JP2018184393A - Condensed ring compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a condensed ring compound having a regioselectively introduced substituent, in a short step and with high purity.SOLUTION: The present invention provides a method for intramolecular cyclization of a compound being represented by a formula (2) and having a specific structure.SELECTED DRAWING: None

Description

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

  In recent years, extensive research has been conducted to create various condensed ring compounds by intramolecular oxidative cyclization reaction. However, as represented by Non-Patent Document 1 and Non-Patent Document 2, many of these oxidative intramolecular cyclization reactions have a problem of low reaction selectivity. In order to obtain a certain reaction selectivity, it is necessary to introduce an electron-donating substituent or a sterically bulky substituent, which makes it difficult to create a novel condensed ring compound. Non-Patent Document 3 describes a method for obtaining a condensed ring compound more directly, but a large amount of impurities are generated in the reaction system, which is not sufficient in terms of high reaction selectivity.

  On the other hand, an attempt has been made to obtain a derivative of a condensed ring compound by directly introducing a substituent into an existing condensed ring compound (for example, Patent Document 1). However, in such a technique, it is extremely difficult to control the position of introduction of the substituent and the number of introductions. Therefore, much effort is required for the isolation and purification of the target compound. Therefore, it is not an effective method from the viewpoint of creating a flexible condensed ring compound.

Patent No. 5939520

Journal of Organic Chemistry 2007, 72, 2279. Organic Letters 2011, 13, 1634. Synlett 2016, 27, 2081.

The objective of this invention is providing the manufacturing method which manufactures the condensed ring compound which introduce | transduced the substituent into position-selection which was difficult to manufacture with the conventional method with a short process and high purity. Another object of the present invention is to provide a condensed ring compound useful for producing an electronic material.
The conventional method has a problem that a large amount of many kinds of impurities are generated.

As a result of intensive studies in order to solve the above problems, the present inventors have carried out intramolecular cyclization of a compound represented by the general formula (2) described later, and represented by the general formula (1) described later. The present inventors have found a production method for obtaining a fused ring compound with high yield and high purity. That is, the present invention relates to such a production method and a condensed ring compound having a substituent at a position that has been conventionally difficult and has been created by the production method.

(Where
X ¹ and X ² are the same or different and represent a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring which may have a substituent.
Aromatic ring represented by the aromatic ring and X ² represented by X ¹ may not be bonded may be bonded at least one binding.
R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an organic group, and adjacent substituents of R ^{1 to} R ⁴ are bonded to each other, and may have a substituent, or A condensed polycyclic aromatic ring may be formed.
When R ¹ and R ² are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ¹ may or may not be bonded by at least one bond. Good.
When R ³ and R ⁴ are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ² may or may not be bonded by at least one bond. Good.
When R ¹ and R ² are bonded to each other to form an aromatic ring, and R ³ and R ⁴ are bonded to each other to form an aromatic ring, these aromatic rings are bonded with at least one bond. Or may not be bonded. )

(Where
X ¹ and X ² are the same or different and represent a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring which may have a substituent.
Aromatic ring represented by the aromatic ring and X ² represented by X ¹ are not bonded.
R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an organic group, and adjacent substituents of R ^{1 to} R ⁴ are bonded to each other, and may have a substituent, or A condensed polycyclic aromatic ring may be formed.
When R ¹ and R ² are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ¹ are not bonded.
When R ³ and R ⁴ are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ² are not bonded.
When R ¹ and R ² are bonded to each other to form an aromatic ring, and R ³ and R ⁴ are bonded to each other to form an aromatic ring, these aromatic rings are bonded with at least one bond. Or may not be bonded. )

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method which manufactures the condensed ring compound which introduce | transduced the substituent into position-selection with a short process and high purity can be provided. Moreover, according to this invention, the condensed ring compound useful for manufacture of an electronic material can be provided.

4 is an HPLC chart of a reaction according to Example 4. 2 is an HPLC chart of a reaction according to Comparative Example 1. 6 is an HPLC chart of a reaction according to Comparative Example 2.

Hereinafter, the present invention will be described in more detail.
In the compound represented by the following general formula (2), X ¹ and X ² are the same or different and may have a substituent, a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring Represents. In the present invention, the intramolecular cyclization in the general formula (2) is highly selective by using an aromatic ring having 3 or more condensed rings which may have a substituent including X ¹ and X ^2. And is found that a compound represented by the general formula (1) is created.

The present invention is a method for producing a compound represented by the following general formula (1),
A production method comprising intramolecular cyclization of a compound represented by the following general formula (2).

(Where
X ¹ and X ² are the same or different and represent a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring which may have a substituent.
Aromatic ring represented by the aromatic ring and X ² represented by X ¹ may not be bonded may be bonded at least one binding.
R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an organic group, and adjacent substituents of R ^{1 to} R ⁴ are bonded to each other, and may have a substituent, or A condensed polycyclic aromatic ring may be formed.
When R ¹ and R ² are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ¹ may or may not be bonded by at least one bond. Good.
When R ³ and R ⁴ are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ² may or may not be bonded by at least one bond. Good.
When R ¹ and R ² are bonded to each other to form an aromatic ring, and R ³ and R ⁴ are bonded to each other to form an aromatic ring, these aromatic rings are bonded with at least one bond. Or may not be bonded. )

(Where
X ¹ and X ² are the same or different and represent a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring which may have a substituent.
Aromatic ring represented by the aromatic ring and X ² represented by X ¹ are not bonded.
R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an organic group, and adjacent substituents of R ^{1 to} R ⁴ are bonded to each other, and may have a substituent, or A condensed polycyclic aromatic ring may be formed.
When R ¹ and R ² are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ¹ are not bonded.
When R ³ and R ⁴ are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ² are not bonded.
When R ¹ and R ² are bonded to each other to form an aromatic ring, and R ³ and R ⁴ are bonded to each other to form an aromatic ring, these aromatic rings are bonded with at least one bond. Or may not be bonded. )

X ¹ and X ² are the same or different and represent a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring which may have a substituent.

The monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring in X ¹ and X ² is not particularly limited. For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring Pyridine ring, quinoline ring, isoquinoline ring, phenanthroline ring, imidazole ring, benzimidazole ring, carbazole ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furan ring, benzofuran ring, dibenzofuran ring and the like. In addition, about these aromatic rings, you may have arbitrary substituents.

Examples of the optional substituent include an organic group, and are not particularly limited. For example, the aromatic group may be a monocyclic, linked, or condensed ring having 6 to 30 carbon atoms, or 3 to 36 carbon atoms. Monocyclic, linked, or condensed heteroaromatic groups (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear or cyclic group having 3 to 18 carbon atoms) Or may have one or more substituents selected from the group consisting of branched alkyl groups, methoxy groups, ethoxy groups, and linear, cyclic, or branched alkoxy groups having 3 to 18 carbon atoms) , Hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, nitro group, cyano group, hydroxyl group, thiol group, amino group (—NH ₂ ), methyl group, ethyl group, direct carbon number 3-18 A chain, cyclic or branched alkyl group, Butoxy group, an ethoxy group, a straight chain 3 to 18 carbon atoms, cyclic, or alkoxy group, etc. branches.

  The monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a terphenyl group, a naphthalenyl group, and a phenylnaphthyl group. Group, naphthylphenyl group, anthracenyl group, pyrenyl group, phenanthrenyl group, perylenyl group, benzofluorenyl group, triphenylenyl group and the like. Of these, a phenyl group, a biphenyl group, a naphthalenyl group, or a triphenylenyl group is preferable.

  Examples of the monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms include, but are not limited to, for example, carbon containing at least one oxygen atom, nitrogen atom, or sulfur atom. Examples thereof include a monocyclic, linked, or condensed heteroaromatic group having 3 to 36, more preferably at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of the monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms contained above include, but are not limited to, for example, pyrrolyl group, thienyl group, furyl group, imidazolyl group , Pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyridyl, pyrimidyl, pyrazyl, 1,3,5-triazyl, indolyl, benzo Enyl, benzofuranyl, benzimidazolyl, indazolyl, benzothiazolyl, benzoisothiazolyl, 2,1,3-benzothiadiazolyl, benzoxazolyl, benzoisoxazolyl, 2,1, Examples include 3-benzooxadiazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, carbazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group, phenazine group, thiantenyl group and the like. Of these, a thienyl group, a furyl group, a benzothienyl group, a benzofuranyl group, a dibenzothienyl group, and a dibenzofuranyl group are preferable, and a benzothienyl group, a benzofuranyl group, a dibenzothienyl group, and a dibenzofuranyl group are more preferable.

  The linear, cyclic or branched alkyl group having 3 to 18 carbon atoms is not particularly limited, and examples thereof include an n-propyl group, an i-propyl group, an n-butyl group, and a sec-butyl group. Tert-butyl group, i-butyl group, n-hexyl group, cyclohexyl group, cyclohexadienyl group, octyl group, trifluoromethyl group, benzyl group, phenethyl group and the like. Of these, a methyl group, an ethyl group, an i-propyl group, an n-butyl group, or a tert-butyl group is preferable.

  The linear, cyclic or branched alkoxy group having 3 to 18 carbon atoms is not particularly limited, and examples thereof include an n-propoxy group, an i-propoxy group, an n-butoxy group, and a sec-butoxy group. Tert-butoxy group, i-butoxy group, n-hexyloxy group, cyclohexyloxy group, cyclohexadienyloxy group, octyloxy group, tetrahydrofuranyloxy group, trifluoromethoxy group, benzyloxy group, phenethyloxy group, etc. Can be mentioned. Of these, a methoxy group, an ethoxy group, or an n-butoxy group is preferable.

In the general formulas (1) and (2), R ^{1 to} R ⁴ are the same or different and represent a hydrogen atom or an organic group, and adjacent substituents of R ^{1 to} R ⁴ are bonded to each other to form a substituent. A monocyclic or polycyclic condensed aromatic ring which may have a ring may be formed. When adjacent substituents of R ^{1 to} R ⁴ are bonded to each other to form an aromatic ring, the aromatic ring is a monocyclic, bicyclic condensed ring, or tricyclic condensed ring optionally having a substituent. An aromatic ring is preferred.

The organic group in R ¹ to R ^4, is not particularly limited, for example, monocyclic expressed by X ¹ and X ^2, 2 fused ring, or 3 substituted on the aromatic ring of the fused ring Examples of the same optional substituents may be exemplified, and the same applies to the preferred range. That is, the organic group in R ^{1 to} R ⁴ is not particularly limited, but for example, a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, or having 3 to 36 carbon atoms. Monocyclic, linked, or condensed heteroaromatic groups (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a straight chain having 3 to 18 carbon atoms, cyclic, Or may have one or more substituents selected from the group consisting of branched alkyl groups, methoxy groups, ethoxy groups, and linear, cyclic, or branched alkoxy groups having 3 to 18 carbon atoms), hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight chain of 3 to 18 carbon atoms , Cyclic or branched alkyl groups Methoxy group, an ethoxy group, or a straight-chain having 3 to 18 carbon atoms, cyclic, or the like branched alkoxy groups.

In the general formulas (1) and (2), the adjacent substituents of R ^{1 to} R ⁴ are bonded to each other to form a monocyclic or polycyclic condensed aromatic ring which may have a substituent. It may be formed.
The aromatic ring of the monocyclic or polycyclic condensed ring which may have the substituent is not particularly limited, but for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, pyridine Ring, quinoline ring, isoquinoline ring, phenanthroline ring, imidazole ring, benzimidazole ring, carbazole ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furan ring, benzofuran ring, dibenzofuran ring, etc. Or a condensed tricyclic aromatic ring; a polyphenylene condensed aromatic ring having four or more rings such as a triphenylene ring, a pyrene ring, a benzo [g] chrysene ring, and a dibenzo [g, p] chrysene ring.

  That is, the general formula (1) in the present invention is preferably the following general formula (1 '), and the general formula (2) is preferably the following general formula (2').

(Where
X ¹ and X ² are the same or different and represent a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring which may have a substituent.
Y ¹ and Y ² are the same or different and represent a monocyclic or polycyclic condensed aromatic ring which may have a substituent.
Aromatic ring represented by the aromatic ring and X ² represented by X ¹ may not be bonded may be bonded at least one binding.
The aromatic ring represented by Y ¹ and the aromatic ring represented by Y ² may or may not be bonded by at least one bond.
The aromatic ring represented by X ¹ and the aromatic ring represented by Y ¹ may or may not be bonded with at least one bond.
The aromatic ring represented by X ² and the aromatic ring represented by Y ² may or may not be bonded by at least one bond. )

(Where
X ¹ and X ² are the same or different and represent a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring which may have a substituent.
Y ¹ and Y ² are the same or different and represent a monocyclic or polycyclic condensed aromatic ring which may have a substituent.
Aromatic ring represented by the aromatic ring and X ² represented by X ¹ are not bonded.
The aromatic ring represented by Y ¹ and the aromatic ring represented by Y ² may or may not be bonded by at least one bond.
Aromatic ring represented by the aromatic ring and Y ¹ represented by X ¹ are not bonded.
The aromatic ring represented by X ² and the aromatic ring represented by Y ² are not bonded. )

The aromatic ring of monocyclic or polycyclic condensed ring which may have a substituent in Y ¹ and Y ² is not particularly limited, but in the general formulas (1) and (2), R ¹ to R ⁴ form, which may have a substituent monocyclic or same can be exemplified as the condensed polycyclic aromatic ring, the same applies to the preferred ranges.

X ¹ , X ² , Y ¹ , and Y ² represented by the above general formulas (1), (1 ′), (2), and (2 ′) are none from the viewpoint of easy availability of raw materials. It is preferably a substituted monocyclic, bi-condensed or tri-fused aromatic ring, more preferably an unsubstituted monocyclic or bi-condensed aromatic ring, and an unsubstituted monocyclic aromatic ring More preferably.

The aromatic rings represented by X ¹ and X ² in the general formulas (1), (1 ′), (2), and (2 ′) are not particularly limited, but availability of raw materials and intramolecular rings In order to achieve high reaction selectivity in the chemical reaction, they are the same or different and are preferably the following general formulas (3) to (16), more preferably general formula (3).

In addition, the aromatic rings represented by X ¹ , X ² , and Y ¹ in the general formulas (1), (1 ′), (2), and (2 ′) are the same or different. Formulas (3) to (16) are more preferable, and general formula (3) is more preferable.

Furthermore, the aromatic rings represented by X ¹ , X ² , Y ¹ , and Y ² in the general formulas (1), (1 ′), (2), and (2 ′) are the same or different, The following general formulas (3) to (16) are more preferable, and the general formula (3) is more preferable.

(Wherein R ^{5 to} R ⁸ are the same or different, and each represents a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic or linked group having 3 to 36 carbon atoms, Or a condensed heteroaromatic group (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms) , A methoxy group, an ethoxy group, and one or more substituents selected from the group consisting of a linear, cyclic, or branched alkoxy group having 3 to 18 carbon atoms), hydrogen atom, deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight chain of 3 to 18 carbon atoms, cyclic, or branched Alkyl group, methoxy group, ethoxy group, or Linear prime 3-18, cyclic, or represents a branched alkoxy group, adjacent substituents may be bonded to each other to form a ring.)

Monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms, carbon number in R ^{5 to} R ⁸ The linear, cyclic or branched alkyl group having 3 to 18 and the linear, cyclic or branched alkoxy group having 3 to 18 carbon atoms are not particularly limited, but in X ¹ and X ² , A monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms, a straight chain having 3 to 18 carbon atoms, The same thing as a cyclic | annular or branched alkyl group and a C3-C18 linear, cyclic | annular, or branched alkoxy group can be illustrated, and its preferable range is also the same.

Although it does not specifically limit as R < ⁵ > -R < ⁸ >, For example, a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group (- NH _2), methyl group, ethyl group, n- butyl group, tert- butyl group, n- hexyl group, an octyl group, a trifluoromethyl group, a methoxy group, an ethoxy group, n- butoxy group, a phenyl group, 4-methyl Phenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6 -Dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 4-biphenyl group, -Biphenyl group, 2-biphenyl group, 2-methyl-1,1'-biphenyl-4-yl group, 3-methyl-1,1'-biphenyl-4-yl group, 2'-methyl-1,1 ' -Biphenyl-4-yl group, 3'-methyl-1,1'-biphenyl-4-yl group, 4'-methyl-1,1'-biphenyl-4-yl group, 2,6-dimethyl-1, 1′-biphenyl-4-yl group, 2,2′-dimethyl-1,1′-biphenyl-4-yl group, 2,3′-dimethyl-1,1′-biphenyl-4-yl group, 2, 4′-dimethyl-1,1′-biphenyl-4-yl group, 3,2′-dimethyl-1,1′-biphenyl-4-yl group, 2 ′, 3′-dimethyl-1,1′-biphenyl -4-yl group, 2 ′, 4′-dimethyl-1,1′-biphenyl-4-yl group, 2 ′, 5′-dimethyl-1,1′-biphenyl-4-y Group, 2 ′, 6′-dimethyl-1,1′-biphenyl-4-yl group, 4-phenylbiphenyl group, 2-phenylbiphenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalene-1 -Yl group, 4-methylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 4- (1-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- (1-naphthyl) ) Phenyl group, 3- (2-naphthyl) phenyl group, 3-methyl-4- (1-naphthyl) phenyl group, 3-methyl-4- (2-naphthyl) phenyl group, 4- (2-methylnaphthalene- 1-yl) phenyl group, 3- (2-methylnaphthalen-1-yl) phenyl group, 4-phenylnaphthalen-1-yl group, 4- (2-methylphenyl) naphthalen-1-yl group, 4- ( 3-methylfe ) Naphthalen-1-yl group, 4- (4-methylphenyl) naphthalen-1-yl group, 6-phenylnaphthalen-2-yl group, 4- (2-methylphenyl) naphthalen-2-yl group, 4 -(3-methylphenyl) naphthalen-2-yl group, 4- (4-methylphenyl) naphthalen-2-yl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9'- Spirobifluorenyl group, 9-phenanthryl group, 2-phenanthryl group, 11,11′-dimethylbenzo [a] fluoren-9-yl group, 11,11′-dimethylbenzo [a] fluoren-3-yl group 11,11′-dimethylbenzo [b] fluoren-9-yl group, 11,11′-dimethylbenzo [b] fluoren-3-yl group, 11,11′-dimethylbenzo [c] fluore N-9-yl group, 11,11′-dimethylbenzo [c] fluoren-2-yl group, 3-fluoranthenyl group, 8-fluoranthenyl group, 1-imidazolyl group, 2-phenyl-1-imidazolyl A group, 2-phenyl-3,4-dimethyl-1-imidazolyl group, 2,3,4-triphenyl-1-imidazolyl group, 2- (2-naphthyl) -3,4-dimethyl-1-imidazolyl group, 2- (2-naphthyl) -3,4-diphenyl-1-imidazolyl group, 1-methyl-2-imidazolyl group, 1-ethyl-2-imidazolyl group, 1-phenyl-2-imidazolyl group, 1-methyl- 4-phenyl-2-imidazolyl group, 1-methyl-4,5-dimethyl-2-imidazolyl group, 1-methyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl-4,5-dimethyl Tyl-2-imidazolyl group, 1-phenyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl-4,5-dibiphenylyl-2-imidazolyl group, 1-methyl-3-pyrazolyl group, 1-phenyl- 3-pyrazolyl group, 1-methyl-4-pyrazolyl group, 1-phenyl-4-pyrazolyl group, 1-methyl-5-pyrazolyl group, 1-phenyl-5-pyrazolyl group, 2-thiazolyl group, 4-thiazolyl group 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group 2-pyridyl group, 3-methyl-2-pyridyl group, 4-methyl-2-pyridyl group, 5-methyl-2-pyridyl group Dil group, 6-methyl-2-pyridyl group, 3-pyridyl group, 4-methyl-3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 2,2′-bipyridin-3-yl group, 2, 2'-bipyridin-4-yl group, 2,2'-bipyridin-5-yl group, 2,3'-bipyridin-3-yl group, 2,3'-bipyridin-4-yl group, 2,3 ' -Bipyridin-5-yl group, 5-pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 4,6-diphenyl-1,3,5-triazin-2-yl group, 1-benzoimidazolyl group, 2 -Methyl-1-benzimidazolyl group, 2-phenyl-1-benzimidazolyl group, 1-methyl-2-benzoimidazolyl group, 1-phenyl-2-benzimidazolyl group, 1-methyl-5-benzimidazolyl group, 1,2-dimethyl- 5- Nzoimidazolyl group, 1-methyl-2-phenyl-5-benzimidazolyl group, 1-phenyl-5-benzoimidazolyl group, 1,2-diphenyl-5-benzimidazolyl group, 1-methyl-6-benzoimidazolyl group, 1,2 -Dimethyl-6-benzimidazolyl group, 1-methyl-2-phenyl-6-benzimidazolyl group, 1-phenyl-6-benzoimidazolyl group, 1,2-diphenyl-6-benzimidazolyl group, 1-methyl-3-indazolyl group, 1-phenyl-3-indazolyl group, 2-benzothiazolyl group, 4-benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, 3-benzoisothiazolyl group, 4-benzoisothiazolyl group, 5-benzoisothiazolyl group, 6-benzoisothia Zolyl group, 7-benzoisothiazolyl group, 2,1,3-benzothiadiazol-4-yl group, 2,1,3-benzothiadiazol-5-yl group, 2-benzoxazolyl group, 4-benzo Oxazolyl group, 5-benzoxazolyl group, 6-benzoxazolyl group, 7-benzoxazolyl group, 3-benzisoxazolyl group, 4-benzoisoxazolyl group, 5-benzo Isoxazolyl group, 6-benzoisoxazolyl group, 7-benzisoxazolyl group, 2,1,3-benzooxadiazolyl-4-yl group, 2,1,3-benzooxadiazolyl -5-yl group, 2-quinolyl group, 3-quinolyl group, 5-quinolyl group, 6-quinolyl group, 1-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 2-quinoxalyl group, 3-phenyl- 2 Quinoxalyl group, 6-quinoxalyl group, 2,3-dimethyl-6-quinoxalyl group, 2,3-diphenyl-6-quinoxalyl group, 2-quinazolyl group, 4-quinazolyl group, 2-acridinyl group, 9-acridinyl group, 1,10-phenanthroline-3-yl group, 1,10-phenanthroline-5-yl group, 2-thienyl group, 3-thienyl group, 2-benzothienyl group, 3-benzothienyl group, 2-dibenzothienyl group, 4-dibenzothienyl group, 2-furanyl group, 3-furanyl group, 2-benzofuranyl group, 3-benzofuranyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 9-methylcarbazol-2-yl group, 9-methylcarbazol-3-yl group, 9-methylcarbazol-4-yl group, 9-phenylcarbazol-2-yl group, -Phenylcarbazol-3-yl group, 9-phenylcarbazol-4-yl group, 9-biphenylcarbazol-2-yl group, 9-biphenylcarbazol-3-yl group, 9-biphenylcarbazol-4-yl group, 2 -Thianthryl group, 10-phenylphenothiazin-3-yl group, 10-phenylphenothiazin-2-yl group, 10-phenylphenoxazin-3-yl group, 10-phenylphenoxazin-2-yl group, 1-methylindole 2-yl group, 1-phenylindol-2-yl group, 9-phenylcarbazol-4-yl group, 1-methylindol-2-yl group, 1-phenylindol-2-yl group, 4- (2 -Pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 4- (4-pyridyl) phenyl group, 3- (2- Pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 3- (4-pyridyl) phenyl group, 4- (2-phenylimidazol-1-yl) phenyl group, 4- (1-phenylimidazole-2- Yl) phenyl group, 4- (2,3,4-triphenylimidazol-1-yl) phenyl group, 4- (1-methyl-4,5-diphenylimidazol-2-yl) phenyl group, 4- (2 -Methylbenzimidazol-1-yl) phenyl group, 4- (2-phenylbenzimidazol-1-yl) phenyl group, 4- (1-methylbenzimidazol-2-yl) phenyl group, 4- (2-phenyl) Benzimidazol-1-yl) phenyl group, 3- (2-methylbenzimidazol-1-yl) phenyl group, 3- (2-phenylbenzimidazole-1) Yl) phenyl group, 3- (1-methylbenzimidazol-2-yl) phenyl group, 3- (2-phenylbenzimidazol-1-yl) phenyl group, 4- (3,5-diphenyltriazin-1-yl) ) Phenyl group, 4- (2-thienyl) phenyl group, 4- (2-furanyl) phenyl group, 5-phenylthiophen-2-yl group, 5-phenylfuran-2-yl group, 4- (5-phenyl) Thiophen-2-yl) phenyl group, 4- (5-phenylfuran-2-yl) phenyl group, 3- (5-phenylthiophen-2-yl) phenyl group, 3- (5-phenylfuran-2-yl) ) Phenyl group, 4- (2-benzothienyl) phenyl group, 4- (3-benzothienyl) phenyl group, 3- (2-benzothienyl) phenyl group, 3- (3-benzothienyl) Phenyl group, 4- (2-dibenzothienyl) phenyl group, 4- (4-dibenzothienyl) phenyl group, 3- (2-dibenzothienyl) phenyl group, 3- (4-dibenzothienyl) phenyl group, 4- ( 2-dibenzofuranyl) phenyl group, 4- (4-dibenzofuranyl) phenyl group, 3- (2-dibenzofuranyl) phenyl group, 3- (4-dibenzofuranyl) phenyl group, 5-phenylpyridine- Illustrate 2-yl group, 4-phenylpyridin-2-yl group, 5-phenylpyridin-3-yl group, 4- (9-carbazolyl) phenyl group, 3- (9-carbazolyl) phenyl group, etc. However, it is not limited to these.

Regarding R ^{5 to} R ⁸ represented by the general formula (3), adjacent substituents may be bonded to each other to form a ring. The ring formed at this time is not particularly limited, and examples thereof include a monocyclic or polycyclic condensed aromatic ring which may have a substituent. The optionally substituted monocyclic, or the aromatic ring of the condensed polycyclic, is not particularly limited, for example, in the general formula (1) and (2), R ¹ to R ⁴ The same thing as the aromatic ring of the monocyclic or polycyclic condensed ring which may have a substituent which forms may be illustrated, and the same applies to the preferred range.

  Although the manufacturing method of this invention is not specifically limited, For example, it is preferable to perform the intramolecular cyclization reaction represented by either of following formula (17)-(29).

(Where
Y ¹ and Y ² are the same or different and represent a monocyclic or polycyclic condensed aromatic ring which may have a substituent.
The aromatic ring represented by Y ¹ and the aromatic ring represented by Y ² may or may not be bonded by at least one bond.
A ^{1 to} A ⁶ are the same or different and each represents a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic, linked or condensed ring having 3 to 36 carbon atoms. A heteroaromatic group (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, a methoxy group, (It may have one or more substituents selected from the group consisting of an ethoxy group and a linear, cyclic, or branched alkoxy group having 3 to 18 carbon atoms), a hydrogen atom, a deuterium atom, a fluorine atom , a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight-chain, cyclic, or branched alkyl group having 3 to 18 carbon atoms, Methoxy group, ethoxy group, or carbon number 3 18 linear, an alkoxy group of cyclic, or branched.
k ¹ , k ² , k ⁵ , and k ⁶ are the same or different and are integers of 0 to 4.
k ³ and ^{k 4} are the same or different, it is an integer of 0-2. )

The definition of each substituent in formulas (17) to (29) is as described above, and the same applies to the preferred range.
That is, in Formulas (17) to (29), the monocyclic or polycyclic condensed aromatic ring which may have a substituent in Y ¹ and Y ² is not particularly limited, In the formulas (1) and (2), the same monocyclic or polycyclic aromatic ring that may have a substituent formed by R ^{1 to} R ⁴ can be exemplified, and is preferable. The same applies to the range. In formulas (17) to (29), a monocyclic ring having 6 to 30 carbon atoms in A ^{1 to} A ⁶ , a linked or condensed aromatic hydrocarbon group, a monocyclic ring having 3 to 36 carbon atoms, a linkage, Or, a condensed heteroaromatic group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, and a linear, cyclic or branched alkoxy group having 3 to 18 carbon atoms are particularly limited. However, in X ¹ and X ² , a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms Examples thereof are the same as the group, linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, and linear, cyclic or branched alkoxy group having 3 to 18 carbon atoms. It is the same.

  Although the manufacturing method of this invention is not specifically limited, For example, it is preferable to perform the intramolecular cyclization reaction represented by either of following formula (30)-(151).

(Where
Y ² represents a monocyclic or polycyclic condensed aromatic ring which may have a substituent.
A ^{1 to} A ⁶ and B ^{1 to} B ⁵ are the same or different and are each a monocyclic ring having 6 to 30 carbon atoms, a linked or condensed aromatic hydrocarbon group, a monocyclic ring having 3 to 36 carbon atoms, Linked or condensed heteroaromatic group (These groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched group having 3 to 18 carbon atoms. One or more substituents selected from the group consisting of an alkyl group, a methoxy group, an ethoxy group, and a linear, cyclic, or branched alkoxy group having 3 to 18 carbon atoms), a hydrogen atom, deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight chain of 3 to 18 carbon atoms, cyclic, Or branched alkyl group, methoxy group, ethoxy , Or represents a straight-chain, cyclic, or branched alkoxy group having a carbon number of 3 to 18.
k ¹ , k ² , k ⁵ , and k ⁶ are the same or different and are integers from 0 to 4.
k ³ and ^{k 4} are the same or different and are an integer of 0 to 2.
m ¹ and m ³ are the same or different and are integers of 0 to 4.
m ² and ^{m 4} are different or the same or an integer of 0-2.
m ⁵ is an integer of 0 to 3. )

The definition of each substituent in formulas (30) to (151) is as described above, and the same applies to the preferred range.
That is, in Formulas (30) to (151), the monocyclic or polycyclic aromatic ring that may have a substituent in Y ² is not particularly limited, but is represented by General Formula (1) ) And (2), the same ring as the monocyclic or polycyclic condensed ring which may have a substituent formed by R ^{1 to} R ⁴ can be exemplified. It is the same. In formulas (30) to (151), a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms in A ^{1 to} A ⁶ and B ^{1 to} B ^5, C ^{3 to} 36 A monocyclic, linked, or condensed heteroaromatic group, a linear, cyclic, or branched alkyl group having 3 to 18 carbon atoms, and a linear, cyclic, or branched alkoxy group having 3 to 18 carbon atoms Is not particularly limited, and X ¹ and X ² are a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic, linked, or 3 to 36 carbon atoms. Examples are the same as the condensed heteroaromatic group, linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, and linear, cyclic or branched alkoxy group having 3 to 18 carbon atoms. The same applies to the preferred range.

The condensed ring compounds represented by the general formulas (1) and (1 ′) are useful in applications of electronic materials, particularly organic semiconductors that require charge transportability. According to one embodiment of the present invention, a condensed ring compound having high yield and high purity and excellent charge transportability can be produced.
The condensed ring compound represented by the general formulas (1) and (1 ′) is a condensed ring compound represented by the following formulas (152) to (156) from the viewpoint of excellent usability as an electronic material. Is preferred.

(Where
Z ¹ represents a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a thiol group, a cyano group, or an amino group.
A ^{1 to} A ⁸ are the same or different and each represents a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic, linked or condensed ring having 3 to 36 carbon atoms. Heteroaromatic groups (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, and a methoxy group) , An ethoxy group, one or more substituents selected from the group consisting of linear, cyclic or branched alkoxy groups having 3 to 18 carbon atoms), hydrogen atom, deuterium atom, fluorine atom , a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight-chain, cyclic, or branched alkyl group having 3 to 18 carbon atoms, Methoxy group, ethoxy group, or carbon number 3 18 linear, cyclic, or represents a branched alkoxy group, adjacent substituents may may form a ring together.
k ¹ , k ² , k ⁵ , and k ⁶ are the same or different and are each an integer of 0 to 4.
k ³ and k ⁴ are the same or different and are each an integer of 0 to 2.
k ⁷ and k ⁸ are the same or different and each is an integer of 0 to 3.
n ¹ is an integer of 1 to 4. )

The definitions and preferred ranges of the substituents in formulas (152) to (156) are the same as described above.
That is, in formulas (152) to (156), a monocyclic ring having 6 to 30 carbon atoms in A ^{1 to} A ⁸ , a linked or condensed aromatic hydrocarbon group, a monocyclic ring having 3 to 36 carbon atoms, a linkage, Or, a condensed heteroaromatic group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, and a linear, cyclic or branched alkoxy group having 3 to 18 carbon atoms are particularly limited. However, in X ¹ and X ² , a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms Examples thereof are the same as the group, linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, and linear, cyclic or branched alkoxy group having 3 to 18 carbon atoms. It is the same.

  Hereinafter, preferred examples of the condensed ring compounds represented by the general formulas (1) and (1 ′) are illustrated, but the present invention is not limited to these compounds.

  Furthermore, although the preferable compound is illustrated about the compound represented by the said General formula (2) and (2 '), this invention is not limited to these compounds.

  The compound (C1) is synthesized by intramolecular cyclization of the compound (D1). Compounds (D2) to (D60) are also cyclized intramolecularly to synthesize compounds (C2) to (C60), respectively.

  The compounds represented by the general formulas (2) and (2 ') can be synthesized by known compounds and known cross-coupling reactions. Furthermore, the compounds represented by the general formulas (1) and (1 ') can be obtained by intramolecular cyclization of the compounds represented by the general formulas (2) and (2'). These reactions are represented by the following route, for example.

  A compound represented by the general formula (159) is reacted with a compound represented by the general formula (158) in the presence of a palladium catalyst using a base as necessary. Get. Furthermore, the compound represented by the general formula (160) is obtained by intramolecular cyclization of the obtained compound represented by the general formula (159).

  (In the formula, A and B are different and each represents an optionally substituted boron atom or a halogen atom (chlorine, bromine, or iodine). For groups other than A and B, the general formula (1) or ( It is synonymous with the group in 2).)

  The compounds represented by the general formulas (157) and (158) can be synthesized based on a generally known method, or commercially available compounds can also be used.

  The method for intramolecular cyclization of the compound represented by the general formula (2) is not particularly limited, and examples thereof include oxidation by an oxidizing agent or oxidation by light irradiation.

As the oxidizing agent used for the oxidation by the oxidizing agent, known ones (for example, those described in Journal of Organic Chemistry 2007, 72, 2279.) can be used, and are not particularly limited. Ferric chloride (FeCl ₃ ), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), molybdenum chloride (MoCl ₅ ), aluminum chloride (AlCl ₃ ), or [bis (trifluoroacetoxy) Iodo] benzene (PIFA) is preferred, and ferric chloride (FeCl ₃ ) or molybdenum chloride (MoCl ₅ ) is more preferred.

  The reaction solvent used for the oxidation with the oxidizing agent is not particularly limited. For example, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, orthodichlorobenzene, benzene, toluene, orthoxylene, Examples include meta-xylene, para-xylene, acetone, pentane, hexane, heptane, octane, nonane, decane, cyclohexane, ethyl acetate, N, N-dimethylformamide, N-methylpyrrolidone, 1,4-dioxane, and tetrahydrofuran. Among these, from the viewpoint of suppressing the generation of impurities, dichloromethane, chloroform, carbon tetrachloride, or 1,2-dichloroethane is preferable, and dichloromethane or chloroform is more preferable. Moreover, when using the said solvent, you may add a different solvent in order to dissolve an oxidizing agent. Although it does not specifically limit as a solvent to add, For example, nitromethane etc. are mentioned. In order to maintain the activity of the oxidizing agent, these are preferably dehydrating solvents.

  Although it does not specifically limit as reaction temperature at the time of oxidizing with the said oxidizing agent, From a viewpoint of suppressing generation | occurrence | production of an impurity, it is preferable that it is -78-50 degreeC, and -78 degreeC-25 degreeC is more preferable.

  Although it does not specifically limit as reaction atmosphere at the time of performing the oxidation by the said oxidizing agent, From a viewpoint of suppressing generation | occurrence | production of an impurity, it is preferable that it is dry nitrogen or dry argon atmosphere.

  Although it does not specifically limit as pH at the time of oxidizing with the said oxidizing agent, From a viewpoint of making an oxidation reaction advance efficiently, it is preferable that it is pH 7 or less.

  When performing the oxidation with the oxidizing agent, further additives may be used as necessary from the viewpoint of suppressing the generation of impurities. For example, a zeolite (molecular sieve) for removing water in the reaction system, a metal scavenger for supplementing impurity metals in the reaction system, and the like can be mentioned.

  Although it does not specifically limit as a wavelength of the light irradiated when oxidizing by light irradiation, In order to advance cyclization efficiently, the wavelength of ultraviolet light-visible light is preferable, and the wavelength of 200 nm-400 nm is more preferable.

Moreover, you may use an additive as needed in order to accelerate | stimulate the oxidative cyclization reaction by the said light irradiation. The additives are not particularly limited, iodine _{(I 2)} and 1,2-epoxypropane or 1,2-epoxy butane are preferred.

  As the reaction solvent used in the oxidation by the light irradiation, the same solvent as described above can be used. From the viewpoint of suppressing the generation of impurities, acetone, pentane, hexane, heptane, octane, nonane, decane, Cyclohexane, benzene, or toluene is preferable, and acetone, pentane, hexane, or benzene is more preferable.

  The reaction temperature at the time of oxidation by light irradiation is not particularly limited, but from the viewpoint of safety, it is preferable to cool the reaction temperature to be equal to or lower than the boiling point of the solvent to be used.

  The reaction atmosphere for the oxidation by the light irradiation is not particularly limited, but is preferably a nitrogen or argon atmosphere from the viewpoint of suppressing the generation of impurities.

  The pH at the time of oxidation by light irradiation is not particularly limited, but when the substrate to be used has a chlorine atom, hydrogen chloride may be generated during the reaction. May be added.

  The production method of the present invention may be used step by step at different positions within the same molecule, if necessary. For example, the compounds represented by the general formulas (G1) to (G4) can provide a condensed ring compound that has undergone two-stage intramolecular cyclization by using the production method of the present invention twice.

(In the formulas (G1) to (G4),
A ^{1 to} A ⁶ are the same or different and each represents a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic, linked or condensed ring having 3 to 36 carbon atoms. A heteroaromatic group (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, a methoxy group, (It may have one or more substituents selected from the group consisting of an ethoxy group and a linear, cyclic, or branched alkoxy group having 3 to 18 carbon atoms), a hydrogen atom, a deuterium atom, a fluorine atom , a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight-chain, cyclic, or branched alkyl group having 3 to 18 carbon atoms, Methoxy group, ethoxy group, or carbon number 3 18 linear, an alkoxy group of cyclic, or branched.
In formulas (G1) to (G4), k ^{1 to} k ⁴ are the same or different and each is an integer of 0 to 4.
In formulas (G1) and (G2), k ⁵ and k ⁶ are the same or different and each is an integer of 0 to 3.
In formulas (G3) and (G4), k ⁵ and k ⁶ are the same or different and each is an integer of 0 to 4. )

  Moreover, you may use the manufacturing method of this invention as an intermediate reaction of the final condensed ring compound. For example, a continuous molecular cyclization reaction is performed on the compounds represented by the general formulas (G5) and (G6) produced in the present invention, and the compounds represented by the general formulas (G7) and (G8), respectively. Can be provided.

(Where
Z ¹ represents a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a thiol group, a cyano group, or an amino group (—NH ₂ ).
A ^{1 to} A ⁴ are the same or different and are each a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic, linked or condensed ring having 3 to 36 carbon atoms. A heteroaromatic group (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, a methoxy group, (It may have one or more substituents selected from the group consisting of an ethoxy group and a linear, cyclic, or branched alkoxy group having 3 to 18 carbon atoms), a hydrogen atom, a deuterium atom, a fluorine atom , a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight-chain, cyclic, or branched alkyl group having 3 to 18 carbon atoms, Methoxy group, ethoxy group, or carbon number 3 18 linear, an alkoxy group of cyclic, or branched.
k ^{1 to} k ⁴ are the same or different and each is an integer of 0 to 4.
k ⁷ is an integer of 1 to 4.
k ⁸ is an integer of 0 to 2. )

(Where
Z ¹ represents a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a thiol group, a cyano group, or an amino group.
A ^{1 to} A ⁴ are the same or different and are each a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic, linked or condensed ring having 3 to 36 carbon atoms. A heteroaromatic group (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, a methoxy group, (It may have one or more substituents selected from the group consisting of an ethoxy group and a linear, cyclic, or branched alkoxy group having 3 to 18 carbon atoms), a hydrogen atom, a deuterium atom, a fluorine atom , a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight-chain, cyclic, or branched alkyl group having 3 to 18 carbon atoms, Methoxy group, ethoxy group, or carbon number 3 18 linear, an alkoxy group of cyclic, or branched.
k ^{1 to} k ² are the same or different and each is an integer of 0 to 4.
k ⁵ and k ⁶ are the same or different and each is an integer of 0 to 3.
k ⁷ is an integer of 1 to 4.
k ⁸ is an integer of 0 to 2. )

  Examples of the general formula (G7) include preferable compounds, but the present invention is not limited to these compounds.

  Examples of the general formula (G8) include preferable compounds, but the present invention is not limited to these compounds.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a condensed ring compound with a high yield and few impurity production amounts can be provided.
According to the method for producing a fused ring compound of the present invention, it is possible to reduce the environmental burden, reduce waste, or reduce waste processing, thereby enabling industrial use of a compound that has been difficult in the past. it can.
In the method for producing a condensed ring compound according to the present invention, an aromatic ring having 3 or more condensed rings, which may have a substituent constituted by including X ¹ and X ² shown in the general formula (2), By performing intramolecular cyclization, the condensed ring compound represented by the general formula (1) can be created with high yield and high purity. Furthermore, by using this production method, it is possible to create a novel condensed ring compound that has never been seen before, or various condensed ring compounds having a substituent at a position difficult in the past.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples at all, and is interpreted.

  The analytical instruments and measurement methods used in this example are listed below.

[Material purity measurement (HPLC analysis)]
Measuring device: Tosoh Multi Station LC-8020
Measurement conditions: Column Inertsil ODS-3V (4.6 mmΦ × 250 mm)
Detector UV detection (wavelength 254nm)
Eluent acetonitrile / tetrahydrofuran = 8/2 (v / v ratio)

[NMR measurement]
Measuring device: Gemini200 manufactured by Varian
[Mass spectrometry]
Mass spectrometer: M-80B manufactured by Hitachi, Ltd.
Measuring method: FD-MS analysis

  Synthesis Example 1 Synthesis of 9- (3-chlorobiphenyl-6-yl) -phenanthrene

  In a 1000 mL three-necked flask under nitrogen flow, 50.0 g (158 mmol) of 2-bromo-4-chloro-iodobenzene, 21.2 g (174 mmol) of phenylboronic acid, tetrakis (triphenylphosphine) palladium (0) 83 g (1.58 mmol), 1,4-dioxane 150 mL, 2 M potassium carbonate aqueous solution 150 mL was added, and the mixture was stirred at 110 ° C. for 5 days. After cooling to room temperature, 200 mL of pure water and 200 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain 57 g of a pale yellow liquid containing 2-bromo-4-chlorobiphenyl. The total amount of the obtained liquid was transferred to a 300 mL two-necked flask under a nitrogen stream, and 34.6 g (156 mmol) of 9-phenanthreneboronic acid, 1.8 g (1.56 mmol) of tetrakis (triphenylphosphine) palladium (0), 80 mL of tetrahydrofuran and 80 mL of 2M potassium carbonate aqueous solution were added, and the mixture was stirred at 105 ° C. for 4 days. After cooling to room temperature, 200 mL of pure water and 100 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Hexane was added to the residue, and the precipitated powder was collected by filtration, and then the obtained powder was recrystallized (acetone) to obtain a pale yellow powder of 9- (3-chlorobiphenyl-6-yl) -phenanthrene. 0.9 g (51.8 mmol) was isolated (yield 33%, HPLC purity 94.7%).

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.67 (d, 1H), 8.65 (d, 1H), 7.76 (m, 1H), 7.65-7.42 (m, 9H), 7 .12-7.10 (m, 2H), 6.98-6.97 (m, 3H)

  Example 1 Synthesis of 2-chlorodibenzo [g, p] chrysene

Under a nitrogen stream, 10.95 g (30.0 mmol) of 9- (3-chlorobiphenyl-6-yl) -phenanthrene and 150 mL of chloroform were added to a 300 mL two-necked eggplant flask. This solution was cooled to 0 ° C. while stirring, 70 mL of a separately prepared 3M ferric chloride (FeCl ₃ ) / nitromethane solution was added, and the mixture was stirred at 0 ° C. for 15 minutes. To the reaction solution, 20 mL of methanol, 150 mL of pure water, and 50 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. By recrystallizing the residue (chloroform / methanol), 10.29 g (28.4 mmol) of 2-chlorodibenzo [g, p] chrysene pale yellow powder was isolated (yield 94%, HPLC purity 92.0). %).

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.73-8.62 (m, 8H), 7.73-7.62 (m, 7H)

  Example 2 Synthesis of 2-chlorodibenzo [g, p] chrysene

窒素気流下、２０ｍＬの二口ナスフラスコに、９−（３−クロロビフェニル−６−イル）−フェナントレン ３６５ｍｇ（１．００ｍｍｏｌ）、クロロホルム ２ｍＬ、及びニトロメタン ０．５ｍＬを加えた。この溶液を撹拌しながら０℃に冷却し、塩化モリブデン（ＭｏＣｌ_５） ４９２ｍｇ（１．８０ｍｍｏｌ）を加え、室温に昇温しながら１７時間撹拌した。反応溶液にメタノールを２０ｍＬ、純水を１５０ｍＬ、クロロホルムを５０ｍＬ添加し攪拌した。水層と有機層を分液し、得られた有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をＨＰＬＣで分析した結果、２−クロロジベンゾ［ｇ，ｐ］クリセンがＨＰＬＣ純度で８７％含まれていた。

Under a nitrogen stream, 365 mg (1.00 mmol) of 9- (3-chlorobiphenyl-6-yl) -phenanthrene, 2 mL of chloroform, and 0.5 mL of nitromethane were added to a 20 mL two-necked eggplant flask. This solution was cooled to 0 ° C. with stirring, 492 mg (1.80 mmol) of molybdenum chloride (MoCl ₅ ) was added, and the mixture was stirred for 17 hours while warming to room temperature. To the reaction solution, 20 mL of methanol, 150 mL of pure water, and 50 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. As a result of analyzing the residue by HPLC, 87% of 2-chlorodibenzo [g, p] chrysene was contained in HPLC purity.

  Synthesis Example 2 Synthesis of 9- [2-bromo- (4-chloro) -phenyl] -phenanthrene

  In a 20 mL glass container under a nitrogen stream, 12.0 g (37.8 mmol) of 2-bromo-4-chloro-iodobenzene, 8.81 g (39.7 mmol) of 9-phenanthreneboronic acid, tetrakis (triphenylphosphine) 437 mg (0.04 mmol) of palladium (0), 100 mL of tetrahydrofuran, and 40 mL of 2M aqueous potassium carbonate solution were added, and the mixture was stirred at 70 ° C. for 24 hours. After cooling to room temperature, 100 mL of pure water and 100 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was recrystallized (methanol) to isolate 6.54 g (17.8 mmol) of a colorless powder of 9- [2-bromo- (4-chloro) -phenyl] -phenanthrene (yield 47%, HPLC purity). 99.8%).

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.78 (d, 1H), 8.75 (d, 1H), 7.91 (dd, 1H), 7.79 (s, 1H), 7.73-7 .62 (m, 4H), 7.56-7.52 (m, 1H), 7.48-7.43 (m, 2H), 7.44 (d, 1H)

  Synthesis Example 3 Synthesis of 9- (4-chlorobiphenyl-2-yl) -phenanthrene

  Under a nitrogen stream, in a 100 mL two-necked eggplant flask, 5.00 g (13.59 mmol) of 9- [2-bromo- (4-chloro) -phenyl] -phenanthrene and 1.82 g (14.95 mmol) of phenylboronic acid , 157 mg (0.03 mmol) of tetrakis (triphenylphosphine) palladium (0), 20 mL of 1,4-dioxane, and 10 mL of 2M aqueous potassium carbonate solution were added, and the mixture was stirred at 105 ° C. for 18 hours. After cooling to room temperature, 100 mL of pure water and 100 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was recrystallized (chloroform / hexane / methanol) to isolate 3.41 g (9.35 mmol) of 9- (4-chlorobiphenyl-2-yl) -phenanthrene as a pale yellow powder (yield 69%, HPLC purity 99.2%).

The compound was identified by ¹ H-NMR measurement and FDMS.
¹ H-NMR (CDCl ₃ ); 8.67 (d, 1H), 8.66 (d, 1H), 7.76 (dd, 1H), 7.65-7.54 (m, 5H), 7 .50 (s, 1H), 7.47-7.39 (m, 3H), 7.15-7.11 (m, 2H), 7.01-6.96 (m, 3H)
FDMS (m / z); 364 (M +)

  Example 3 Synthesis of 3-chlorodibenzo [g, p] chrysene

窒素気流下、５０ｍＬのシュレンク管に、９−（４−クロロビフェニル−２−イル）−フェナントレン １．８２ｇ（５．００ｍｍｏｌ）、及びクロロホルム １０ｍＬを加えた。この溶液を撹拌しながら０℃に冷却し、別途調整した濃度３Ｍの塩化鉄（ＩＩＩ）／ニトロメタン溶液 １３ｍＬを加え、０℃のまま２時間撹拌した。反応溶液にメタノールを２０ｍＬ、純水を１００ｍＬ、クロロホルムを８０ｍＬ添加し攪拌した。水層と有機層を分液し、得られた有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣を再結晶（クロロホルム／メタノール）することにより、３−クロロジベンゾ［ｇ，ｐ］クリセンの薄黄色粉末を１．６１ｇ（４．４５ｍｍｏｌ）単離した（収率８９％、ＨＰＬＣ純度９４．２％）。

Under a nitrogen stream, 1.82 g (5.00 mmol) of 9- (4-chlorobiphenyl-2-yl) -phenanthrene and 10 mL of chloroform were added to a 50 mL Schlenk tube. The solution was cooled to 0 ° C. while stirring, 13 mL of a separately prepared 3M iron (III) chloride / nitromethane solution having a concentration of 3 M was added, and the mixture was stirred at 0 ° C. for 2 hours. To the reaction solution, 20 mL of methanol, 100 mL of pure water, and 80 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was recrystallized (chloroform / methanol) to isolate 1.61 g (4.45 mmol) of 3-chlorodibenzo [g, p] chrysene as a pale yellow powder (yield 89%, HPLC purity 94.2). %).

The compound was identified by ¹ H-NMR measurement and FDMS.
¹ H-NMR (CDCl ₃ ); 8.72-8.58 (m, 8H), 7.72-7.57 (m, 7H)
FDMS (m / z); 362 (M +)

  Synthesis Example 4 Synthesis of 2,2'-di (9-phenanthryl) biphenyl

窒素気流下、３００ｍＬの二口ナスフラスコに、２，２’−ジブロモビフェニル ５．２２ｇ（１６．７３ｍｍｏｌ）、９−フェナントレンボロン酸 １２．６４ｇ（５６．９２ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（０） ５７８ｍｇ（０．５０ｍｍｏｌ）、テトラヒドロフラン ７０ｍＬ、及び濃度２Ｍの炭酸カリウム水溶液 ２５ｍＬを加え、７０℃で３日間攪拌した。室温まで冷却後、純水を１００ｍＬ、クロロホルムを１００ｍＬ添加し攪拌した。水層と有機層を分液し、得られた有機層を無水硫酸ナトリウムで乾燥後、減圧下で濃縮した。残渣を再結晶（トルエン／メタノール）することで２，２’−ジ（９−フェナントリル）ビフェニルの無色粉末を４．７９ｇ（９．４５ｍｍｏｌ）単離した（収率５６％、ＨＰＬＣ純度９９．７％）。

Under a nitrogen stream, in a 300 mL two-necked eggplant flask, 5.22 g (16.73 mmol) of 2,2′-dibromobiphenyl, 12.64 g (56.92 mmol) of 9-phenanthreneboronic acid, tetrakis (triphenylphosphine) palladium ( 0) 578 mg (0.50 mmol), tetrahydrofuran 70 mL, and 2 M potassium carbonate aqueous solution 25 mL were added, and the mixture was stirred at 70 ° C. for 3 days. After cooling to room temperature, 100 mL of pure water and 100 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was recrystallized (toluene / methanol) to isolate 4.79 g (9.45 mmol) of colorless powder of 2,2′-di (9-phenanthryl) biphenyl (yield 56%, HPLC purity 99.7). %).

The compound was identified by FDMS.
FDMS (m / z); 506 (M +)

  Example 4 Synthesis of Compound (C11)

  Under a nitrogen stream, 256 mg (0.50 mmol) of 2,2′-di (9-phenanthryl) biphenyl and 5 mL of chloroform were added to a 50 mL Schlenk tube. This solution was cooled to 0 ° C. with stirring, 1.25 mL of a separately prepared 4M iron chloride (III) chloride / nitromethane solution was added, and the mixture was stirred at 0 ° C. for 2 hours. By adding 30 mL of methanol to the reaction solution and reprecipitating, 218 mg (0.43 mmol) of a yellow powder of compound (C11) was obtained (yield 87%, HPLC purity 87.5%). The analyzed HPLC chart is shown in FIG.

The compound was identified by ¹ H-NMR measurement and FDMS.
¹ H-NMR (CDCl ₃ ); 9.01 (d, 4H), 8.90 (d, 4H), 8.80 (d, 4H), 8.10 (t, 2H), 7.77-7 .67 (m, 8H)
FDMS (m / z); 502 (M +)

  Comparative Example 1 Synthesis of tetrabenzo [a, fg, j, op] naphthacene

  In the same manner as in Example 4, 407 mg (1.00 mmol) of 2,2′-di (2-naphthyl) biphenyl and 20 mL of chloroform were added to a 100 mL Schlenk tube under a nitrogen stream. The solution was cooled to 0 ° C. with stirring. A separately prepared iron (III) chloride / nitromethane solution having a concentration of 4 M was added, but a total of 6.00 mL was required until the HPLC peak of the raw material disappeared. After stirring for 1 hour at 0 ° C., 30 mL of methanol was added to the reaction solution to cause reprecipitation, and the resulting brown powder was analyzed by HPLC. As a result, tetrabenzo [a, fg, j, op] naphthacene had an HPLC purity of 38. % Was included. The analyzed HPLC chart is shown in FIG. 2, and significantly more impurities-derived peaks were observed as compared with the case of Example 4. This powder was sequentially purified by silica gel column chromatography (chloroform / hexane = 1: 2) and recrystallization (chloroform / methanol), but only 22 mg (0.05 mmol) of tetrabenzo [a, fg, j, op] naphthacene was obtained. (Yield 5%, HPLC purity 98.64%).

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.15 (t, 4H), 8.98 (d, 2H), 8.88 (d, 2H), 8.16-8.08 (m, 6H), 7 .71-7.64 (m, 4H)

  Comparative Example 2 Synthesis of tetrabenzo [a, fg, j, op] naphthacene

  In the same manner as in Example 4, 407 mg (1.00 mmol) of 2,2′-di (1-naphthyl) biphenyl and 20 mL of chloroform were added to a 100 mL Schlenk tube under a nitrogen stream. This solution was cooled to 0 ° C. with stirring, and 2.50 mL of a 4 M iron chloride (III) / nitromethane solution prepared separately was added and stirred at 0 ° C. for 2 hours. Was not consumed, the temperature was raised to room temperature and the mixture was further stirred for 2 hours. 30 mL of methanol was added to the reaction solution for reprecipitation, and the resulting brown powder was analyzed by HPLC, but formation of tetrabenzo [a, fg, j, op] naphthacene could not be confirmed, and the raw material 2,2′- Only di (1-naphthyl) biphenyl was recovered with an HPLC purity of 72%. The analyzed HPLC chart is shown in FIG.

  Synthesis Example 5 Synthesis of 9- [2- (9-phenanthryl) phenyl] -phenanthrene

  Under a nitrogen stream, in a 100 mL two-necked eggplant flask, 8.49 g (30.00 mmol) of 2-bromo-1-iodobenzene, 16.65 g (75.00 mmol) of 9-phenanthreneboronic acid, 67 mg (0.30 mmol) of palladium acetate ), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (Xphos) 286 mg (0.60 mmol), tetrahydrofuran 40 mL, 2 M potassium carbonate aqueous solution 40 mL was added, and the mixture was stirred at 75 ° C. for 3 days. . After cooling to room temperature, 200 mL of methanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol. The residue was recrystallized (toluene / methanol) to isolate 10.15 g (23.40 mmol) of a colorless powder of 9- [2- (9-phenanthryl) phenyl] -phenanthrene (yield 79%, HPLC purity 96 .9%).

The compound was identified by FDMS.
FDMS (m / z); 430 (M +)

  Example 5 Synthesis of dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene

  Under a nitrogen stream, 431 mg (1.00 mmol) of 9- [2- (9-phenanthryl) phenyl] -phenanthrene and 20 mL of chloroform were added to a 50 mL Schlenk tube. This solution was cooled to 0 ° C. with stirring, 4.40 mL of a separately prepared 3M iron (III) chloride / nitromethane solution having a concentration of 3M was added, and the mixture was stirred at 0 ° C. for 20 minutes. 20 mL of methanol was added to the reaction solution, and the precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (toluene / methanol), 232 mg (0.54 mmol) of a yellow powder of dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene was isolated (yield 54%, HPLC purity 95.1%).

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.17 (dd, 2H), 9.03-9.01 (m, 2H), 8.93 (t, 4H), 8.89-8.86 (m, 2H), 8.05 (t, 2H), 7.79-7.72 (m, 6H)

  Synthesis Example 6 Synthesis of 9- [4-chloro-2- (9-phenanthryl)]-phenanthrene

  Under a nitrogen stream, in a 300 mL two-necked eggplant flask, 22.21 g (70.00 mmol) of 2-bromo-4-chloro-1-iodobenzene, 35.75 g (161.0 mmol) of 9-phenanthreneboronic acid, 157 mg of palladium acetate (0.70 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (Xphos) 667 mg (1.40 mmol), tetrahydrofuran 80 mL, and 2 M aqueous potassium carbonate solution 70 mL were added, and 75 ° C. For 24 hours. After cooling to room temperature, 200 mL of methanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol, whereby 9- [4-chloro-2- (9-phenanthryl) -phenyl]- 27.23 g (58.56 mmol) of a colorless powder of phenanthrene was isolated (yield 84%, HPLC purity 94.7%).

The compound was identified by FDMS.
FDMS (m / z); 464 (M +)

  Example 6 Synthesis of Compound (C22) and Compound (F1)

  Under a nitrogen stream, 353 mg (0.76 mmol) of 9- [4-chloro-2- (9-phenanthryl) -phenyl] -phenanthrene and 15 mL of chloroform were added to a 50 mL Schlenk tube. This solution was cooled to 0 ° C. with stirring, 2.50 mL of a separately prepared 3M iron (III) chloride / nitromethane solution having a concentration of 3 M was added, and the mixture was stirred at 0 ° C. for 10 minutes. 50 mL of methanol was added to the reaction solution and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol to obtain 213 mg of yellow powder containing Compound (C22) and Compound (F1) at 1: 9. It was.

The compound was identified by FDMS.
FDMS (m / z); Compound (C22) 462 (M +), Compound (F1) 460 (M +)

  Example 7 Synthesis of Compound (F1)

  Under a nitrogen stream, 4.65 g (10.00 mmol) of 9- [4-chloro-2- (9-phenanthryl) -phenyl] -phenanthrene and 150 mL of chloroform were added to a 300 mL two-necked eggplant flask. The solution was cooled to 0 ° C. with stirring, 43.0 mL of a separately prepared 3M iron (III) chloride / nitromethane solution having a concentration of 3M was added, and the mixture was stirred at 0 ° C. for 25 minutes. Methanol (300 mL) was added to the reaction solution, and the precipitated solid was collected by filtration, and washed with pure water and methanol to isolate 3.84 g (8.33 mmol) of the yellow powder of compound (F1) (yield 83). %, HPLC purity 94.1%).

The compound was identified by ¹ H-NMR measurement and FDMS.
¹ H-NMR (DMSO-d ₆ ); 9.24-9.06 (m, 8H), 8.92-8.74 (m, 2H), 8.21-8.16 (m, 2H), 7.92-7.83 (m, 5H)
FDMS (m / z); 460 (M +)

  Synthesis Example 7 Synthesis of 9- [4-chloro-2- (2-naphthyl) -phenyl] -phenanthrene

  Under a nitrogen stream, 20 mL of Schlenk was charged with 368 mg (1.00 mmol) of 9- [2-bromo- (4-chloro) -phenyl] -phenanthrene, 172 mg (1.00 mmol) of 2-naphthaleneboronic acid, tetrakis (triphenyl). 12 mg (0.01 mmol) of phosphine) palladium (0), 2 mL of tetrahydrofuran, and 1 mL of 2M potassium carbonate aqueous solution were added, and the mixture was stirred at 75 ° C. for 24 hours. After cooling to room temperature, 10 mL of pure water and 10 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. 227 mg (0.55 mmol) of a colorless powder of 9- [4-chloro-2- (2-naphthyl) -phenyl] -phenanthrene was isolated by recrystallizing the residue (chloroform / acetonitoryl) (yield 55%, HPLC purity 98.2%).

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.65 (d, 1H), 8.63 (d, 1H), 7.74-7.66 (m, 4H), 7.62-7.42 (m, 9H), 7.37-7.30 (m, 3H), 7.12 (dd, 1H)

  Example 8 Synthesis of Compound (C20) and Compound (E1)

  Under a nitrogen stream, 104 mg (0.25 mmol) of 9- [4-chloro-2- (2-naphthyl) -phenyl] -phenanthrene and 1 mL of chloroform were added to a 50 mL Schlenk tube. The solution was cooled to 0 ° C. with stirring, 0.58 mL of a separately prepared 3M iron (III) chloride / nitromethane solution having a concentration of 3M was added, and the mixture was stirred at 0 ° C. for 1 hour. To the reaction solution, 10 mL of methanol, 10 mL of pure water, and 10 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was recrystallized (chloroform / methanol) to obtain 41 mg of a yellow powder containing 9: 1 of the compound (C20) and the compound (E1).

The compound was identified by FDMS.
FDMS (m / z); Compound (C20) 412 (M +), Compound (E1) 410 (M +)

  Synthesis Example 8 Synthesis of 9- [4-chloro-2- (1-naphthyl) -phenyl] -phenanthrene

  Under a nitrogen stream, 20 mL Schlenk was charged with 9- [2-bromo- (4-chloro) -phenyl] -phenanthrene 2.10 mg (0.57 mmol), 1-naphthaleneboronic acid 133 mg (0.77 mmol), tetrakis (tri 7 mg (0.06 mmol) of phenylphosphine) palladium (0), 2 mL of tetrahydrofuran, and 1 mL of 2M aqueous potassium carbonate solution were added, and the mixture was stirred at 75 ° C. for 2 days. After cooling to room temperature, 30 mL of pure water and 30 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. By recrystallizing the residue (chloroform / methanol), 154 mg (0.37 mmol) of a colorless powder of 9- [4-chloro-2- (1-naphthyl) -phenyl] -phenanthrene was isolated (yield 65%, HPLC purity 97.1%).

The compound was identified by FDMS.
FDMS (m / z); 414 (M +)

  Example 9 Synthesis of Compound (C18)

  Under a nitrogen stream, 100 mg (0.24 mmol) of 9- [4-chloro-2- (1-naphthyl) -phenyl] -phenanthrene and 5 mL of chloroform were added to 50 mL of Schlenk. This solution was cooled to 0 ° C. with stirring, 0.76 mL of a separately prepared 3M iron (III) chloride / nitromethane solution having a concentration of 3 M was added, and the mixture was stirred at 0 ° C. for 20 minutes. To the reaction solution, 20 mL of methanol and 30 mL of pure water were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 41 mg of a yellow powder containing Compound (C18) with an HPLC purity of 66.2%.

The compound was identified by FDMS.
FDMS (m / z); 412 (M +)

  Synthesis Example 9 Synthesis of synthesis of 9- [4-cyano-2- (9-phenanthryl) -phenyl] -phenanthrene

  In a 50 mL Schlenk tube under a nitrogen stream, 3.52 g (11.43 mmol) of 3-bromo-4-iodobenzonitrile, 6.35 g (28.58 mmol) of 9-phenanthreneboronic acid, 51 mg (0.23 mmol) of palladium acetate. , 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (Xphos) (218 mg, 0.46 mmol), tetrahydrofuran (15 mL), and 2 M aqueous potassium carbonate solution (15 mL) were added, and the mixture was stirred at 75 ° C. for 15 hours. . After cooling to room temperature, 100 mL of methanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (chloroform / methanol), 1.62 g (3.56 mmol) of a colorless powder of 9- [4-cyano-2- (9-phenanthryl) -phenyl] -phenanthrene was isolated (yield) 31%, HPLC purity 98.4%).

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.60-8.57 (m, 1H), 8.49-8.45 (m, 2H), 7.95-7.86 (m, 2H), 7. 78-7.61 (m, 8H), 7.56-7.30 (m, 8H)

Example 10 Synthesis of Compound (F9)

  Under a nitrogen stream, 456 mg (1.00 mmol) of 9- [4-cyano-2- (9-phenanthryl) -phenyl] -phenanthrene, 40 mL of chloroform, and 2 mL of nitromethane were added to a 100 mL Schlenk ring. The solution was cooled to 0 ° C. with stirring, 3.89 g (24.0 mmol) of iron (III) chloride was added, and the mixture was stirred at 0 ° C. for 20 minutes. 150 mL of methanol was added to the reaction solution, and the precipitated solid was collected by filtration, and washed with methanol to isolate 234 mg (0.52 mmol) of a yellow powder of compound (F9) (yield 52%, HPLC purity 94). .7%).

The compound was identified by ¹ H-NMR measurement and FDMS.
¹ H-NMR (DMSO-d ₆ ); 9.43 (s, 1H), 9.17 (d, 1H), 8.91-8.78 (m, 8H), 8.06 (t, 2H) , 7.83-7.75 (m, 5H)

Claims (10)

A method for producing a compound represented by the following general formula (1),
A production method comprising intramolecular cyclization of a compound represented by the following general formula (2).

(Where
X ¹ and X ² are the same or different and represent a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring which may have a substituent.
Aromatic ring represented by the aromatic ring and X ² represented by X ¹ may not be bonded may be bonded at least one binding.
R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an organic group, and adjacent substituents of R ^{1 to} R ⁴ are bonded to each other, and may have a substituent, or A condensed polycyclic aromatic ring may be formed.
When R ¹ and R ² are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ¹ may or may not be bonded by at least one bond. Good.
When R ³ and R ⁴ are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ² may or may not be bonded by at least one bond. Good.
When R ¹ and R ² are bonded to each other to form an aromatic ring, and R ³ and R ⁴ are bonded to each other to form an aromatic ring, these aromatic rings are bonded with at least one bond. Or may not be bonded. )

(Where
X ¹ and X ² are the same or different and represent a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring which may have a substituent.
Aromatic ring represented by the aromatic ring and X ² represented by X ¹ are not bonded.
R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an organic group, and adjacent substituents of R ^{1 to} R ⁴ are bonded to each other, and may have a substituent, or A condensed polycyclic aromatic ring may be formed.
When R ¹ and R ² are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ¹ are not bonded.
When R ³ and R ⁴ are bonded to each other to form an aromatic ring, the aromatic ring and the aromatic ring represented by X ² are not bonded.
When R ¹ and R ² are bonded to each other to form an aromatic ring, and R ³ and R ⁴ are bonded to each other to form an aromatic ring, these aromatic rings are bonded with at least one bond. Or may not be bonded. ) The compound represented by the general formula (1) is a compound represented by the following general formula (1 ′),
The production method according to claim 1, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (2 ').

(Where
X ¹ and X ² are the same or different and represent a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring which may have a substituent.
Y ¹ and Y ² are the same or different and represent a monocyclic or polycyclic condensed aromatic ring which may have a substituent.
Aromatic ring represented by the aromatic ring and X ² represented by X ¹ may not be bonded may be bonded at least one binding.
The aromatic ring represented by Y ¹ and the aromatic ring represented by Y ² may or may not be bonded by at least one bond.
The aromatic ring represented by X ¹ and the aromatic ring represented by Y ¹ may or may not be bonded with at least one bond.
The aromatic ring represented by X ² and the aromatic ring represented by Y ² may or may not be bonded by at least one bond. )

(Where
X ¹ and X ² are the same or different and represent a monocyclic, bicyclic condensed ring, or tricyclic condensed aromatic ring which may have a substituent.
Y ¹ and Y ² are the same or different and represent a monocyclic or polycyclic condensed aromatic ring which may have a substituent.
Aromatic ring represented by the aromatic ring and X ² represented by X ¹ are not bonded.
The aromatic ring represented by Y ¹ and the aromatic ring represented by Y ² may or may not be bonded by at least one bond.
Aromatic ring represented by the aromatic ring and Y ¹ represented by X ¹ are not bonded.
The aromatic ring represented by X ² and the aromatic ring represented by Y ² are not bonded. ) The production method according to claim 1, wherein the X ¹ and X ² are the same or different and each is any one of the general formulas (3) to (16).

(Wherein R ^{5 to} R ⁸ are the same or different, and each represents a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic or linked group having 3 to 36 carbon atoms, Or a condensed heteroaromatic group (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms) , A methoxy group, an ethoxy group, and one or more substituents selected from the group consisting of a linear, cyclic, or branched alkoxy group having 3 to 18 carbon atoms), hydrogen atom, deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight chain of 3 to 18 carbon atoms, cyclic, or branched Alkyl group, methoxy group, ethoxy group, or It represents a straight-chain, cyclic, or branched alkoxy groups of primes 3-18.
Of the groups represented by R ^{5 to} R ⁸ , adjacent groups may be bonded to each other to form a ring. ) The production method according to claim ² , wherein the X ¹ , X ² , Y ¹ and Y ² are the same or different and each is any one of the general formulas (3) to (16).

(Wherein R ^{5 to} R ⁸ are the same or different, and each represents a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic or linked group having 3 to 36 carbon atoms, Or a condensed heteroaromatic group (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms) , A methoxy group, an ethoxy group, and one or more substituents selected from the group consisting of a linear, cyclic, or branched alkoxy group having 3 to 18 carbon atoms), hydrogen atom, deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight chain of 3 to 18 carbon atoms, cyclic, or branched Alkyl group, methoxy group, ethoxy group, or It represents a straight-chain, cyclic, or branched alkoxy groups of primes 3-18.
Of the groups represented by R ^{5 to} R ⁸ , adjacent groups may be bonded to each other to form a ring. ) The production method according to claim 1 or 2, wherein an intramolecular cyclization reaction represented by any one of the following formulas (17) to (29) is performed.

(Where
Y ¹ and Y ² are the same or different and represent a monocyclic or polycyclic condensed aromatic ring which may have a substituent.
The aromatic ring represented by Y ¹ and the aromatic ring represented by Y ² may or may not be bonded by at least one bond.
A ^{1 to} A ⁶ are the same or different and each represents a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic, linked or condensed ring having 3 to 36 carbon atoms. A heteroaromatic group (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, a methoxy group, (It may have one or more substituents selected from the group consisting of an ethoxy group and a linear, cyclic, or branched alkoxy group having 3 to 18 carbon atoms), a hydrogen atom, a deuterium atom, a fluorine atom , a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight-chain, cyclic, or branched alkyl group having 3 to 18 carbon atoms, Methoxy group, ethoxy group, or carbon number 3 18 linear, an alkoxy group of cyclic, or branched.
k ¹ , k ² , k ⁵ , and k ⁶ are the same or different and are integers of 0 to 4.
k ³ and ^{k 4} are the same or different, it is an integer of 0-2. ) The production method according to claim 1 or 2, wherein an intramolecular cyclization reaction represented by any one of the following formulas (30) to (151) is performed.

(Where
Y ² represents a monocyclic or polycyclic condensed aromatic ring which may have a substituent.
A ^{1 to} A ⁶ and B ^{1 to} B ⁵ are the same or different and are each a monocyclic ring having 6 to 30 carbon atoms, a linked or condensed aromatic hydrocarbon group, a monocyclic ring having 3 to 36 carbon atoms, Linked or condensed heteroaromatic group (These groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched group having 3 to 18 carbon atoms. One or more substituents selected from the group consisting of an alkyl group, a methoxy group, an ethoxy group, and a linear, cyclic, or branched alkoxy group having 3 to 18 carbon atoms), a hydrogen atom, deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight chain of 3 to 18 carbon atoms, cyclic, Or branched alkyl group, methoxy group, ethoxy , Or represents a straight-chain, cyclic, or branched alkoxy group having a carbon number of 3 to 18.
k ¹ , k ² , k ⁵ , and k ⁶ are the same or different and are integers from 0 to 4.
k ³ and ^{k 4} are the same or different and are an integer of 0 to 2.
m ¹ and m ³ are the same or different and are integers of 0 to 4.
m ² and ^{m 4} are different or the same or an integer of 0-2.
m ⁵ is an integer of 0 to 3. )   The production method according to any one of claims 1 to 6, wherein the intramolecular cyclization is performed by oxidation with an oxidizing agent or oxidation by light irradiation. The oxidizing agent is ferric chloride (FeCl ₃ ), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), molybdenum chloride (MoCl ₅ ), aluminum chloride (AlCl ₃ ), [bis (tri The production method according to claim 7, which is any one of (fluoroacetoxy) iodo] benzene (PIFA). The production method according to claim 7, wherein iodine (I ₂ ) and 1,2-epoxypropane or 1,2-epoxybutane are used as additives in the oxidation by light irradiation. A condensed ring compound represented by any one of general formulas (152) to (156).

(Where
Z ¹ represents a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a thiol group, a cyano group, or an amino group.
A ^{1 to} A ⁸ are the same or different and each represents a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, a monocyclic, linked or condensed ring having 3 to 36 carbon atoms. Heteroaromatic groups (these groups are each independently a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a linear, cyclic or branched alkyl group having 3 to 18 carbon atoms, and a methoxy group) , An ethoxy group, one or more substituents selected from the group consisting of linear, cyclic or branched alkoxy groups having 3 to 18 carbon atoms), hydrogen atom, deuterium atom, fluorine atom , a chlorine atom, a bromine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group _(-NH 2), a methyl group, an ethyl group, a straight-chain, cyclic, or branched alkyl group having 3 to 18 carbon atoms, Methoxy group, ethoxy group, or carbon number 3 18 linear, cyclic, or represents a branched alkoxy group, adjacent substituents may may form a ring together.
k ¹ , k ² , k ⁵ , and k ⁶ are the same or different and are each an integer of 0 to 4.
k ³ and k ⁴ are the same or different and are each an integer of 0 to 2.
k ⁷ and k ⁸ are the same or different and each is an integer of 0 to 3.
n ¹ is an integer of 1 to 4. )

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