (A). Next, after ligand exchange with a carboxylic acid to form a compound (B), the hydrogen atom located at the ortho position is deprotonated (CMD) by a base, thereby forming palladium as a reaction key Benzene complex (C) is formed. Another molecule of compound (2) undergoes oxidative addition to this palladium-benzyne complex to form compound (D), and then benzyne is inserted into a Pd-C bond to form intermediate (E). It is induced. The subsequent intramolecular cyclization reaction provides the desired triarylene compound and simultaneously regenerates zero-valent palladium to complete the catalytic cycle.

  In addition, although the above showed about the reaction mechanism in the case of using carboxylic acid, when not using carboxylic acid, in ligand exchange reaction, the anion derived from a base (cesium fluoride instead of the anion derived from carboxylic acid) In this case, it is assumed that the fluoride ion is introduced and the reaction proceeds along the same reaction mechanism. Therefore, even if the type of substrate is changed, the reaction proceeds according to the same reaction mechanism, so that various triarylene compounds can be synthesized.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

Unless otherwise limited, all reagents and reagents including dry solvents were commercially available. PdCl ₂ , Cs ₂ CO ₃ and cyclopentyl methyl ether (CPME) were purchased from Wako Pure Chemical Industries, Ltd. n-Butyldiadamantylphosphine (P ⁿ Bu (Ad) ₂ ) was purchased from Aldrich. Unless otherwise limited, all reactions were carried out using a dry solvent under N ₂ gas atmosphere in a dry glass container, using standard vacuum line techniques. All work-up and purifications were performed using reagent grade solvents in air. Analytical thin layer chromatography (TLC) was performed using E. Merck silica gel 60 F 254 precoated plates (0.25 mm). The developed chromatograms were analyzed with a UV lamp (254 nm or 365 nm). Flash column chromatography was performed using E. Merck silica gel 60 (230-400 mesh). Silica gel column chromatography was performed using an Isolera Spektra instrument equipped with Biotage SNAP Ultra 25 g cartidge. Nuclear magnetic resonance (NMR) spectra were recorded on a JEOL JNM-ECA-600 ( ¹ H 600 MHz, ¹³ C 150 MHz) spectrometer. Chemical shifts of ¹ H NMR were expressed in relative parts per million (ppm) of tetramethylsilane (δ 0.00 ppm). The chemical shifts of ¹³ C NMR were expressed as relative parts per million (ppm) of CDCl ₃ (δ 77.2 ppm). Data are chemical shift, multiplicity (s = singlet, d = doublet, dd = doublet of doublets, t = triplet, dt = doublet of triplets, td = triplet of doublets, q = quartet, m = multiplet, brs = broad singlet ), coupling constant (Hz), and integration reported in this order.

Synthesis Example 1
Synthesis Example 1-1: Compound 1p

Potassium carbonate (1.05 g, 7.60 mmol), 2-chloroiodobenzene (712 mg, 2.98 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (21.0 mg, 30 μmol) in a Schlenk tube with a magnetic stirrer in the air And 4-biphenylboronic acid (713 mg, 3.60 mmol) were added. The tube was filled with N ₂ gas. Toluene (10 mL), H ₂ O (2.5 mL) and ethanol (2.5 mL) were subsequently charged to the tube. The mixture was stirred at 80 ° C. for 10.5 hours. After cooling the mixture to room temperature. The reaction was quenched with H ₂ O (20 mL) and the mixture was extracted with hexane (10 mL) then dichloromethane (10 mL × 3). The organic layer was dried over anhydrous sodium sulfate and the resulting solution was filtered through a silica gel pad and concentrated in vacuo. The crude product was recrystallized with CH ₂ Cl ₂ / methanol to give the target compound 1p as white solid (46%, 367 mg, 1.39 mmol).
2-Chloro-1,1 ′: 4 ′, 1 ′ ′-terphenyl (Compound 1p):
¹ H NMR (CDCl ₃ ) δ 7.29-7.40 (m, 4H), 7.45-7.50 (m, 3H), 7.54 (d, J = 8.4 Hz, 2H), 7.65-1.68 (m, 4H); ¹³ C NMR HRCD (DART, positive): m / z = 265.0785. Calcd for C ₁₈ (CDCl ₃ ) δ 126.98, 127.09, 127.60, 128.77, 129.00, 130.30, 130.23, 131.58, 132.54, 140.31, 140.64, 140.90; HRMS (DART, positive): H ₁₄ Cl: 265.078 [M + H] ⁺ .

Synthesis Example 1-2-1: Compound 1b

Potassium carbonate (3.47 g, 25.1 mmol), 1,4-dibromo-2-chlorobenzene (1.35 g, 5.00 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (42.1) in a Schlenk tube equipped with a magnetic stirrer in the air. mg, 60 μmol), and phenylboronic acid (1.46 g, 12.0 mmol) were added. The tube was filled with N ₂ gas. Toluene (17 mL), H ₂ O (4.2 mL) and ethanol (4.2 mL) were subsequently charged to the tube. The mixture was stirred at 80 ° C. for 18 hours. After cooling the mixture to room temperature, the reaction was quenched with H ₂ O (20 mL) and the mixture was extracted with hexane (10 mL) then dichloromethane (20 mL × 3). The organic layer was dried over anhydrous sodium sulfate and the resulting solution was filtered through a silica gel pad and concentrated in vacuo. The crude product was recrystallized from methanol to give the target compound 1b as a white solid (71%, 933 mg, 3.50 mmol).
2′-Chloro-1,1 ′: 4 ′, 1 ′ ′-terphenyl (Compound 1b):
¹ H NMR (CDCl ₃ ) δ 7.38-7.50 (m, 9 H), 7.54 (dd, J = 7.8, 1.8 Hz, 1 H), 7.61-7.63 (m, 2 H), 7.71 (d, J = 1.2 Hz, 1 H ; ¹³ C NMR (CDCl ₃ ) δ 125.71, 127.25, 128.08, 128.27, 128.67, 129.66, 131.86, 133.07, 139.27, 139.62, 139.63, 141.95; HRMS (DART, positive): m / z = 265.0782 calcd for C ₁₈ H ₁₄ Cl: 265.078 [M + H] ⁺ .

Synthesis example 1-2-2
On the other hand, compound 1b could be obtained with higher yield also by another process. In a Schlenk tube equipped with a magnetic stirrer in the air, potassium carbonate (10.4 g, 75 mmol), 1,4-dibromo-2-chlorobenzene (4.06 g, 15.0 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (211 mg, 0.30 mmol) and phenylboronic acid (4.39 g, 36.0 mmol) were charged. The tube was filled with N ₂ gas. Toluene (50 mL), H ₂ O (12.5 mL) and ethanol (12.5 mL) were subsequently charged to the tube. The mixture was stirred at 80 ° C. for 18 hours. After cooling the mixture to room temperature, the reaction was quenched with H ₂ O (60 mL) and the mixture was extracted with hexane (30 mL) then dichloromethane (60 mL × 3). The organic layer was dried over sodium sulfate and the resulting solution was filtered through a silica gel pad and concentrated in vacuo. The crude product was recrystallized from methanol to give target compound 1b as a white solid (86%, 3.43 g, 13.0 mmol).

Synthesis Example 1-3: Compound 1c to Compound 1m
The following compounds 1c to 1m were synthesized in the same manner as in Synthesis Example 1-2-1 except that compounds having various substituents (R) were used instead of phenylboronic acid as raw materials.

2 ''-Chloro-1, 1 ': 4', 1 '': 4 '', 1 ''':4''': 1 ''''-quinkiphenyl (Compound 1c):
¹ H NMR (CDCl ₃ ) δ 7.37-7.39 (m, 2H), 7.46-7.50 (m, 5H), 7.59-7.62 (m, 3H), 7.65-7.73 (m, 10H), 7.79 (d, J = 1.8 Hz, 1 H); ¹³ C NMR (CDCl ₃ ) δ 125.65, 127.04, 127.27, 127.58, 127.63, 127.72, 127.62, 129.62, 129.06, 130.09, 131.94, 133.16, 138.18, 138.43, 139.06, 140.68, 140.74, 140.89, 141.02, 141.48; HRMS (DART, positive): m / z = 417.1411. Calcd for C ₃₀ H ₂₂ Cl: 417.1410 [M + H] ⁺ .
2′-Chloro-3,3 ′ ′-dimethyl-1,1 ′: 4 ′, 1 ′ ′-terphenyl (compound 1e):
¹ H NMR (CDCl ₃ ) δ 2.43 (s, 3H), 2.44 (s, 3H), 7.21 (t, J = 6.3 Hz, 2H), 7.30 (brs, 2H), 7.33-7.43 (m, 5H), 7.51 to 7.53 (m, 1H), 7.69 to 7.70 (m, 1H); ¹³ C NMR (CDCl ₃ ) δ 21.69, 21.72, 124.33, 125.65, 127.99, 127.99, 128.14, 128.57, 128.60, 128.80, 129.03, 130.33 HRMS (DART, positive): m / z = 293.1099. Calcd for C ₂₀ H ₁₈ Cl: 293.1097 [M + H] ⁺ . 131.80, 132.97, 137.89, 138.77, 139.43, 139.63, 141.95;
2-Chloro-1,4-di (1-naphthyl) benzene (compound 1f):
¹ H NMR (CDCl ₃ ) δ 7.48-7.61 (m, 10H), 7.66 (d, J = 8.4 Hz, 1 H), 7.71 (d, J = 1.2 Hz, 1 H), 7.91-7.95 (m, 4 H), 8.03-8.05 (m, 1 H); ¹³ C NMR (CDCl ₃ ) δ 125.45, 125.59, 125.91, 126.13, 126.20, 126.43, 126.61, 127.31, 127.52, 128.54, 128.64, 131.11, 131.60, 131.96, 132.09 HRMS (DART, positive): m / z = 365.1098. Calcd for C ₂₆ H ₁₈ Cl: 365.1097 [M.S, 133.73, 134.06, 134.18, 137.40, 138.32, 141.95 (two sp 2 signals were not observed because of overlapping); + H] ⁺ .
4,4 ′ ′-Bis (methoxycarbonyl) -2′-chloro-1,1 ′: 4 ′, 1 ′ ′-terphenyl (compound 1 g):
¹ H NMR (CDCl ₃ ) δ 3.96 (s, 3 H), 3.96 (s, 3 H), 7.45 (d, J = 7.8 Hz, 1 H), 7.56-7.58 (m, 2 H), 7.59 (dd, J = 8.1 , 1.5 Hz, 1 H), 7.68-7. 70 (m, 2 H), 7. 76 (d, J = 1.8 Hz, 1 H), 8.13-8.15 (m, 4 H); ¹³ C NMR (CDCl ₃ ) δ 52.42, 125. 96, 127. 20 HRMS (DART, positive): 129.00, 129.64, 129.90, 130.49, 131.83, 133.18, 139.28, 141.34, 143.57, 143.76, 166.94 (one aryl sp2 signal and one sp3 signal were not reflected because of HR) (DART, positive): m / z = 381.0894. calcd for C ₂₂ H ₁₈ ClO ₄ : 381.0894 [M + H] ⁺ .
2-Chloro-1,4-di (2-benzothienyl) benzene (compound 1k):
1 H NMR (CDCl ₃ ) δ 7.34-7.41 (m, 4H), 7.63 (s, 1H), 7.67 (brs, 3H), 7.81 (d, J = 7.2 Hz, 1H), 7.83-7.88 (m, 4H) ¹³ C NMR (CDCl ₃ ) δ 120.91, 122.24, 122.59, 124.16, 124.84, 124.82, 125.00, 125.06, 125.11, 128.43, 132.37, 132.86, 135.42, 135.60, 139.92, 139.97, 140.11, 140.67 HRMS (DART, positive): m / z = 377.0226. Calcd for C ₂₂ H ₁₄ ClS ₂ : 377.0225 [M + H] ⁺ .
2′-Chloro-4,4 ′ ′-dimethoxy-1,1 ′: 4 ′, 1 ′ ′-terphenyl (compound 1 l):
¹ H NMR (CDCl ₃ ) δ 3.86 (s, 3H), 3.87 (s, 3H), 6.98-7.00 (m, 4H), 7.37 (d, J = 7.8 Hz, 1H), 7.42-7.43 (m, 2H) ), 7.48 (dd, J = 7.8, 1.8 Hz, 1 H), 7.54-7.55 (m, 2 H), 7.65 (d, J = 1.8 Hz, 1 H); ¹³ C NMR (CDCl ₃ ) δ 55.49, 55.57, 113.72 HRMS (DART, positive): m / z = 325.0995. Calcd for C ₂₀ H ₁₈ ClO ₂ : 325.0995, 114.56, 125.23, 128.16, 128.25, 130.73, 131.80, 132.15, 133.39, 141.21, 159.32, 159.77; [M + H] ⁺ .
2′-Chloro-4,4 ′ ′-bis (trifluoromethyl) -1,1 ′: 4 ′, 1 ′ ′-terphenyl (compound 1m):
¹ H NMR (CDCl ₃ ) δ 7.44 (d, J = 7.8 Hz, 1 H), 7.58 (dd, J = 7.8, 1.8 Hz, 1 H), 7.61 (d, J = 7.8 Hz, 2 H), 7.72-7. m, 7 H); ¹³ C NMR (CDCl ₃ ) δ 124. 31 (q, J _CF = 271 Hz), 124. 34 (q, J _CF = 270 Hz), 125. 37 (q, J _CF = 4.2 Hz), 126.04, 126. 18 ( q, J _CF = 4.4 Hz), 127.60, 129.04, 130.03, 130.22 (q, J _CF = 33.0 Hz), 130.41 (q, J _CF = 33.0 Hz), 131.91, 133.26, 138.99, 141.20, 142.51, 142.85; HRMS (DART, positive):. m / z = 401.0535 calcd for C 20 H 12 Cl 1 F 8: 401.0532 [M + H] +.
2′-Chloro-4,4 ′ ′-bis (trimethylsilyl) -1,1 ′: 4 ′, 1 ′ ′-terphenyl (compound 1 n):
¹ H NMR (CDCl ₃ ) δ 0.31 (s, 9 H), 0.32 (s, 9 H), 7.41 (d, J = 8.4 Hz, 1 H), 7.48-7.49 (m, 2 H), 7.54 (dd, J = 8.1 , 1.5 Hz, 1 H), 7.59-7.63 (m, 6 H), 7.71 (d, J = 1.8 Hz, 1 H); ¹³ C NMR (CDCl ₃ ) δ -1.03, -1.00, 125.61, 126.41, 128.57, 128.79, HRMS (DART, positive): m / z = 409.1571. Calcd for C ₂₄ H ₃₀ ClSi ₂ : 409.1575 [M + H] ⁺ . 131.79, 132.93, 133.18, 134.06, 139.49, 139.93, 140.24, 141.78;

  Example 1

[Wherein, Ar represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. ]

Example 1-1 (compound 2b; Ar = phenyl group)
In air, a magnetic stirrer was placed in a 10 mL glass container equipped with a J. Young O ring tap, and cesium carbonate (489 mg, 1.50 mmol, 3 equivalents) was charged. The vessel was dried with a heat gun under vacuum and then cooled to room temperature over 1 hour. Compound 1b (132 mg, 500 μmol) obtained in Synthesis Example 1-2, PdCl ₂ (4.40 mg, 25.0 μmol, 5.0 mol%), n-butyl diadamantyl phosphine (P ⁿ Bu (Ad) ₂ ; 18.0 mg, 50.0 μmol, 10 mol%) and pivalic acid (26.0 mg, 25.0 μmol, 0.50 equivalents) were added. The glass vessel was filled with N ₂ gas and then cyclopentyl methyl ether (CPME; 5.0 mL) was added under N ₂ atmosphere. The mixture was stirred at 140 ° C. for 14 hours. After the mixture was cooled to room temperature, the reaction was quenched with H ₂ O and the mixture was extracted with dichloromethane (20 mL × 3). The organic layer was dried over anhydrous sodium sulfate, and the resulting solution was filtered through a silica gel pad or Celite® and concentrated in vacuo. The crude product was purified by column chromatography to give target compound 2b as a white solid (52%, 59.6 mg, 0.130 mmol).
1,4,6-triphenyltriphenylene (compound 2b):
¹ H NMR (CDCl ₃ ) δ 7.04-7.10 (m, 3H), 7.24-7.31 (m, 3H), 7.36-7.56 (m, 13H), 7.71-7.73 (m, 2H), 8.09 (d, J = 1.2 Hz, 1 H), 8. 46 (d, J = 7.8 Hz, 1 H), 8. 50 (d, J = 8.4 Hz, 1 H); ¹³ C NMR (CDCl ₃ ) δ 123.36, 123.85, 125.45, 125.59, 126.93, 127.16, 127.18, 127.26, 127.29, 128.67, 129.28, 129.58, 129.95, 130.11, 130.24, 130.32, 130.50, 131.27, 131.31, 131.48, 139.31, 140.73, 144.88, 145.44 (three sp ² signals presente HRMS (DART, positive): m / z = 457.1955. calcd for C ₃₆ H ₂₅ : 457.1956 [M + H] ⁺ .

Example 1-2 (Compound 2c to Compound 2k)
The following compounds 2c to 2k were synthesized in the same manner as in Example 1-1 except that the compounds 1c to 1k obtained in Synthesis Example 1-3 were used as raw materials in place of the compound 1b. The yield of the compound 2b obtained in Example 1-1 is also shown below.

1,4,11-Tris [(1,1'-biphenyl) -4-yl] -6-phenyltriphenylene (2c): ¹ H NMR (CDCl ₃ ) δ 7.07-7.78 (m, 36 H), 8.16 (s, 1H), 8.19 (s, 1H), 8.56 (brs, 2H); ¹³ C NMR (CDCl ₃ ) δ 123.88, 123.92, 125.55, 125.07, 127.25, 127.31, 127.37, 127.42, 127.52, 127.58, 127.68, 127.73 , 128.42, 128.44, 128.94, 129.28, 129.47, 130.36, 130.54, 131.59, 131.40, 137.96, 139.20, 136.50, 140.50, 140.55, 140.78, 140.82, 141.45, 144.45 HRMS (MALDI-TOF, positive): m / z = 760.3094. calcd for C ₆₀ H ₄₀ : 760.3130 [M] ⁺ . sp2 signals were not observed because of overlapping.
6- (tert-Butyl) -1,4,11-tris (4- (tert-butyl) phenyl) triphenylene (compound 2d):
¹ H NMR (CDCl ₃ ) δ 1.01 (s, 9 H), 1.32 (s, 9 H), 1. 36 (s, 9 H), 1.41 (s, 9 H), 7.02 (d, J = 8.4 Hz, 2 H), 7.30 ( d, J = 8.4 Hz, 2 H), 7.42-7.52 (m, 11 H), 7. 68 (dd, J = 7.8, 1.8 Hz, 1 H), 7. 91 (d, J = 1.8 Hz, 1 H), 8.08 (d, J = 1.2 Hz, 1 H), 8. 38 (d, J = 9.0 Hz, 1 H), 8. 45 (d, J = 9.0 Hz, 1 H); ¹³ C NMR (CDCl ₃ ) δ 31.17, 31.50, 31.59, 31.69, 34.62, 34.66 , 34.75, 34.83, 122.88, 124.45, 125.21, 125.62, 126.34, 126.60, 127.62, 128.87, 129.56, 129.52, 120.01, 130.01, 130.05, 130.25, 130.49, 131.53, 131.84, 137.00, 139.00, 139.00 HRMS (DART, positive): m / z = 681.4461. Calcd for C ₅₂ H ₅₇ : 681.4460 [M + H], 139.07, 142.45, 147.97, 149.89, 150.14 (one sp ² signal was not observed because of overlapping); ] ^+.
10-methyl-1,4,6-tris (3-methylphenyl) triphenylene (compound 2e):
¹ H NMR (CDCl ₃ ) δ 2.36 (s, 3H), 2.38 (s, 3H), 2.42 (s, 3H), 2.49 (s, 3H), 6.74 (s, 1H), 6.93 (dd, J = 8.4 , 1, 2 Hz, 1 H), 7.02 (d, J = 7.2 Hz, 1 H), 7.08 (d, J = 7.8 Hz, 1 H), 7.17-7.41 (m, 9 H), 7.49 (s, 2 H), 7.63 (d, J = 8.4 Hz, 1 H), 7. 69 (dd, J = 8.4, 1.8 Hz, 1 H), 8.12 (d, J = 1.8 Hz, 1 H), 8. 26 (s, 1 H), 8. 48 (d, J = 9.0 Hz, 1 H); ¹³ C NMR (CDCl ₃ ) δ 21.46, 21.72, 21.78, 123.67, 124.20, 125.32, 127.23, 127.90, 127.94, 128.00, 128.24, 128.52, 129.01, 129.34, 129.40, 129.66, 130.09, 130.19, 130.27, 130.33, 130.42, 130.66, 131.02, 131.50, 136.52, 1376, 138.39, 138.92, 139.19, 139.34, 140.85, 145.63 (one sp 3 signals and two sp 2 signals being out of view HRMS (DART, positive): m / z = 513.2583. calcd for C ₄₀ H ₃₃ : 513.2582 [M + H] ⁺ .
1,4,13-tri (naphthalen-1-yl) benzo [g] chrysene (compound 2f):
¹ H NMR (C ₂ D ₂ Cl ₄ , 130 ° C.) δ 6.61-6.62 (m, 1 H), 7. 27-8. 08 (m, 29 H), 8. 78 (d, J = 8.4 Hz, 1 H), 9.02 (d, J ^13C NMR (C ₂ D ₂ Cl ₄ , 130 ° C.) δ 124.75, 125.01, 125.10, 125.34, 125.48, 125.61, 125.68, 125.71, 125.82, 125.92, 126.03, 126.17, 126.22 126.27, 127.04, 127.48, 127.56, 127.74, 127.88, 128.13, 128.26, 128.60, 128.79, 129.01, 129.05, 129.63, 129.87, 130.81, 130.86, 131.15, 131.39, 131.53, 131.16, 131. HRMS (DART, positive): m / z = 657.2584. Calcd for ₅₂ 132.02, 133.05, 133.55, 134.22, 136.98, 137.92, 137.32, 139.47, 142.41, 142.79 (two sp 2 signals were not observed because of overlapping); H ₃₃ : 657.2582 [M + H] ⁺ .
6- (Methoxycarbonyl) -1,4,11-tris [4- (methoxycarbonyl) phenyl] triphenylene (compound 2 g):
¹ H NMR (CDCl ₃ ) δ 3.70 (s, 3H), 3.94 (s, 3H), 3.97 (s, 3H), 4.03 (s, 3H), 7.05 (d, J = 8.4 Hz, 2H), 7.56 ( d, J = 8.4 Hz, 2 H), 7.61-7. 64 (m, 4 H), 7. 79 (dd, J = 8.4, 1.8 Hz, 1 H), 7. 92 (d, J = 8.4 Hz, 2 H), 8.01 (d, J = 1.8 Hz, 1 H), 8. 10 (dd, J = 9.0, 1.8 Hz, 1 H), 8. 14 (d, J = 7.8 Hz, 2 H), 8. 20 (d, J = 8.4 Hz, 2 H), 8. 40 (d, J = 1.8 Hz, 1 H), 8.54 (d, J = 8.4 Hz, 1 H), 8. 58 (d, J = 7.8 Hz, 1 H); ¹³ C NMR (CDCl ₃ ) δ 51.99, 52.34, 52.39, 52.55, 123.69, 124.81 , 126.03, 126.97, 127.40, 127.55, 128.23, 129.28, 129.58, 129.70, 129.76, 129.17, 130.34, 130.41, 130.48, 130.81, 130.96, 131.30, 132.38, 134.50, 137.83, 138.940, 138601, 139. HRMS (DART, positive): m / z = 689.2174. Calcd for C ₄₄ H ₃₃ O ₈ : 689.2175 [M +, 148.91, 149.58, 166.71, 166.98, 167.17 (one sp2 signal was not observed because of overlapping); H] ⁺ .
10-methoxy-1,4,6-tris (3-methoxyphenyl) triphenylene (compound 2j):
¹ H NMR (CDCl ₃ ) δ 3.78 (s, 6H), 3.81 (s, 3H), 3.95 (s, 3H), 6.69 (s, 1H), 6.72 (d, J = 7.2 Hz, 1H), 6.75 ( dd, J = 9.6, 2.4 Hz, 1 H), 6.82 (dd, J = 8.1, 2.4 Hz, 1 H), 6. 92 (dd, J = 8.4, 2.4 Hz, 1 H), 6. 98 (dd, J = 7.8, 2.4 Hz , 1H), 7.04-7.12 (m, 3H), 7.22 (t, J = 7.8 Hz, 1 H), 7.32 (t, J = 7.5 Hz, 1 H), 7.37 (t, J = 7.8 Hz, 1 H), 7.46 -7.50 (m, 2H), 7.68-7.71 (m, 2H), 7.88 (d, J = 2.4 Hz, 1 H), 8.14 (s, 1 H), 8.43 (d, J = 9.0 Hz, 1 H); ¹³ C _{NMR (CDCl 3) δ 55.32,} 55.35, 55.41, 55.44, 105.92, 112.49, 112.73, 112.82, 113.73, 115.13, 119.70, 122.14, 122.34, 123.68, 124.12, 125.33, 128.94, 129.03, 129.45, 129.85, 130.02, 130.05, 130.15, 130.24, 130.63, 131.35, 131.57, 137.56, 138.30, 142.14, 146.19, 146.53, 158.30, 159.93, 160.15, 160.47 (two sp ² signals were not seen because of overlapping).
Compound 2k:
¹ H NMR (CDCl ₃ ) δ 6.62 (s, 1 H), 6.87 (t, J = 7.8 Hz, 1 H), 7.05 (s, 1 H), 7.12 (t, J = 7.8 Hz, 1 H), 7.19-7. m, 4H), 7.30 (d, J = 7.8 Hz, 1 H), 7.43 (d, J = 7.2 Hz, 1 H), 7.47-7.52 (m, 2 H), 7.56-7.58 (m, 2 H), 7.73 (d , J = 7.8 Hz, 1 H), 7.75 (d, J = 7.8 Hz, 1 H), 7.81-7. 84 (m, 3 H), 7. 90 (d, J = 7.8 Hz, 1 H), 7.94 (d, J = 7.2 Hz , 1H), 7.96 (d, J = 7.8 Hz, 1H), 8.17 (d, J = 8.4 Hz, 1 H), 8.63 (d, J = 1.8 Hz, 1 H); ¹³ C NMR (CDCl ₃ ) δ 120.29, 122.25, 122.27, 122.37, 122.83, 123.84, 123.83, 124.38, 124.45, 124.58, 124.56, 124.81, 124.95, 125.00, 125.49, 125.52, 125.90, 127.24, 128.12, 98.12, 12,12. HRMS (DART, positive): m / z = 681.0829. Calc. 129.94, 130.19, 131.59, 132.14, 132.41, 137.55, 138.30, 139.98, 140.03, 140.57, 140.83, 141.21, 141.84, 144.26, 145.21; HRMS (DART, positive): m / z = 681.0829. Calcd for C ₄₄ H ₂₅ S ₄ : 681.0839 [M + H] ⁺ .

  In the present example, first, the scope of the present reaction was examined using an aromatic hydrocarbon as a substrate. When chloroterphenyl 1b was used as a substrate, cyclized dimerization 2b was obtained in a yield of 52% or 81%. The reaction also proceeded to the compound 1c substituted with biphenylyl and the compound 1d having a tert-butyl group as a substituent, and compounds 2c and 2d were obtained in moderate yields, respectively. In particular, the production method of the present invention was applicable to a low solubility molecule such as compound 1c, although the yield slightly decreased. Next, when Compound 1e was used as a substrate, Compound 2e was selectively obtained. Although formation of a regioisomer is assumed when the triphenylene skeleton is formed, it is considered that the reaction at a position with less steric hindrance preferentially proceeded. Also when Compound 1f was used as a substrate, no intramolecular cyclized compound was obtained, and cyclized dimer 2f was obtained. From the above results, it can be understood that the cyclodimerization reaction takes precedence over the intramolecular cyclization reaction, even when a 5-membered ring can be formed in the molecule.

  Next, the application range of the substrate having a polar functional group and a heteroaromatic ring was examined. The reaction proceeded with a low yield for a substrate having a methoxycarbonyl group to obtain 2 g of a compound. The reaction proceeded with a low yield even with a substrate having a methylthio group, a cyano group and a methoxy group, and Compound 2h, Compound 2i and Compound 2j were obtained, respectively. In the case of a heteroaromatic ring, compound 2k was obtained in a moderate yield when the reaction was performed using stable 2-chloro-1,4-di (2-benzothienyl) benzene as a substrate. From this, it can be understood that the reaction proceeds even with a substrate containing a hetero atom or a substrate containing a five-membered ring.

  Example 2

  The reaction was performed in the same manner as in Example 1-1 except that the compound 1p obtained in Synthesis Example 1-1 was used as a raw material instead of the compound 1b.

  In order to prove that benzine is generated, the reaction was carried out using a substrate 1p in which a chloro group was introduced to the terminal phenyl group of terphenyl. Since the generated benzine X has an asymmetric reaction point, it was expected that the subsequent reaction would yield regioisomers 2p and 2p '.

However, in practice, the yield of compound 2p ′ was trace, and it was observed that in addition to compound 2p, compound 2b was formed as a main product (2p: 2b = 1: 2.3).
1-([1,1′-biphenyl] -4-yl) -11-phenyltriphenylene (compound 2p):
¹ H NMR (CDCl ₃ ) δ 7.06-7.07 (m, 2H), 7.14-7.15 (m, 3H), 7.41-7.43 (m, 1H), 7.52 (t, J = 7.5 Hz, 2H), 7.57-7.60 (m, 3H), 7.68-7.78 (m, 8H), 8.19 (s, 1H), 8.61-8.68 (m, 4H); ¹³ C NMR (CDCl ₃ ) δ 122.71, 123.40, 123.88, 123.92, 125.55, 126.72 , 127.21, 127.28, 127.37, 127.55, 127.64, 127.69, 128.81, 128.98, 129.11, 129.92, 130.30, 130.30, 131.52, 132.06, 137.44, 140.28, 140.61, 140.65, 141.10, 145.10 (one sp 2 signal signal HRMS (DART, positive): m / z = 457.1954. calcd for C ₃₆ H ₂₅ : 457.1956 [M + H] ⁺ .
1-([1,1′-biphenyl] -4-yl) -6-phenyltriphenylene (compound 2p ′):
¹ H NMR (CDCl ₃ ) δ 7.09 (t, J = 7.8 Hz, 1 H), 7.38 (t, J = 7.5 Hz, 1 H), 7.44 (t, J = 7.5 Hz, 1 H), 7.47-7.59 (m, 8H), 7.67-7.72 (m, 5H), 7.82-7.85 (m, 3H), 7.91 (dd, J = 8.4, 1.8 Hz, 1 H), 8.57 (d, J = 7.8 Hz, 1 H), 8.68 (d , J = 9.0 Hz 1H, 8.74 (d, J = 7.8 Hz, 1 H), 8.85 (d, J = 1.8 Hz, 1 H); ¹³ C NMR (CDCl ₃ ) δ 122.41, 122.58, 123.37, 123.94, 125.32, 126.64, 126.76, 126.96, 127.22, 127.63, 127.75, 129.16, 129.61, 129.78, 129.37, 130.50, 131.05, 131.94, 131.94, 131.83, 140.31, 140.60, 140.88, 141.46, one hundred and one sp HRMS (DART, positive): m / z = 457.1956. Calcd for C ₃₆ H ₂₅ : 457.1956 [M + H] ⁺ . ² signal was not observed because of overlapping.

[Example 3]
The presence of side reactions found in Example 2 above was found. Further, in the crude product of Example 1-1-1 using chloroterphenyl 1b as a substrate, in addition to compound 2b, compound 2p was by-produced in a ratio of 2b: 2p = 3.3: 1.

  From this result, the simplification of the isolation operation and the improvement of the yield were expected, and a search for reaction conditions for suppressing side reactions was conducted. Since the ratio of by-products obtained from chloroterphenyl 1b was determined in the initial deprotonation step, it was considered that side reactions can be suppressed by selecting an appropriate base.

  In this reaction, when pivalic acid is used as a carboxylic acid and cesium carbonate is used as a base, cesium pivalate is generated from both of these, and this also functions as a base. For this reason, the following experiment was conducted on the assumption that the transition state of deprotonation can be controlled and the desired benzine can be selectively generated by examining the carboxylic acid.

A reaction was carried out by the same treatment as in Example 1-1 except that the type of carboxylic acid was changed as shown in Table 1 below. In any of the reactions, the yield of compound 2p ′ was trace. The yield was calculated by ¹ H NMR using benzyl phenyl ether as an internal standard. Also, the yields in parentheses in the table are isolated yields. The results are shown in Table 1.

  As a result, when bulky carboxylic acid was used, the reaction proceeded with good yield in all cases, but did not lead to complete control of selectivity. However, as a result of conducting further examination, it was found that the side reaction can be completely suppressed by conducting the reaction without adding the carboxylic acid. As a result, the yield of the desired product was the highest.

  Example 4

  In order to improve the yield, the effects of the base and the ligand compound were examined under the condition that no carboxylic acid was added. A reaction was carried out by the same treatment as in Example 1-1 except that the type of the base and the ligand compound was changed as shown in Table 2 below without using a carboxylic acid. In all of the reactions, the yield of compound 2p 'was trace.

  As a result, selectivity and yield were excellent when cesium carbonate was 3 equivalents. In addition, when cesium fluoride was used as a base, in the case of 3 equivalents to 5 equivalents, an improvement in yield was observed.

  [Example 5]

  In order to improve the yield, the substrate applicability was examined under the condition that no carboxylic acid was added. In the same manner as in Example 1-1 except that a carboxylic acid was not used, and Compound 1c to Compound 1g and Compound 1k to Compound 1n obtained in Synthesis Example 1-3 were used instead of Compound 1b as a substrate, Compound 2c to Compound 2g, and Compound 2k to Compound 2n were synthesized.

The spectral data of the compound which has not described spectral data above among each compound obtained is as follows.
Compound 2 g (main product) + compound 2 g ′ (by-product) (2 g / 2 g ′ = 3: 1):
¹ H NMR (CDCl ₃ ) δ 3.70 (s, 9H), 3.89 (s, 3H), 3.94 (s, 9H), 3.97 (s, 9H), 3.98 (s, 3H), 3.99 (s, 3H), 4.03 (s, 12 H), 7.05 (d, J = 8.4 Hz, 6 H), 7.09 (d, J = 7.8 Hz, 2 H), 7.56 (d, J = 8.4 Hz, 6 H), 7. 60-7. 66 (m, 15 H ), 7.76-7.82 (m, 10H), 7.91-7.94 (m, 7H), 8.01 (s, 3H), 8.09-8.11 (m, 4H), 8.14 (d, J = 9.0 Hz, 6H), 8.19- 8.21 (m, 8H), 8.30 (d, J = 7.8 Hz, 1H), 8.40 (s, 3H), 8.53-8.63 (m, 8H), 8.81 (s, 1H) (The integral proton value is normalized based on the 8.81 peak as 1H); ¹³ C NMR (CDCl ₃ ) δ 51.99, 52.32, 52.34, 52.59, 52.58, 53.12, 123.80, 124.80, 124.84, 126.15, 126.96, 127.01, 127.26, 127.54, 128.21 , 128.40, 128.65, 128.68, 128.97, 129.26, 129.28, 129.35, 129.58, 129.70, 129.91, 130.17, 130.17, 130.17, 130.29, 130.33, 130.39, 130.42, 130.42, 130.57, 130.76, 130.75 , 130.80, 130.89, 130.95, 131.28, 131.53, 134.17, 134.48, 137.82, 137.85, 138.19, 139.94, 141.95, 144.24, 144.33, 144.59, 144.65, 145.00, 148.89, 14 9.57, 166.69, 166.91, 166.97, 167.10, 167.15, 171.58 (one sp 3 signals and four sp 2 signals were not observed because of overlapping). The structure of 2 g '(minor product) was assigned by analogy from the structures of 2 p and 2g can be separated from the mixture of 2g and 2g with extensive purification with silica-gel column chromatography, gel-permeation chromatography, and recrystallization to take the compound data.
6- (Methoxy) -1,4,11-tris [4- (methoxy) phenyl] triphenylene (compound 2l):
¹ H NMR (CDCl ₃ ) δ 3.32 (s, 3H), 3.83 (s, 3H), 3.86 (s, 3H), 3.92 (s, 3H), 6.84 (d, J = 8.4 Hz, 2H), 6.98 ( d, J = 9.0 Hz, 2 H), 7.04-7.06 (m, 5 H), 7.33 (d, J = 8.4 Hz, 1 H), 7.42-7.46 (m, 4 H), 7.48-7.52 (m, 2 H), 7.64 (dd, J = 8.4, 1.5 Hz, 1H), 8.03 (d, J = 1.8 Hz, 1H), 8.34 (d, J = 9.0 Hz, 1H), 8.38 (d, J = 8.4 Hz, 1H); 13 _{C NMR (CDCl 3) δ 54.71} , 55.51, 55.65, 55.71, 111.92, 114.10, 114.84, 115.03, 116.92, 123.20, 124.64, 125.03, 125.09, 128.20, 128.50, 129.80, 129.95, 130.04, 130.93, 131.00, 131.33, 131.71 HRMS (DART, positive): m / z = 577.2378. Calcd for C., 131.80, 133.62, 136.37, 137.76, 138.67, 138.63, 157.15, 159.94, 159.29 (one sp 2 signal was not observed because of overlapping); ₄₀ H ₃₃ O ₄ : 577.2379 [M + H] ⁺ .
6- (Trifluoromethyl) -1,4,11-tris [4- (trifluoromethyl) phenyl] triphenylene (compound 2m):
¹ H NMR (CDCl ₃ ) δ 7.05 (d, J = 7.8 Hz, 2 H), 7.56 (d, J = 8.4 Hz, 2 H), 7. 59 (d, J = 7.8 Hz, 2 H), 7. 64 (s, 2 H) , 7.69-7.71 (m, 3H), 7.74 (d, J = 8.4 Hz, 2 H), 7. 77 (dd, J = 8.4, 1.8 Hz, 1 H), 7.83 (d, J = 8.4 Hz, 2 H), 7.87 (7 s, 1 H), 7. 91 (d, J = 1.8 Hz, 1 H), 8.5-8. 61 (m, 2 H); ¹³ C NMR (CDCl ₃ ) δ 121.61, 121.72, 123.06, 123.47, 124.27, 124.78, 124.86, 125.22, 125.22 125.32, 125.85, 125.87, 126.33, 126.59, 126.61, 126.73, 127.12, 127.57, 127.59, 127.89, 129.10, 129.69, 129.94, 129.96, 130.06, 130.12, 130.18, 130.130, 1300.50, 1300.50 130.85, 130.95, 131.42, 133.57, 137.95, 138.95, 143.72, 147.25, 148.48 (The coupling constants (J _CF ) were not determined because the signals are too complicated. Thus, the observed peaks are as HRMS (DART, positive): m / z = 729.1452. Calcd for C ₄₀ H ₂₁ F ₁₂ : 729.1452 [M + H] ⁺ .
6- (trimethylsilyl) -1,4,11-tris [4- (trimethylsilyl) phenyl] triphenylene (compound 2n):
¹ H NMR (CDCl ₃ ) δ 0.01 (s, 9 H), 0.28 (s, 9 H), 0.31 (s, 9 H), 0.36 (s, 9 H), 7.02 (d, J = 7.8 Hz, 2 H), 7.44 ( d, J = 7.8 Hz, 2 H), 7. 50 (d, J = 8.4 Hz, 2 H), 7.52-7.55 (m, 4 H), 7.58-7.59 (m, 3 H), 7. 66 (d, J = 7.8 Hz, 2 H) ), 7.72 (dd, J = 8.4, 1.8 Hz, 1 H), 8.04 (s, 1 H), 8. 10 (d, J = 1.8 Hz, 1 H), 8.43 (d, J = 7.8 Hz, 1 H), 8.51 (d , J = 8.4 Hz, 1 H); ¹³ C NMR (CDCl ₃ ) δ -1.18, -0.94, -0.85, -0.73, 122.41, 123.85, 125.39, 126.32, 129.12, 129.23, 129.27, 129.46, 130.00, 130.29, 130.56 , 130.67, 131.36, 131.54, 131.61, 133.77, 134.41, 134.55, 136.29, 137.69, 139.11, 139.21, 139.26, 139.32, 141.08, 145.58, 145.77 (two sp 2 signals were not observed because of overlapping); TOF, positive): m / z = 744.3438. Calcd for C ₄₈ H ₅₆ Si ₄ : 744.3459 [M] ⁺ .

  On the other hand, when the reaction was carried out in the same manner as Example 2 except that pivalic acid was not used, a mixture of compound 2p and compound 2p 'was obtained in a yield of 72%. The compound 2p and the compound 2p 'could be isolated by silica gel column chromatography, gel permeation chromatography, recrystallization and the like.

  [Example 6]

  The reaction was carried out in the same manner as in Example 1-1 except that Compound 1a was used as a raw material instead of Compound 1b, to obtain Target Compound 2a in a yield of 83%. This reaction is considered to be via a palladium-benzyne intermediate as described above, and is a novel aromatic halide cyclodimerization reaction.

1-phenyltriphenylene (32.4 mg, 0.106 mmol) and iron (III) chloride (62.3 mg, 0.384 mmol) were added to a Schlenk tube equipped with a magnetic stirrer under the atmosphere. It was filled with N ₂ in a Schlenk tube. Dichloromethane (10 mL) was continuously added to the Schlenk tube. The mixture was stirred at 0 ° C. for 2.5 hours. The reaction was quenched with methanol (MeOH; 5.0 mL). The reaction mixture was washed with H ₂ O (40 mL) and the aqueous layer was extracted with dichloromethane (10 mL). The organic layer was dried over sodium sulfate and the resulting solution was filtered through a silica gel pad and concentrated in vacuo. The resulting solid was washed with methanol (MeOH) and dichloromethane to give dibenzo [e, l] pyrene in 76% yield (24.6 mg, 0.081 mmol).
Dibenzo [e, l] pyrene:
¹ H NMR (C ₂ D ₂ Cl ₄ ) δ 7.78-7.79 (m, 4H), 8.10 (t, J = 7.8 Hz, 2 H), 8.84-8.86 (m, 4 H), 8.95 (d, J = 7.8 Hz , 4H); ¹³ C NMR (C ₂ D ₂ Cl ₄ ) δ 124.84, 127.09, 129.93, 131.08, 132.78, 133.18 (one sp 2 signal was not observed because of overlapping); HRMS (DART, positive): m / z = 303.1171. Calcd for C ₃₀ H ₂₁ : 303.1174 [M + H] ⁺ .

[Example 7]
The Scholl reaction of compounds 2b and 2c was performed as follows.

Compound 2b (46.5 mg, 0.102 mmol) and iron (III) chloride (206 mg, 1.27 mmol) were added to a Schlenk tube equipped with a magnetic stirrer under the atmosphere. It was filled with N ₂ in a Schlenk tube. Dichloromethane (10 mL) was continuously added to the Schlenk tube. The mixture was stirred at 0 ° C. for 2.5 hours. The reaction was quenched with methanol (MeOH; 8.0 mL). The reaction mixture was washed with H ₂ O (40 mL) and the aqueous layer was extracted with dichloromethane (10 mL). The organic layer was dried and the resulting solution was concentrated in vacuo. The resulting solid was washed with methanol (MeOH) and dichloromethane to give compound 3b in 77% yield (35.4 mg, 0.0786 mmol).
Compound 3b:
¹ H NMR (C ₆ D ₄ Cl ₂ , 150 ° C.) δ 7.67-7.70 (m, 4H), 8.05-8.06 (m, 2H), 8.75-8.76 (m, 2H), 8.85-8.88 (m, 4H) , 9.09-9.10 (m, 2H), 9.15-9.17 (m, 2H), 9.28-9.29 (m, 2H); HRMS (MALDI-TOF, positive): m / z = 450.1390. Calcd for C ₃₆ H ₁₈ : 450.1409 [M] ^<+> . ^{< 13} > C NMR peaks were barely detected because of the low solubility of 3b.

The starting compound, Compound 2c (7.8 mg, 0.010 mmol), was added to a Schlenk tube equipped with a magnetic stirrer under the atmosphere. It was filled with N ₂ in a Schlenk tube. Dichloromethane (2.0 mL) and iron (III) chloride (75.6 mg, 0.466 mmol) were sequentially added to the Schlenk tube. The mixture was stirred at room temperature for 42 hours. The reaction was quenched with methanol (MeOH; 5.0 mL). The mixture was filtered and washed with methanol (MeOH; 40 mL) and dichloromethane (40 mL). The target substance C ₆₀ H ₂₆ (compound 3c) was obtained in a yield of 72% (5.5 mg, 0.0072 mmol). The reaction was complete and neither partial ring closure product nor starting material 2c was detected by MALDI-TOF measurement. A small amount of chlorinated compound 3c was detected by MALDI-TOF measurement.
Compound 3c:
HR-MS (MALDI-TOF, positive):. M / z = 746.2072 calcd for C 60 H 26:. 746.2035 [M] + 1 H and 13 C NMR peaks were not detected because of the low solubility of 3c.

[X-ray structural analysis]
The crystal data details of the compounds 2b, 2p and 2p ′ obtained in Examples 2 and 5 are shown in Table 3. The structures of the compounds 2b, 2p and 2p 'according to thermal vibration ellipsoid drawing software (ORTEP) are shown in FIGS. In each case, the crystals were soaked in mineral oil, placed on glass fibers and transferred to Rigaku PILATUS. In addition, graphite monochromatic light Mo Kα radiation (λ = 0.71075 Å) was used.

[Raman microscopy analysis]
The Raman spectrum of compound 3c was measured using a confocal Raman microscope (invia Reflex, Renishaw) equipped with a 488 nm semiconductor laser. The Raman signal was detected by a thermoelectric cooled charge coupling device (CCD). The laser light was focused on the sample using a 100 × objective lens with a numerical aperture of 0.85. The laser output was 6.45 μW. The measurement was performed at room temperature and atmospheric conditions. The Gaussian 09 program (40 running on a SGI Altix 4700 sustem) was used for DFT calculations. The structure of compound 3c was optimized by theory at B3LYP / 6-31G (d) level without symmetry assumption. The results are shown in FIG.

[Photophysical research]
For all measurements, a diluted solution of degassed spectral grade dichloromethane in a 1 cm square quartz cell was used. UV-Vis absorption spectra were recorded on a Shimadzu UV-3510 spectrometer with a resolution of 0.5 nm. The fluorescence spectrum was measured with an F-4500 Hitachi spectrometer or Shimadzu RF-6000 at a resolution of 0.4 nm. The absolute fluorescence quantum yield ( _{F F} ) was measured using a Shimadzu RF-6000 equipped with a calibrated integrating sphere system (207-21460-41). The results are shown in FIGS.

Claims (14)

General formula (1):

[Wherein, R ¹ and R ^{1 ′} represent a hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ³ represents a hydrogen atom. R ′ represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. R ¹ and R ³ may combine to form a ring. R ^{1 ′} and R ³ may combine to form a ring. R ² and R ′ may combine to form a ring. ]
A process for producing a polycyclic aromatic compound represented by
In the presence of a palladium catalyst and a base
General formula (2):

[Wherein, R ¹ and R ² are as defined above. X represents a halogen atom. ]
A production method comprising a reaction step of reacting a compound represented by The production method according to claim 1, wherein R ¹ is a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzothienyl group. The method according to claim 1, wherein R ² is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzothienyl group. The method according to any one of claims 1 to 3, wherein R 'is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted benzothiophene ring. The method according to any one of claims 1 to 4, wherein a ligand compound is added in the reaction step. The method according to claim 5, wherein the ligand compound is a phosphine compound. The method according to any one of claims 1 to 6, wherein the base is an alkali metal carbonate or an alkali metal fluoride salt. The method according to any one of claims 1 to 7, wherein a carboxylic acid is added in the reaction step. The method according to any one of claims 1 to 8, further comprising the step of causing an intramolecular cyclization reaction in the presence of an oxidizing agent after the reaction step. General formula (1A1):

[Wherein, R ¹ and R ^{1 ′} represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ′ represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. Provided that R ¹ , R ^{1 ′} and R ² are all unsubstituted phenyl groups, R ′ is 4- (9,12-diphenyltriphenyl) -2,5-dimethylphenyl group, 4- (2,9) , 12-triphenyltriphenyl) -2,5-dimethylphenyl group, or compounds which are benzene substituted with triphenylphenyl group. ]
, General formula (1A2):

[Wherein, R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ′ represents a substituted aromatic hydrocarbon ring or a substituted or unsubstituted heteroaromatic ring. However, when R ² is a substituted phenyl group and R ′ is a substituted benzene ring, 1,5-bis [3- (9,9-dimethyl-9H-fluoren-3-yl) phenyltriphenylene, 7,7 '-(1,5-triphenylenediyl) -bisbenzoxazole, 1,12-bis ([1,1': 3 ', 1-terphenyl] -3-yl) triphenylene, 3,3'-(1- 12-triphenylenediyl) bis [9-phenyl-9H-carbazole] ,, 3 '-(1-12-triphenylenediyl) bisdibenzothiophene, 1- [3- (bromomethyl) -5-methylphenyl] -12- 3,5-Dimethylphenyl) -triphenylene, 1- [3- (bromomethyl) -5-methylphenyl] -12-phenyltriphenylene, 1-phenyl-12- (2,4,6-trimethylphenyl) -triphenylene, 1 -(4-Methylphenyl) -12-phenyl-triphenylene, 1- (3,5-dimethylphenyl) -12-phenyltriphenylene, 1,12-bis (3,5-dimethylphenyl) -triphenylene, 8,9- The Enirujibenzo except [f, j] picene, 2-iodo-1,12-diphenyl triphenylene, and 1,12 diphenyl triphenylene. When R ′ is a non-substituted benzene ring, R ² is a substituted or non-substituted phenyl group, a substituted naphthyl group, a substituted pyridyl group, a substituted pyrazyl, a substituted or non-substituted dibenzofuran group, or a substituted or non-substituted dibenzothiophene group Excluding substituted or unsubstituted carbazole group, substituted or unsubstituted benzotriazole group, substituted or unsubstituted quinoline group, triphenylene group, phenanthrene group, indandione group, and flowene group. ]
A triarylene compound represented by The triarylene compound according to claim 10, wherein R ¹ and R ^{1 ′} are a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzothienyl group. The triarylene compound according to claim 10, wherein R ² is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzothienyl group. The triarylene compound according to any one of claims 10 to 12, wherein R 'is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted benzothiophene ring. General formula (1B):

Polycyclic aromatic compound represented by

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