JP2012176928A - Pyrene derivative, production method of pyrene derivative, complex, catalyst, electronic material, light-emitting material and pigment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide pyrene derivatives having a new structure and new properties.SOLUTION: There are provided pyrene derivatives represented by chemical formula (I) synthesized from a compound of chemical formula (II) and a compound of chemical formula (III), their tautomers, geometrical isomers and stereoisomers or salts thereof. [Wherein, at least one of Ais (substituted) aryl or the like, and each Amay be the same or different; Ris a hydrocarbon and may be linear or branched; Ris H or an optional substituent; and Ris an optional substituent].

Description

  The present invention relates to a pyrene derivative, a method for producing a pyrene derivative, a complex, a catalyst, an electronic material, a light emitting material, and a dye.

  Aromatic compounds have long been extremely important in organic chemistry due to their unique chemical properties. By bonding various groups to the aromatic ring, it is possible to obtain various characteristics that cannot be realized with non-aromatic compounds, and it is widely used in various industrial fields. For example, according to recent research, when an aromatic ring is bonded directly without a linker (bonding chain) or via a short linker, a space rich in π electrons (hereinafter referred to as “π electron space” for convenience) May be formed). In such a π-electron space, a phenomenon different from a normal space may occur. For example, it is known that a compound called normally hemiaminal or hemiaminal ether can be stably present by using a cage-type molecule in which a benzene ring is bound by a short linker (Non-patent Document 1). And 2). Further, there is a 1,2,3,4,5,6-hexaphenylbenzene structure in which one benzene ring is covalently bonded to each carbon atom of the central benzene ring and surrounded by six benzene rings. By using this structure as a part of the ligand of the asymmetric synthesis catalyst, a high catalyst rotation speed is realized (Non-patent Document 3). Thus, the π-electron space is expected to be used in various industries because it can cause unusual chemical or physical phenomena.

  On the other hand, pyrene is a macrocyclic aromatic compound in which a large number of aromatic rings are condensed. For this reason, pyrene has a more specific property among aromatic compounds, and is attracting attention in the field of organic material chemistry and the like. By introducing various substituents into pyrene, spectral characteristics, optoelectronic characteristics, etc. can be adjusted (Non-Patent Documents 4 to 7, etc.). For example, there is a compound in which a pyrene ring and another aromatic ring are directly bonded instead of a benzene ring (Patent Document 1).

JP 2010-150235 A

Iwasawa, T .; Mann, E .; Rebek, J., Jr. J. Am. Chem. Soc. 2006, 128, 9308-9309. Iwasawa, T .; Hooley, R. J .; Rebek, J., Jr. Science, 2007, 317, 493. Iwasawa, T .; Kamei, T .; Nishimoto, Y .; Nishiuchi, M .; Kawamura, Y. Tetrahedron Lett. 2008, 49, 7430-7433. Lackowicz, J. R. In Principles of Flurorescenece Spectroscopy, 2nd ed .; Kluwer Academic / Plenum Publishers: New York, 1999; pp 595-614. Birks, J. B. In Photophysics of Aromatic Molecules; Wiley-Interscience: London, 1970. Berlman, I. B. J. Phys. Chem. 1970, 74, 3085. Oyamada, T .; Uchiuzou, H .; Akiyama, S .; Oku, Y .; Shimoji, N .; Matsushige, K .; Sasabe, H .; Adachi, C. J. Appl. Phys. 2005, 98, 074506.

  As described above, pyrene has more specific properties among aromatic compounds, and can exhibit various properties by introducing various substituents. For this reason, the technique which can introduce | transduce a substituent into a pyrene ring more freely is calculated | required. For example, in Non-Patent Document 3, it is presumed that a π-electron space formed by a 1,2,3,4,5,6-hexaphenylbenzene structure serves as a host, and a substrate is taken in as a guest therein. Thereby, it is considered that a stable reaction field is formed and a high catalyst rotation speed is realized. If the central benzene ring is replaced with pyrene, which is a large aromatic ring, a wider π-electron space can be formed, and utilization of a substrate having a larger molecular size can be expected.

  However, it is difficult to synthesize (manufacture) a compound in which a substituent (for example, an aromatic ring) is further bonded to pyrene, which is a large aromatic ring, due to problems such as solubility and reactivity of pyrene. For this reason, there are few examples of the synthesis | combination of such a compound, and only the compound of the very limited structure is synthesize | combined also in patent document 1 and nonpatent literature 4-7.

  Therefore, the present invention provides a pyrene derivative having a novel structure and characteristics and a production method capable of easily producing the pyrene derivative. Furthermore, the present invention also provides a complex, a catalyst, an electronic material, a light emitting material, and a dye using the pyrene derivative.

前記化学式（Ｉ）中、
Ａｒは、水素原子または任意の置換基であり、各Ａｒは同一でも異なっていても良く、
Ａｒのうち少なくとも一方は、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロアリール基、 −Ｓｉ（Ｒ^１００）_３で表される置換もしくは無置換のシリル基、トリアルキルシリル基、置換もしくは無置換のエチニレン基、トリアルキルシリルエチニレン基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアリールオキシ基、アリールアミノ基、ジアリールアミノ基、アルキルアミノ基、ジアルキルアミノ基、ビス（トリアルキルシリル）アミノ基、置換もしくは無置換の飽和もしくは不飽和脂環式炭化水素基、置換もしくは無置換の飽和もしくは不飽和非芳香族性ヘテロ環、置換もしくは無置換のピペリジル基、置換もしくは無置換のピペラジル基、置換もしくは無置換のピロリジル基、または置換もしくは無置換のモルホリノ基であり、
Ｒ^１００は、水素原子または炭化水素基であり、前記炭化水素基は、直鎖状でも分枝状でも環状でも良く、飽和でも不飽和でも良く、置換基を有していても有していなくても良く、各Ｒ^１００は同一でも異なっていても良く、
Ｒ^１は、炭化水素基であり、直鎖状でも分枝状でも環状でも良く、飽和でも不飽和でも良く、置換基を有していても有していなくても良く、各Ｒ^１は同一でも異なっていても良く、
Ｒ^２は、水素原子または任意の置換基であり、各Ｒ^２は、同一でも異なっていても良く、
Ｒ^３は、任意の置換基であり、各Ｒ^３は、同一でも異なっていても良く、ａは、０から２までの置換数であり、各ａは、同一でも異なっていても良い。 In order to achieve the above object, the pyrene derivative of the present invention is a pyrene derivative represented by the following chemical formula (I), a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof.

In the chemical formula (I),
Ar is a hydrogen atom or an arbitrary substituent, and each Ar may be the same or different;
At least one of Ar is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ , a trialkylsilyl group, a substituted or Unsubstituted ethynylene group, trialkylsilylethynylene group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, arylamino group, diarylamino group, alkylamino group, dialkylamino group, bis (trialkyl Silyl) amino group, substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group, substituted or unsubstituted saturated or unsaturated non-aromatic heterocyclic ring, substituted or unsubstituted piperidyl group, substituted or unsubstituted A piperazyl group, a substituted or unsubstituted pyrrolidyl group, or a substituted or An unsubstituted morpholino group,
R ¹⁰⁰ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group may be linear, branched or cyclic, saturated or unsaturated, and may have a substituent. Each R ¹⁰⁰ may be the same or different,
R ¹ is a hydrocarbon group, which may be linear, branched, or cyclic, saturated or unsaturated, may or may not have a substituent, and each R ¹ is the same But it can be different,
R ² is a hydrogen atom or an arbitrary substituent, and each R ² may be the same or different,
R ³ is an arbitrary substituent, each R ³ may be the same or different, a is the number of substitutions from 0 to 2, and each a may be the same or different.

前記化学式（II）中、
Ｒ^１、Ｒ^２、Ｒ^３およびａは、前記化学式（Ｉ）と同じであり、
Ｘは、ハロゲノ基であり、各Ｘは、同一でも異なっていても良く、
前記化学式（III）中、
Ａｒは、前記化学式（Ｉ）で定義される置換または無置換のアリール基である。 The first production method of the present invention comprises:
In the chemical formula (I), Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,
The book comprising a cross-coupling step in which a halogenated pyrene derivative represented by the following chemical formula (II) and an aryl boronic acid represented by the following chemical formula (III) are subjected to a cross-coupling reaction in the presence of a palladium catalyst. It is a process for producing the pyrene derivatives of the invention, tautomers, geometric isomers or stereoisomers thereof, or salts thereof.

In the chemical formula (II),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I),
X is a halogeno group, and each X may be the same or different;
In the chemical formula (III),
Ar is a substituted or unsubstituted aryl group defined by the chemical formula (I).

前記化学式（Ｉ’）中、
Ａｒは、前記化学式（Ｉ）で定義される置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基であり、
Ｒ^１、Ｒ^２、Ｒ^３およびａは、前記化学式（Ｉ）と同じであり、
Ｒ^４は、アリール基以外の任意の置換基であり、
前記化学式（II）、（IV）および（Ｖ）中、
Ｒ^１、Ｒ^２、Ｒ^３およびａは、前記化学式（Ｉ’）と同じであり、
Ｘは、ハロゲノ基であり、前記化学式（II）中における各Ｘは、同一でも異なっていても良く、
前記化学式（IV）中、
Ｍは、金属であり、
前記化学式（Ｖ）中、
Ｒ^４は、前記化学式（Ｉ’）と同じであり、
前記化学式（III）中、
Ａｒは、前記化学式（Ｉ’）と同じである。 The second production method of the present invention comprises:
The pyrene derivative represented by the chemical formula (I) is a pyrene derivative represented by the following chemical formula (I ′),
A metalation step of producing a pyrene derivative represented by the following chemical formula (IV) by metallizing a halogenated pyrene derivative represented by the following chemical formula (II);
Following chemical formula is reacted with a cation of the pyrene derivative and R ⁴ of formula (IV) by introducing a substituent R ⁴ in a substituted group introduction step for producing a pyrene derivative represented by the following formula (V) and,
A cross-coupling step in which a pyrene derivative represented by the following chemical formula (V) and an aryl boronic acid represented by the following chemical formula (III) are subjected to a cross-coupling reaction in the presence of a palladium catalyst,
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

In the chemical formula (I ′),
Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined by the chemical formula (I),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I),
R ⁴ is an optional substituent other than an aryl group,
In the chemical formulas (II), (IV) and (V),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I ′),
X is a halogeno group, and each X in the chemical formula (II) may be the same or different;
In the chemical formula (IV),
M is a metal,
In the chemical formula (V),
R ⁴ is the same as the chemical formula (I ′),
In the chemical formula (III),
Ar is the same as in the chemical formula (I ′).

前記化学式（Ｉ’）および（III’）中、
Ａｒは、前記化学式（Ｉ）で定義される置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基であり、各Ａｒは同一でも異なっていても良く、
前記化学式（Ｉ’）中、
Ｒ^１、Ｒ^２、Ｒ^３およびａは、前記化学式（Ｉ）と同じであり、
Ｒ^４は、 −Ｓｉ（Ｒ^１００）_３で表される置換もしくは無置換のシリル基であり、
前記化学式（Ｖ’’）中、
Ａｒは、前記化学式（Ｉ）で定義される置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基であり、
Ｒ^１、Ｒ^２、Ｒ^３およびａは、前記化学式（Ｉ）と同じである。 The third production method of the present invention comprises:
In the chemical formula (I), Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,
By the second production method of the present invention, a silylpyrene derivative for producing a silylpyrene derivative in which R ⁴ in the chemical formula (I ′) is a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ Manufacturing process,
A halogenation step of producing a halogenated pyrene derivative represented by the following chemical formula (V ″) by reacting the silylpyrene derivative represented by the chemical formula (I ′) with a halogenating agent; and
A halogenated pyrene derivative represented by the following chemical formula (V ″) and an aryl boronic acid represented by the following chemical formula (III ′) are subjected to a cross-coupling reaction in the presence of a palladium catalyst to obtain the following chemical formula (I): Including a second cross-coupling step to produce the represented pyrene derivative,
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

In the chemical formulas (I ′) and (III ′),
Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined by the chemical formula (I), and each Ar may be the same or different;
In the chemical formula (I ′),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I),
R ⁴ is a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ ;
In the chemical formula (V ″),
Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined by the chemical formula (I),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I).

The fourth production method of the present invention comprises:
The pyrene derivative represented by the chemical formula (I) is a pyrene derivative represented by the chemical formula (V),
In the chemical formula (V), R ⁴ is a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ ;
A metalation step of producing a pyrene derivative represented by the chemical formula (IV) by metallizing the halogenated pyrene derivative represented by the chemical formula (II); and
Said formula is reacted with a cation of the pyrene derivative and R ⁴ of formula (IV) by introducing a substituent R ^4, including substituents introduction step of producing a pyrene derivative represented by the formula (V),
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

The fifth production method of the present invention comprises:
The pyrene derivative represented by the chemical formula (I) is a pyrene derivative represented by the chemical formula (V ″),
A silylpyrene derivative production process for producing a silylpyrene derivative represented by the chemical formula (I ′) by the third production method of the present invention, and
A halogenation step of producing a halogenated pyrene derivative represented by the chemical formula (V ″) by reacting the silylpyrene derivative represented by the chemical formula (I ′) with a halogenating agent,
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

The sixth production method of the present invention comprises:
In the first, second, third or fifth manufacturing method of the present invention,
In the cross-coupling step, a substituted or unsubstituted saturated or unsaturated non-aromatic heterocyclic compound, a substituted or unsubstituted alcohol, substituted or unsubstituted, instead of the arylboronic acid represented by the chemical formula (III) Using substituted phenol, arylamine, diarylamine, alkylamine, dialkylamine, or bis (trialkylsilyl) amine,
In the cross-coupling step, Ar introduced into the pyrene derivative (I ′) is substituted or unsubstituted aryl group or substituted or unsubstituted heteroaryl group, substituted or unsubstituted saturated or unsaturated non-aromatic An aromatic heterocycle, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, an arylamino group, a diarylamino group, an alkylamino group, a dialkylamino group, or a bis (trialkylsilyl) amino group,
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

The seventh manufacturing method of the present invention comprises:
In the third or sixth production method of the present invention,
In the second cross-coupling step, in place of the arylboronic acid represented by the chemical formula (III), a substituted or unsubstituted saturated or unsaturated non-aromatic heterocyclic compound, a substituted or unsubstituted alcohol, a substituted Or using unsubstituted phenol, arylamine, diarylamine, alkylamine, dialkylamine, or bis (trialkylsilyl) amine,
In the second cross-coupling step, Ar introduced into the pyrene derivative (I) is substituted or unsubstituted aryl group or substituted or unsubstituted heteroaryl group, substituted or unsubstituted saturated or unsaturated non-substituted An aromatic heterocycle, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, an arylamino group, a diarylamino group, an alkylamino group, a dialkylamino group, or a bis (trialkylsilyl) amino group ,
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

The eighth production method of the present invention comprises:
In the first, second, third or fifth manufacturing method of the present invention,
In the cross-coupling step, substituted or unsubstituted acetylene is used instead of the arylboronic acid represented by the chemical formula (III),
Ar introduced into the pyrene derivative (I ′) in the cross-coupling step is a substituted or unsubstituted ethynylene group instead of a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

The ninth production method of the present invention comprises:
In the third, sixth or eighth manufacturing method of the present invention,
In the second cross-coupling step, substituted or unsubstituted acetylene is used instead of the arylboronic acid represented by the chemical formula (III),
Ar introduced into the pyrene derivative (I) in the second cross-coupling step is a substituted or unsubstituted ethynylene group instead of a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

  The complex of the present invention is a complex comprising the pyrene derivative of the present invention, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof as a ligand.

  The catalyst of the present invention is a catalyst comprising the pyrene derivative of the present invention, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof, or the complex of the present invention.

  The electronic material of the present invention is an electronic material containing the pyrene derivative of the present invention, a tautomer, geometric isomer or stereoisomer thereof, a salt thereof, or the complex of the present invention.

  The light-emitting material of the present invention is a light-emitting material containing the pyrene derivative of the present invention, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof, or the complex of the present invention.

  The dye of the present invention is a dye containing the pyrene derivative of the present invention, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof, or the complex of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the pyrene derivative which has a novel structure and characteristic, and the manufacturing method which can manufacture the pyrene derivative simply can be provided. Furthermore, according to the present invention, it is possible to provide a complex, a catalyst, an electronic material, a light emitting material, and a dye using the pyrene derivative.

FIG. 1 is a ¹ H NMR chart of 1,6-dibromopyrene synthesized in Reference Example. FIG. 2 is a ¹ H NMR chart of 1,6-dibutylpyrene synthesized in the reference example. FIG. 3 is a ¹ H NMR chart of 1,6-dibutyl-3,8-dibromopyrene synthesized in the reference example. 4 is a ¹ H NMR chart of 1,6-dibutyl-3,8-bis (2-methoxyphenyl) pyrene (compound (101)) synthesized in Example 1. FIG. 5 is a ¹³ C NMR chart of 1,6-dibutyl-3,8-bis (2-methoxyphenyl) pyrene (compound (101)) synthesized in Example 1. FIG. 6 is a ¹ H NMR chart of 1,6-dibutyl-3,8-bis (o-tolyl) pyrene (compound (102)) synthesized in Example 2. FIG. 7 is a ¹³ C NMR chart of 1,6-dibutyl-3,8-bis (o-tolyl) pyrene (compound (102)) synthesized in Example 2. FIG. 8 is a ¹ H NMR chart of 2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (103)) synthesized in Example 3. FIG. FIG. 9 is a ¹³ C NMR chart of 2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (103)) synthesized in Example 3. FIG. 10 shows {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (methylsulfane) synthesized in Example 4 (compound (104) ¹ H NMR chart. FIG. 11 shows {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (methylsulfane) synthesized in Example 4 (compound (104) ¹³ C NMR chart. 12 is a ¹ H NMR chart of 1,6-dibutyl-3,8-dimesitylpyrene (compound (105)) synthesized in Example 5. FIG. 13 is a ¹³ C NMR chart of 1,6-dibutyl-3,8-dimesitylpyrene (compound (105)) synthesized in Example 5. FIG. 14 is a ¹ H NMR chart of 1,6-dibutyl-3,8-bis (1-naphthyl) pyrene (compound (106)) synthesized in Example 6. FIG. 15 is a ¹³ C NMR chart of 1,6-dibutyl-3,8-bis (1-naphthyl) pyrene (compound (106)) synthesized in Example 6. FIG. FIG. 16 is a ¹ H NMR chart of dimethyl-2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (107)) synthesized in Example 7. 17 is a ¹³ C NMR chart of dimethyl-2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (107)) synthesized in Example 7. FIG. 18 is a ¹ H NMR chart of (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) synthesized in Example 9. FIG. 19 is a ¹³ C NMR chart of (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) synthesized in Example 9. FIG. 20 is a ¹ H NMR chart of methyl 4- (6-bromo-3,8-dibutylpyren-1-yl) benzoate (compound (1014)) synthesized in Example 10. FIG. 21 is a ¹³ C NMR chart of methyl 4- (6-bromo-3,8-dibutylpyren-1-yl) benzoate (compound (1014)) synthesized in Example 10. FIG. 22 is a ¹ H NMR chart of 4- (6-bromo-3,8-dibutylpyren-1-yl) benzaldehyde (Compound (1015)) synthesized in Example 11. FIG. 23 is a ¹³ C NMR chart of 4- (6-bromo-3,8-dibutylpyren-1-yl) benzaldehyde (Compound (1015)) synthesized in Example 11. FIG. 24 is a ¹ H NMR chart of ¹ -bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)) synthesized in Example 12. FIG. 25 is a ¹³ C NMR chart of 1-bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)) synthesized in Example 12. FIG. 26 is a ¹ H NMR chart of methyl 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1002)) synthesized in Example 13. FIG. 27 is a ¹³ C NMR chart of methyl 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1002)) synthesized in Example 13. FIG. 28 is a ¹ H NMR chart of methyl 3- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (Compound (1003)) synthesized in Example 14. FIG. 29 is a ¹³ C NMR chart of methyl 3- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (Compound (1003)) synthesized in Example 14. FIG. 30 is a ¹ H NMR chart of methyl 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1004)) synthesized in Example 15. FIG. FIG. 31 is a ¹³ C NMR chart of methyl 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1004)) synthesized in Example 15. 32 is a ¹ H NMR chart of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (Compound (1005)) synthesized in Example 16. FIG. 33 is a ¹³ C NMR chart of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (compound (1005)) synthesized in Example 16. FIG. 34 is a ¹ H NMR chart of 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (Compound (1006)) synthesized in Example 17. FIG. 35 is a ¹³ C NMR chart of 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (Compound (1006)) synthesized in Example 17. FIG. 36 is a ¹ H NMR chart of (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1007)) synthesized in Example 18. FIG. FIG. 37 is a ¹³ C NMR chart of (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1007)) synthesized in Example 18. 38 is a ¹ H NMR chart of (3,8-dibutyl-6- (2-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1008)) synthesized in Example 19. FIG. 39 is a ¹³ C NMR chart of (3,8-dibutyl-6- (2-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1008)) synthesized in Example 19. FIG. 40 is a ¹ H NMR chart of (6- (2-bromophenyl) -3,8-dibutylpyren-1-yl) trimethylsilane (compound (1009)) synthesized in Example 20. FIG. 41 is a ¹³ C NMR chart of (6- (2-bromophenyl) -3,8-dibutylpyren-1-yl) trimethylsilane (compound (1009)) synthesized in Example 20. FIG. 42 is a ¹ H NMR chart of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzamide (Compound (1010)) synthesized in Example 21. FIG. 43 is a ¹³ C NMR chart of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzamide (Compound (1010)) synthesized in Example 21. FIG. 44 is a ¹ H NMR chart of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyridine (compound (1011)) synthesized in Example 22. FIG. 45 is a ¹³ C NMR chart of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyridine (compound (1011)) synthesized in Example 22. FIG. 46 is a ¹ H NMR chart of (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) trimethylsilane (compound (1012)) synthesized in Example 23. FIG. 47 is a ¹³ C NMR chart of (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) trimethylsilane (compound (1012)) synthesized in Example 23. FIG. 48 is a ¹ H NMR chart of 1- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyrrolidine (Compound (1013)) synthesized in Example 24. FIG. 49 is a ¹³ C NMR chart of 1- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyrrolidine (Compound (1013)) synthesized in Example 24. FIG. 50 is a ¹ H NMR chart of methyl 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzoate (Compound (1017)) synthesized in Example 25. FIG. 51 is a ¹³ C NMR chart of methyl 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzoate (Compound (1017)) synthesized in Example 25. FIG. 52 is a ¹ H NMR chart of 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzaldehyde (Compound (1018)) synthesized in Example 26. FIG. 53 is a ¹³ C NMR chart of 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzaldehyde (Compound (1018)) synthesized in Example 26. FIG. 54 is a ¹ H NMR chart of 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyridine (compound (1019)) synthesized in Example 27. FIG. 55 is a ¹³ C NMR chart of 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyridine (compound (1019)) synthesized in Example 27. FIG. FIG. 56 is a ¹ H NMR chart of ((3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) ethynyl) trimethylsilane (compound (1020)) synthesized in Example 28. FIG. 57 is a ¹³ C NMR chart of ((3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) ethynyl) trimethylsilane (compound (1020)) synthesized in Example 28. 58 is a ¹ H NMR chart of 1- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyrrolidine (compound (1021)) synthesized in Example 29. FIG. 59 is a ¹³ C NMR chart of 1- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyrrolidine (compound (1021)) synthesized in Example 29. FIG. 60 is a ¹ H NMR chart of dimethyl 2,4 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (1022)) synthesized in Example 30. FIG. 61 is a ¹³ C NMR chart of dimethyl 2,4 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (Compound (1022)) synthesized in Example 30. FIG. 62 is a ¹ H NMR chart of methyl 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzoate (Compound (1023)) synthesized in Example 31. FIG. 63 is a ¹³ C NMR chart of methyl 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzoate (Compound (1023)) synthesized in Example 31. FIG. 64 is a ¹ H NMR chart of 2,4 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (Compound (1024)) synthesized in Example 32. FIG. 65 is a ¹³ C NMR chart of 2,4 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (Compound (1024)) synthesized in Example 32. FIG. 66 is a ¹ H NMR chart of 4- (3,8-dibutyl-1,11-bipyren-6-yl) benzaldehyde (compound (1025)) synthesized in Example 33. FIG. 67 is a ¹³ C NMR chart of 4- (3,8-dibutyl-1,11-bipyrene-6-yl) benzaldehyde (Compound (1025)) synthesized in Example 33. FIG. 68 is a ¹ H NMR chart of 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzaldehyde (Compound (1026)) synthesized in Example 34. FIG. 69 is a ¹³ C NMR chart of 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzaldehyde (Compound (1026)) synthesized in Example 34. FIG.

  Hereinafter, the present invention will be described with examples. However, the present invention is not limited to the following description.

前記化学式（Ｉ）中、
Ａｒは、水素原子または任意の置換基であり、各Ａｒは同一でも異なっていても良く、
Ａｒのうち少なくとも一方は、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロアリール基、 −Ｓｉ（Ｒ^１００）_３で表される置換もしくは無置換のシリル基、トリアルキルシリル基、置換もしくは無置換のエチニレン基、トリアルキルシリルエチニレン基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアリールオキシ基、アリールアミノ基、ジアリールアミノ基、アルキルアミノ基、ジアルキルアミノ基、ビス（トリアルキルシリル）アミノ基、置換もしくは無置換の飽和もしくは不飽和脂環式炭化水素基、置換もしくは無置換の飽和もしくは不飽和非芳香族性ヘテロ環、置換もしくは無置換のピペリジル基、置換もしくは無置換のピペラジル基、置換もしくは無置換のピロリジル基、または、置換もしくは無置換のモルホリノ基であり、
Ｒ^１００は、水素原子または炭化水素基であり、前記炭化水素基は、直鎖状でも分枝状でも環状でも良く、飽和でも不飽和でも良く、置換基を有していても有していなくても良く、各Ｒ^１００は同一でも異なっていても良く、
Ｒ^１は、炭化水素基であり、直鎖状でも分枝状でも環状でも良く、飽和でも不飽和でも良く、置換基を有していても有していなくても良く、各Ｒ^１は同一でも異なっていても良く、
Ｒ^２は、水素原子または任意の置換基であり、各Ｒ^２は、同一でも異なっていても良く、
Ｒ^３は、任意の置換基であり、各Ｒ^３は、同一でも異なっていても良く、ａは、０から２までの置換数であり、各ａは、同一でも異なっていても良い。 <1. Pyrene derivatives>
As described above, the pyrene derivative of the present invention is a pyrene derivative represented by the following chemical formula (I), a tautomer, a geometric isomer or a stereoisomer thereof, or a salt thereof.

In the chemical formula (I),
Ar is a hydrogen atom or an arbitrary substituent, and each Ar may be the same or different;
At least one of Ar is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ , a trialkylsilyl group, a substituted or Unsubstituted ethynylene group, trialkylsilylethynylene group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, arylamino group, diarylamino group, alkylamino group, dialkylamino group, bis (trialkyl Silyl) amino group, substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group, substituted or unsubstituted saturated or unsaturated non-aromatic heterocyclic ring, substituted or unsubstituted piperidyl group, substituted or unsubstituted Piperazyl group, substituted or unsubstituted pyrrolidyl group, or substituted or Is an unsubstituted morpholino group,
R ¹⁰⁰ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group may be linear, branched or cyclic, saturated or unsaturated, and may have a substituent. Each R ¹⁰⁰ may be the same or different,
R ¹ is a hydrocarbon group, which may be linear, branched, or cyclic, saturated or unsaturated, may or may not have a substituent, and each R ¹ is the same But it can be different,
R ² is a hydrogen atom or an arbitrary substituent, and each R ² may be the same or different,
R ³ is an arbitrary substituent, each R ³ may be the same or different, a is the number of substitutions from 0 to 2, and each a may be the same or different.

  When the pyrene derivative of the present invention includes isomers such as tautomers or stereoisomers (eg, geometrical isomers, conformational isomers, and optical isomers), any isomers are included in the present invention. Can be used. For example, when the optical isomer is used for asymmetric synthesis or the like, it is preferable to selectively use either the R isomer or the S isomer depending on the purpose. Moreover, the salt of the pyrene derivative of this invention can be used for this invention similarly. The salt may be an acid addition salt or a base addition salt. Furthermore, the acid forming the acid addition salt may be an inorganic acid or an organic acid, and the base forming the base addition salt may be an inorganic base or an organic base. The inorganic acid is not particularly limited. For example, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypofluorite, hypochlorous acid, hypobromite, Hypoiodous acid, fluorinated acid, chlorous acid, bromic acid, iodic acid, fluoric acid, chloric acid, bromic acid, iodic acid, perfluoric acid, perchloric acid, perbromic acid, periodic acid, etc. Can be mentioned. Although the organic acid is not particularly limited, for example, p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, p-bromobenzenesulfonic acid, carbonic acid, succinic acid, citric acid, benzoic acid, acetic acid, hydroxycarboxylic acid, propionic acid , Malonic acid, adipic acid, fumaric acid, maleic acid and the like. Examples of the inorganic base include, but are not limited to, ammonium hydroxide, alkali metal hydroxide, alkaline earth metal hydroxide, carbonate, bicarbonate, sulfate, and the like. More specifically, Examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydroxide, calcium carbonate, potassium sulfate, calcium sulfate and the like. The organic base is not particularly limited, and examples thereof include alcohol amine, trialkylamine, tetraalkylammonium, and tris (hydroxymethyl) aminomethane. Examples of the alcohol amine include ethanolamine. Examples of the trialkylamine include trimethylamine, triethylamine, tripropylamine, tributylamine, and trioctylamine. Examples of the tetraalkylammonium include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetraoctylammonium and the like. The method for producing these salts is not particularly limited, and for example, the salt can be produced by a method such as appropriately adding the above acid or base to the pyrene derivative by a known method.

  In the present invention, examples of the chain hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. An alkenyl group may have a structure in which any carbon-carbon bond of an alkyl group is converted to a double bond by dehydrogenation, and an alkynyl group is a structure in which any carbon-carbon bond of an alkyl group is converted to a triple bond by dehydrogenation. It may be a structure. Although carbon number of the said chain | strand-shaped hydrocarbon group is not specifically limited, For example, 1-32, 1-24, 1-18, 1-12, 1-6, or 1-2 may be sufficient. The same applies to groups derived from chain hydrocarbon groups (for example, haloalkyl groups, hydroxyalkyl groups, aminoalkyl groups, alkanoyl groups, alkoxy groups, alkoxyalkyl groups, alkylamino groups, perfluoroalkyl groups, etc.). However, when the chain hydrocarbon group contains a substituent, the carbon number does not include the carbon number of the substituent. In the present invention, the alkyl group specifically includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group, pentyl group, Examples include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and the like. A group derived from an alkyl group or a group containing an alkyl group in the structure (for example, alkenyl group, alkynyl group, haloalkyl group, hydroxyalkyl group, aminoalkyl group, alkanoyl group, alkoxy group, alkylamino group, perfluoroalkyl group, The same applies to an alkenyl group, an alkoxyalkyl group, a trialkylsilyl group, and the like. In the present invention, the acyl group is not particularly limited. For example, formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, cyclohexanoyl group, benzoyl group, ethoxycarbonyl The same applies to groups containing an acyl group in the structure (acyloxy group, alkanoyloxy group, etc.). In the present invention, the carbon number of the acyl group includes carbonyl carbon. For example, an alkanoyl group having 1 carbon atom (acyl group) refers to a formyl group. Furthermore, in the present invention, “halogen” refers to any halogen element, and examples thereof include fluorine, chlorine, bromine and iodine. Similarly, the halogeno group includes, for example, a fluoro group, a chloro (chloro) group, a bromo group, and an iodo group.

  In the present invention, the number of ring members (the number of atoms constituting the ring) of a cyclic group such as an alicyclic hydrocarbon group or an aryl group is not particularly limited, but is, for example, 5 to 32, 5 to 24, 6 to 18 6-12, or 6-10. In the present invention, the alicyclic hydrocarbon group means a non-aromatic cyclic hydrocarbon group. In the alicyclic hydrocarbon group, for example, at least one of carbon atoms constituting the ring may be replaced by a heteroatom such as oxygen (O), sulfur (S), nitrogen (N), or the like. It does not have to be. In the present invention, the aryl group is not limited to an aromatic hydrocarbon group unless otherwise specified, and includes a heteroaryl group. In the present invention, examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclopropyl group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a pyridyl group, a quinolyl group, an acridyl group, a furanyl group, a thienyl group, a carbazoyl group, a fluorenyl group, an orthoxyl group, and a tolyl group. It is done.

  In the present invention, when the aryl group, heteroaryl group, chain hydrocarbon group, alicyclic hydrocarbon group, non-aromatic heterocycle and the like further have a substituent, the substituent is not particularly limited. , Alkyl group, alkoxy group, alkylthio group, acyl group, alkanoyl group, carboxy group, alkoxycarbonyl group, hydroxyalkyl group, mercaptoalkyl group, hydroxy group, mercapto group, amino group, aminoalkyl group, alkylamino group, dialkylamino Group, aryl group, chain hydrocarbon group, alicyclic hydrocarbon group, alkylsilyl group, dialkylsilyl group, trialkylsilyl group, deuterium atom, formyl group and the like. The substituent may be one, plural, or absent unless specifically limited, and in the case of plural, they may be the same or different.

  In the present invention, a chain group such as a chain hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group, etc.), an alkoxy group, an alkanoyl group or the like is linear or branched unless otherwise specified. But you can. In the present invention, when an isomer is present in a substituent, a functional group, etc., any isomer may be used unless otherwise limited. For example, when simply referring to “propyl group”, it may be either an n-propyl group or an isopropyl group. When simply referred to as “butyl group”, any of n-butyl group, isobutyl group, sec-butyl group and tert-butyl group may be used. When simply referred to as “naphthyl group”, either a 1-naphthyl group or a 2-naphthyl group may be used.

  In the chemical formula (I), in each Ar, the aryl group is not particularly limited, and examples thereof include a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted phenyl group. Or a substituted or unsubstituted condensed polycyclic aromatic group. In each Ar, the aryl group is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyrenyl group. In each Ar, the heteroaryl group is preferably a substituted or unsubstituted pyridyl group.

  In the chemical formula (I), in each Ar, the aryl group may be unsubstituted or an alkyl group, an alkoxy group, an alkylthio group, an acyl group, a halocarbonyl group, a carboxy group, an alkoxycarbonyl group, or a hydroxyalkyl group. , Mercaptoalkyl group, hydroxy group, mercapto group, amino group, aminoalkyl group, alkylamino group, dialkylamino group, aryl group, chain hydrocarbon group, alicyclic hydrocarbon group, alkylsilyl group, dialkylsilyl group, It may be substituted with at least one substituent selected from the group consisting of a trialkylsilyl group and a deuterium atom. Examples of the acyl group include an alkanoyl group, and examples of the alkanoyl group include a formyl group. Examples of the halocarbonyl group include a chlorocarbonyl group. The substituent is more preferably a methoxy group, a methyl group, a formyl group, a methylthio group, a methoxycarbonyl group, or a hydroxymethyl group. Moreover, the said substituent may be substituted by the further substituent and may not be substituted. The further substituent is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylthio group, an acyl group, a halocarbonyl group, a carboxy group, an alkoxycarbonyl group, a hydroxyalkyl group, a mercaptoalkyl group, a hydroxy group, a mercapto group, Group consisting of amino group, aminoalkyl group, alkylamino group, dialkylamino group, aryl group, chain hydrocarbon group, alicyclic hydrocarbon group, alkylsilyl group, dialkylsilyl group, trialkylsilyl group and deuterium atom It is preferable that it is at least one selected from. Examples of the acyl group include an alkanoyl group, and examples of the alkanoyl group include a formyl group. Examples of the halocarbonyl group include a chlorocarbonyl group. The further substituent is more preferably a phenyl group, for example. For example, the hydroxymethyl group as the substituent may be a hydroxydiphenylmethyl group substituted with a phenyl group as the further substituent.

  In the chemical formula (1), Ar is more preferably an ortho-substituted phenyl group. The ortho-substituted phenyl group may be a group in which the ortho-position substituent is integrated with the phenyl group to form a condensed ring. Specifically, for example, a 1-naphthyl group may be used. In addition to the ortho position, it may or may not have a substituent. The ortho-substituted phenyl group is more preferably 2-methoxyphenyl group, 2-methylphenyl group, 2-formylphenyl group, 2- (methylthio) phenyl group, mesityl group, 1-naphthyl group, 2- (methoxycarbonyl). ) Phenyl group, 2- (hydroxydiphenylmethyl) phenyl group, 2- (triphenylmethyl) phenyl group, 2-hydroxyphenyl group, or 2- (chlorocarbonyl) phenyl group.

In the chemical formula (I), each R ¹ is preferably a linear or branched alkyl group or a cycloalkyl group from the viewpoint of the solubility of the pyrene derivative, the ease of synthesis, and the like. In this case, each R ¹ may or may not have a substituent. From the same viewpoint, each R ¹ is more preferably a linear or branched alkyl group. The number of carbon atoms in each case ^{R 1} is a linear or branched alkyl group is not particularly limited, for example, be a like 1～2,3～10,11～12 or 13-20. The carbon number is preferably as large as possible in the range of 20 or less in consideration of the solubility of the pyrene derivative. The number of carbon atoms is more preferably 3 to 10 from the viewpoint of both the solubility of the pyrene derivative and the ease of synthesis. From the same viewpoint, each R ¹ is particularly preferably an n-butyl group.

In the chemical formula (I), each R ² is not particularly limited, and examples thereof include a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxy group, an alkoxycarbonyl group, a hydroxyalkyl group, a mercaptoalkyl group, and a hydroxy group. Group, mercapto group, amino group, aminoalkyl group, alkylamino group, dialkylamino group, aryl group, chain hydrocarbon group, alicyclic hydrocarbon group, alkylsilyl group, dialkylsilyl group, trialkylsilyl group or heavy group It may be a hydrogen atom. Examples of the acyl group include an alkanoyl group, and examples of the alkanoyl group include a formyl group. Each R ³ is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxy group, an alkoxycarbonyl group, a hydroxyalkyl group, a mercaptoalkyl group, a hydroxy group, a mercapto group, an amino group, and an aminoalkyl group. , An alkylamino group, a dialkylamino group, an aryl group, a chain hydrocarbon group, an alicyclic hydrocarbon group, an alkylsilyl group, a dialkylsilyl group, a trialkylsilyl group, or a deuterium atom. Examples of the acyl group include an alkanoyl group, and examples of the alkanoyl group include a formyl group. For example, in view of the ease of synthesis of pyrene derivatives and the like, in the chemical formula (I), each R ² is a hydrogen atom, and each a that is the number of substitutions of R ³ is 0 (that is, the substituent R ³ Is preferably absent).

  In the chemical formula (I), it is preferable that at least one of Ar is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, because a space rich in π electrons is easily formed. . Further, it is preferable that both Ars are each a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, because a space rich in π electrons is easily formed. In Ar, the substituted or unsubstituted aryl group and the substituted or unsubstituted heteroaryl group are not particularly limited, and are, for example, as described above.

In the chemical formula (I), each Ar is, as described above, a substituted or unsubstituted silyl group, a trialkylsilyl group, a substituted or unsubstituted ethynylene group represented by -Si (R ¹⁰⁰ ) ₃ , tri Alkylsilylethynylene group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, arylamino group, diarylamino group, alkylamino group, dialkylamino group, bis (trialkylsilyl) amino group, substituted or Unsubstituted saturated or unsaturated alicyclic hydrocarbon group, substituted or unsubstituted saturated or unsaturated non-aromatic heterocyclic ring, substituted or unsubstituted piperidyl group, substituted or unsubstituted piperazyl group, substituted or unsubstituted Or a substituted or unsubstituted morpholino group. Said -Si substituted or unsubstituted silyl group represented by (R ¹⁰⁰⁾ _3, a trialkylsilyl group, a substituted or unsubstituted ethynylene group, trialkylsilyl ethynylene group, an alkylamino group, a dialkylamino group, and bis ( The alkyl group in the trialkylsilyl) amino group is not particularly limited, and is, for example, as described above. In addition, the aryl group in the arylamino group and diarylamino group is not particularly limited, and is, for example, the same as each of the aryl groups, and may be a substituted aryl group or an unsubstituted aryl group. In the substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ , R ¹⁰⁰ is a hydrogen atom or a hydrocarbon group as described above, and the hydrocarbon group is linear or branched. However, it may be cyclic, saturated or unsaturated, may or may not have a substituent, and each R ¹⁰⁰ may be the same or different. It is preferred that at least one of R ¹⁰⁰ is a hydrocarbon group, and more preferably all R ¹⁰⁰ is a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an aryl group, an aralkyl group, and the like. More preferably, —Si (R ¹⁰⁰ ) ₃ is a trialkylsilyl group. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and the like. Examples of the trialkylsilylethynylene group include a trimethylsilylethynyl group and a triethylsilylethynyl group. As said arylamino group, a phenylamino group etc. are mentioned, for example. Examples of the diarylamino group include a diphenylamino group. Examples of the alkylamino group include a methylamino group, an ethylamino group, and a propylamino group. Examples of the dialkylamino group include a dimethylamino group, a diethylamino group, and a dipropylamino group. Examples of the bis (trialkylsilyl) amino group include a bis (trimethylsilyl) amino group. The substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group is not particularly limited and is, for example, as described above. The substituted or unsubstituted saturated or unsaturated non-aromatic heterocycle is not particularly limited, and is, for example, as described above, preferably a substituted or unsubstituted piperidyl group, a substituted or unsubstituted piperazyl group, A substituted or unsubstituted pyrrolidyl group, or a substituted or unsubstituted morpholino group.

前記化学式（Ｉ’）中、Ａｒは、前記化学式（Ｉ）で定義される置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基であり、
Ｒ^４は、アリール基を除く任意の置換基であり、
Ｒ^１、Ｒ^２、Ｒ^３およびａは、前記化学式（Ｉ）と同じである。 In the pyrene derivative represented by the chemical formula (I), when only one of Ar is an aryl group, for example, a pyrene derivative represented by the following chemical formula (I ′) may be used.

In the chemical formula (I ′), Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined by the chemical formula (I),
R ⁴ is an optional substituent except an aryl group,
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I).

In the chemical formula (I ′), R ⁴ is not particularly limited, and examples thereof include alkyl groups, alkoxy groups, alkylthio groups, acyl groups, alkanoyl groups, carboxy groups, alkoxycarbonyl groups, hydroxyalkyl groups, mercaptoalkyl groups, hydroxy groups. Group, mercapto group, amino group, aminoalkyl group, alkylamino group, dialkylamino group, chain hydrocarbon group, alicyclic hydrocarbon group, alkylsilyl group, dialkylsilyl group, -Si (R ¹⁰⁰ ) ₃ It may be a substituted or unsubstituted silyl group, trialkylsilyl group, deuterium atom, or formyl group.

Particularly preferable among the pyrene derivatives are, for example, pyrene derivatives represented by any of the following chemical formulas (101) to (108) and (1001) to (1026).

The pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof is represented by the chemical formula (I), for example, as shown in (1) to (4) below. Can have excellent properties. However, the following properties (1) to (4) are exemplifications, and do not limit the pyrene derivative of the present invention, tautomers, geometric isomers or stereoisomers thereof, or salts thereof.

(1) When at least one of Ar is an aryl group (which may be a heteroaryl group), the aryl group is directly bonded to the pyrene ring, and thus a space rich in π electrons centered on pyrene ( π electron space). If both Ar are aryl groups, a space rich in π electrons can be formed. Further, by directly bonding an aryl group to pyrene, which is a large aromatic ring, for example, a much wider π-electron space can be formed as compared with the case where benzene rings are bonded to each other.
(2) Even when Ar is a substituent other than an aryl group, various characteristics according to the type of the substituent can be exhibited. For example, when Ar is a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ (for example, a trialkylsilyl group), the substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ or By converting an unsubstituted silyl group into another substituent (such as an aryl group), it can be used as a synthetic intermediate. In addition, when Ar is an arylamino group, diarylamino group, alkylamino group, dialkylamino group, bis (trialkylsilyl) amino group, or heteroaryl group, the absorption band of the pyrene ring is longer wavelength side It is also possible to use a compound transferred to Such a compound can be used as a pigment, for example.
(3) Since the hydrocarbon group R ¹ is introduced at two locations, it has excellent solubility in organic solvents and is easy to use for various applications.
(4) Since all of the 1-position, 3-position, 6-position and 8-position having the highest activity in the pyrene ring are substituted with Ar and R ¹ , it is stable and durable, and has low toxicity.

In order to achieve the effect of forming a space rich in π-electrons centered on pyrene, the aryl group (Ar) in the chemical formula (I) may be further arylated directly or via a linker (bonding chain) or the like. More preferably, the groups are attached. For example, in the pyrene derivative (108), as shown in the following chemical formula (108-3D), by taking a cage-type molecular structure in which the bottom surface is formed of pyrene and the side surface is formed of a benzene ring, It is considered that a wide π electron space can be formed. The following chemical formula (108-3D) is a diagram schematically showing an example of a three-dimensional structure that the pyrene derivative (108) can take, and the results of X-ray crystal structure analysis, molecular orbital calculation, etc. It is not a reflected figure. Moreover, a pyrene derivative (108) and this invention are not limited at all by the following chemical formula (108-3D).

Furthermore, the pyrene derivative represented by the chemical formula (I) is not limited to the above (101) to (108) and (1001) to (1026), and is arbitrary. Specifically, for example, arbitrary options can be selected and combined freely from the examples of R ¹ , R ² , R ³ , a and Ar. Specifically, for example, a pyrene derivative represented by any of the numbers (109) to (117) in Table 1 below may be used. The pyrene derivatives in Table 1 below are examples in which two R ¹ are the same and two Ar are the same, but the two R ¹ may be different, Ar may be different. According to the IUPAC nomenclature and the like, the number given to the pyrene carbon varies depending on the combination of the substituents bonded thereto, but in Table 1 below, for convenience, the carbon to which R ¹ is bonded is represented by The 6th position is unified, and the carbon to which Ar is bonded is unified at the 3rd and 8th positions.

<2. Method for producing pyrene derivative>
The production method of the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof is not particularly limited, but it is convenient and preferable to produce the pyrene derivative according to the present invention. . Hereinafter, the production method of the present invention will be described.

前記化学式（II）中、
Ｒ^１、Ｒ^２、Ｒ^３およびａは、前記化学式（Ｉ）と同じであり、
Ｘは、ハロゲノ基であり、各Ｘは、同一でも異なっていても良く、
前記化学式（III）中、
Ａｒは、前記化学式（Ｉ）で定義される置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基である。 <2-1. First Manufacturing Method>
As described above, in the first production method of the present invention, in the chemical formula (I), Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. Derivatives, tautomers, geometric isomers or stereoisomers thereof, or salts thereof. As described above, the first production method comprises cross-coupling a halogenated pyrene derivative represented by the following chemical formula (II) and an aryl boronic acid represented by the following chemical formula (III) in the presence of a palladium catalyst. It includes a cross-coupling step (Scheme 1 below) for ring reaction.

In the chemical formula (II),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I),
X is a halogeno group, and each X may be the same or different;
In the chemical formula (III),
Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined by the chemical formula (I).

The cross-coupling reaction between the organic halide and the organic boronic acid is sometimes referred to as the Suzuki-Miyaura cross-coupling reaction or simply the Suzuki-Miyaura reaction. In particular, as in the coupling step (Scheme 1), biaryl can be easily synthesized by cross-coupling of aryl halide and arylboronic acid. In the coupling step (Scheme 1), other aryl boron compounds can be used instead of aryl boronic acids, but aryl boronic acids are preferred from the viewpoint of high reactivity and convenience. Similarly, pyrene triflate (a compound in which X in the chemical formula (II) is a CF ₃ —SO ₃ — group) can be used instead of the halogenated pyrene derivative. Pyrene derivatives are preferred.

In the cross-coupling step, that is, in the coupling reaction of the halogenated pyrene derivative (II) and the arylboronic acid (III), conditions such as a solvent, a reaction temperature, a reaction time, and a reagent are not particularly limited. It may be set appropriately with reference to the known Suzuki-Miyaura reaction. For example, the palladium catalyst is not particularly limited, but Pd ₂ (dba) ₃ .CHCl ₃ (tris (dibenzylideneacetone) dipalladium (0) chloroform adduct), PdCl ₂ (palladium chloride), Pd (OAc ) ₂ (palladium acetate) and the like. The cross-coupling step is preferably performed, for example, in the presence of a base in addition to the halogenated pyrene derivative (II), the arylboronic acid (III) and the palladium catalyst. The base is not particularly limited, and examples thereof include alkali metal fluorides such as potassium fluoride, cesium fluoride, calcium fluoride, and sodium fluoride, potassium phosphate, cesium carbonate, potassium carbonate, sodium hydroxide, and barium hydroxide. The base etc. generally used by Suzuki-Miyaura reaction etc. are mentioned, etc., and may be used independently or may be used together. The cross coupling step can also be performed under mild conditions that do not use strong alkali or the like, for example. The cross coupling step may be performed without a solvent, but is preferably performed in the presence of a solvent. The solvent is not particularly limited. For example, Suzuki such as THF (tetrahydrofuran), diethyl ether, dioxane, dimethyl ether, ethyl methyl ether, cyclopentyl methyl ether, toluene, benzene, N, N-dimethylformamide, hexane, etc. -The solvent etc. which are generally used by Miyaura reaction are mentioned, You may use independently or may use multiple types together. Moreover, although the said cross coupling process may be performed in air | atmosphere, it is preferable to carry out in inert gas atmosphere, such as nitrogen and argon.

  In the cross-coupling step, the reaction temperature and reaction time may be appropriately set according to the structure of the substrate (the halogenated pyrene derivative (II) and the arylboronic acid (III)), and are not particularly limited. The said reaction temperature is 40-160 degreeC, for example, Preferably it is 60-140 degreeC, More preferably, it is 80-120 degreeC. The reaction time is, for example, 3 to 24 hours (hr), preferably 3 to 12 hours (hr), more preferably 3 to 6 hours (hr). The amount ratio of the reactants, the solvent, etc. is not particularly limited, and may be, for example, a stoichiometric ratio or other ratio, and may be set appropriately.

  In the cross coupling process, two Ars may be introduced at a time (in one step), or cross coupling is performed twice (in two steps), and one Ar is used in each step. They may be introduced separately. The cross coupling step is preferably performed in two steps when each Ar is different, and is preferably performed in one step when each Ar is the same.

  In addition, the purification or isolation method of the target product (pyrene derivative (I)) produced in the cross coupling step is not particularly limited, and can be performed according to a conventional method. Specifically, for example, a method as in an embodiment described later may be used, and the method is not limited thereto, and any other method may be used.

前記化学式（Ｉ’）中、
Ａｒは、前記化学式（Ｉ）で定義される置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基であり、
Ｒ^１、Ｒ^２、Ｒ^３およびａは、前記化学式（Ｉ）と同じであり、
Ｒ^４は、アリール基以外の任意の置換基であり、
前記化学式（II）、（IV）および（Ｖ）中、
Ｒ^１、Ｒ^２、Ｒ^３およびａは、前記化学式（Ｉ’）と同じであり、
Ｘは、ハロゲノ基であり、前記化学式（II）中における各Ｘは、同一でも異なっていても良く、
前記化学式（IV）中、
Ｍは、金属であり、
前記化学式（Ｖ）中、
Ｒ^４は、前記化学式（Ｉ’）と同じであり、
前記化学式（III）中、
Ａｒは、前記化学式（Ｉ’）と同じである。 <2-2. Second and third production methods>
Next, as described above, the second production method of the present invention is represented by the following chemical formula (I ′) (only one of the 3-position and 8-position is aryl-substituted): It is a method for producing the tautomer, geometric isomer or stereoisomer, or a salt thereof. In this production method, a metallization step of metallizing a halogenated pyrene derivative represented by the following chemical formula (II) to produce a pyrene derivative represented by the following chemical formula (IV), pyrene represented by the following chemical formula (IV) reacting the derivative with R ⁴ cation by introducing a substituent R ⁴ in a substituted group introduction step of producing a pyrene derivative represented by the following formula (V), and, pyrene represented by the following chemical formula (V) A cross-coupling step is included in which a derivative and an aryl boronic acid represented by the following chemical formula (III) are subjected to a cross-coupling reaction in the presence of a palladium catalyst.

In the chemical formula (I ′),
Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined by the chemical formula (I),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I),
R ⁴ is an optional substituent other than an aryl group,
In the chemical formulas (II), (IV) and (V),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I ′),
X is a halogeno group, and each X in the chemical formula (II) may be the same or different;
In the chemical formula (IV),
M is a metal,
In the chemical formula (V),
R ⁴ is the same as the chemical formula (I ′),
In the chemical formula (III),
Ar is the same as in the chemical formula (I ′).

  In the metallization step, the metal M is preferably, for example, an alkali metal, and more preferably lithium. The metallization step may be, for example, metallization using an organic alkali metal. The organic alkali metal is not particularly limited, but n-BuLi (normal butyl lithium), MeLi (methyl lithium), sec-BuLi (secondary butyl lithium), t-BuLi (tertiary butyl lithium), PhLi (phenyl lithium). N-BuLi is particularly preferable. The solvent is preferably an ether such as THF, diethyl ether, dioxane, dimethyl ether, ethyl methyl ether or cyclopentyl methyl ether, or an aromatic hydrocarbon such as toluene or benzene. The reaction temperature and reaction time are not particularly limited, and may be appropriately set with reference to similar known reactions. For example, the reaction may be started while cooling in a dry ice bath or a liquid nitrogen bath so that the reaction does not run away, and the reaction temperature may be gradually raised to room temperature. In the present invention, “room temperature” is not particularly limited, but is, for example, 5 to 35 ° C. The reaction time is, for example, 1 to 12 hours (hr), preferably 1 to 6 hours (hr), more preferably 1 to 2 hours (hr). The metallization is preferably performed in an inert gas atmosphere such as nitrogen or argon from the viewpoint of preventing side reactions. The amount ratio of the reactants, the solvent, etc. is not particularly limited, and may be, for example, a stoichiometric ratio or other ratio, and may be set appropriately.

In the substituent introduction step, the compound (IV) is, for example, TMEDA (tetramethylethylenediamine), TEA (triethylamine), DME (1,2-dimethoxyethane), PMDETA (N, N, N ′, N ″). , N ″ -pentamethyldiethylenetriamine), CPME (methoxycyclopentane), or the like, and may be reacted after stabilizing the metalated moiety (M). Other reaction conditions are not particularly limited, and can be appropriately set according to the structure of R ⁴ with reference to, for example, known similar reactions. In the substituent introduction step, for example, after the metalation step, a reagent for introducing R ⁴ may be added as it is without isolating the compound (IV), and a so-called one-pot reaction may be performed. Moreover, the reaction conditions in the cross coupling step are not particularly limited, and may be the same as those in the cross coupling step in the first manufacturing method, for example.

In the second production method of the present invention, in the chemical formulas (V) and (I ′), R ⁴ is preferably a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ , More preferably, it is a trialkylsilyl group. If R ⁴ is a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ , for example, as described later, the —Si (R ¹⁰⁰ ) ₃ is replaced with a halogeno group (for example, a bromo group). By using it as a synthetic equivalent, R ⁴ can be easily substituted with another substituent. In addition, although not necessarily clear, for example, it is considered that the solubility of the pyrene derivative may be further increased when R ⁴ is —Si (R ¹⁰⁰ ) (for example, a trialkylsilyl group). When R ⁴ is —Si (R ¹⁰⁰ ) ₃ , for example, in the substituent introduction step, for example, the TMEDA (tetramethylethylenediamine), TEA (triethylamine), DME (1,2-dimethoxyethane), It is also possible to carry out the reaction simply without using a stabilizer such as PMDETA (N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine) or CPME (methoxycyclopentane). When R ⁴ is —Si (R ¹⁰⁰ ) ₃ in the substituent introduction step, the reagent for introducing the —Si (R ¹⁰⁰ ) ₃ is not particularly limited, and examples thereof include halogenated trialkylsilanes. Can be mentioned. The amount of the reagent used is not particularly limited, and may be, for example, a stoichiometric amount or other amount, and may be set appropriately. Although the reaction temperature in this case is not specifically limited, For example, -78-50 degreeC, Preferably it is -20-50 degreeC, More preferably, it can be 0-50 degreeC. Although the reaction time is not particularly limited, it can be, for example, 1 to 24 hr, preferably 1 to 10 hr, more preferably 1 to 3 hr.

前記化学式（Ｉ’）および（III’）中、
Ａｒは、前記化学式（Ｉ）で定義される置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基であり、各Ａｒは同一でも異なっていても良く、
前記化学式（Ｉ’）中、
Ｒ^１、Ｒ^２、Ｒ^３およびａは、前記化学式（Ｉ）と同じであり、
Ｒ^４は、 −Ｓｉ（Ｒ^１００）_３で表される置換もしくは無置換のシリル基であり、
前記化学式（Ｖ’’）中、
Ａｒは、前記化学式（Ｉ）で定義される置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基であり、
Ｒ^１、Ｒ^２、Ｒ^３およびａは、前記化学式（Ｉ）と同じである。 Next, the third manufacturing method of the present invention is as described above.
In the chemical formula (I), Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,
By the second production method of the present invention, a silylpyrene derivative for producing a silylpyrene derivative in which R ⁴ in the chemical formula (I ′) is a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ Manufacturing process,
A halogenation step of producing a halogenated pyrene derivative represented by the following chemical formula (V ″) by reacting the silylpyrene derivative represented by the chemical formula (I ′) with a halogenating agent; and
A halogenated pyrene derivative represented by the following chemical formula (V ″) and an aryl boronic acid represented by the following chemical formula (III ′) are subjected to a cross-coupling reaction in the presence of a palladium catalyst to obtain the following chemical formula (I): Including a second cross-coupling step to produce the represented pyrene derivative,
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

In the chemical formulas (I ′) and (III ′),
Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined by the chemical formula (I), and each Ar may be the same or different;
In the chemical formula (I ′),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I),
R ⁴ is a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ ;
In the chemical formula (V ″),
Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined by the chemical formula (I),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I).

  The silylpyrene derivative production process for producing the silylpyrene derivative represented by the chemical formula (I ′) is as described in the second production method of the present invention.

The halogenation step for producing the halogenated pyrene derivative represented by the chemical formula (V ″) by reacting the pyrene derivative represented by the chemical formula (I ′) with a halogenating agent is not particularly limited, It can be suitably carried out with reference to the reaction conditions of known similar reactions. Specifically, for example, the reaction can be carried out simply by dissolving or suspending the pyrene derivative represented by the chemical formula (I ′) and the halogenating agent in a halogenated solvent and stirring them. The halogenating agent is not particularly limited, and may be, for example, a source of halogen cations (for example, Cl ⁺ , Br ⁺ , I ^+, etc.). Examples of the halogenating agent include bromine (Br ₂ ), NBS (N-bromosuccinimide), NCS (N-chlorosuccinimide), NIS (N-iodosuccinimide), and the like. The halogenated solvent is not particularly limited, and examples thereof include methylene chloride, chloroform, and carbon tetrachloride. The reaction temperature in the halogenation step is not particularly limited, and can be appropriately set depending on the pyrene derivative represented by the chemical formula (I ′), the type of the halogenating agent, and the like. The reaction temperature may be, for example, −78 to 50 ° C., preferably −20 to 30 ° C., more preferably −5 to 30 ° C. For example, at the start of the reaction, the solution of the halogenating agent may be dropped while cooling so that the reaction does not run away, and the reaction temperature may be raised after the reaction is stabilized. The reaction time of the halogenation step is not particularly limited, but may be, for example, 1 to 24 hr, preferably 1 to 12 hr, more preferably 1 to 5 hr. The longer the reaction time, the more easily the reaction proceeds. However, for example, the reaction may be performed for a necessary time while confirming the progress of the reaction by TLC (thin layer chromatography) or the like. The amount ratio of the reactants, the solvent, etc. is not particularly limited, and may be, for example, a stoichiometric ratio or other ratio, and may be set appropriately.

  Moreover, the reaction conditions of the second cross coupling step are not particularly limited, but may be the same as, for example, the cross coupling step in the first or second production method of the present invention.

  In the second or third production method of the present invention, the two Ars in the chemical formula (I) are introduced in two stages one by one, so that the two Ars are different from each other. Suitable for the synthesis of derivatives. Conventionally, it has been very difficult to introduce such different substituents at the 1-position and 6-position (or 3-position and 8-position) of pyrene. This is because it is difficult to appropriately control the reactivity of pyrene and introduce a predetermined substituent only at a predetermined position. However, according to the second or third production method of the present invention, an asymmetric pyrene derivative in which different substituents are introduced into the 1-position and 6-position (or 3-position and 8-position) of pyrene, respectively, is synthesized. But it can be done very easily. Specifically, for example, as described in Examples 9 to 34 described later.

  In addition, as described above, such an asymmetric pyrene derivative is subjected to cross-coupling twice (in two stages) in the first production method of the present invention, and each Ar is separately separated in each stage. It can also be synthesized by introduction. However, the synthesis by the second or third production method of the present invention makes the control of the reaction much easier, and the desired asymmetric pyrene derivative can be obtained simply, reliably and in high yield. preferable. On the other hand, a symmetrical pyrene derivative in which two Ars in the chemical formula (I) are the same can be synthesized by the second or third production method of the present invention. However, such a symmetric pyrene derivative is preferable in the first production method of the present invention because it is easier to produce two Ars at a time by one (one step) cross-coupling, because it can be produced easily. .

In the first, second and third production methods of the present invention, two substituents R ¹ are introduced into the pyrene derivative (II) which is the starting material of the schemes 1 and 2. Thus, as compared with no R ¹ pyrene derivatives, the solubility in organic solvents, for example may be about 5 to 15 times. However, this numerical value is merely an example and does not limit the present invention. By increasing the solubility in this way, usability in various reactions and the like is significantly improved. In addition, since the pyrene derivative (II) has two halogeno groups X, two aryl groups can be introduced using this as a starting material, for example, as in the first production method of the present invention. .

The method for producing (synthesizing) the pyrene derivative (II) is not particularly limited. For example, the method shown in the following scheme 3 is simple and preferable.

Specifically, the scheme 3 can be performed as follows, for example. That is, first, a halogenating agent is reacted with pyrene (VI) to synthesize (manufacture) halogenated pyrene (VII) (first halogenation step). In the chemical formula (VII), Hal ¹ is halogen and may be the same as or different from X in the chemical formula (II). The reaction conditions in the first halogenation step are not particularly limited. For example, the halogenating agent that is a source of (Hal ¹ ) ⁺ ions is not particularly limited, and examples thereof include bromine (Br ₂ ), NBS (N-bromosuccinimide), NCS (N-chlorosuccinimide), and the like. Is mentioned. The reaction solvent is not particularly limited, and examples thereof include halogenated solvents such as methylene chloride, chloroform, and carbon tetrachloride. Although reaction temperature is not specifically limited, either, it is 10-40 degreeC, for example, Preferably it can be set to 20-35 degreeC. The higher the reaction temperature, the faster the reaction proceeds, but it may be set as appropriate according to the reaction scale and the like. Although reaction time is not specifically limited, either, it is 0.5-8 hr, for example, Preferably, it can be set as 0.5-1 hr, 1-4 hr, or 4-8 hr. The longer the reaction time, the more easily the reaction proceeds. However, for example, the reaction may be performed for a necessary time while confirming the progress of the reaction by TLC (thin layer chromatography) or the like. The amount ratio of the reactants, the solvent, etc. is not particularly limited, and may be, for example, a stoichiometric ratio or other ratio, and may be set appropriately.

Next, the halogen (Hal ¹ ) of the halogenated pyrene derivative (VII) is substituted (metalated) with a metal M ′ to obtain a metallated pyrene derivative (VIII) (metalation step). The metal M ′ is preferably an alkali metal, and particularly preferably lithium. The metal M ′ may be the same as or different from the metal M in the second manufacturing method. The reaction conditions in this metallization step are not particularly limited, and may be the same as, for example, the metallization step described in the second production method of the present invention.

Then, the M 'metal pyrene derivative (VIII) is reacted with R ¹ -Hal ^2, by substituting the substituents R ^1, the pyrene derivative obtained by introducing a R ¹ (IX) (R ¹ introduction step ). The ^{R 1} is the same as ^{R 1} in the formula (II) or (I). Hal ² is halogen and may be the same as or different from X in chemical formula (II) and Hal ¹ in chemical formula (VII). In this R ¹ introduction step, the metallated pyrene derivative (VIII) is, for example, TMEDA (tetramethylethylenediamine), TEA (triethylamine), DME (1,2-dimethoxyethane), PMDETA (N, N, N You may make it react, after stabilizing a metalation part (M ') by', N '', N ''-pentamethyldiethylenetriamine), CPME (methoxycyclopentane), etc. In the R ¹ introduction step, the reaction solvent is not particularly limited. For example, the reaction may be carried out using the solvent in the metalation step as it is (in one pot) without isolating the metalated pyrene derivative (VIII). The reaction temperature is not particularly limited, but may be, for example, −78 to 40 ° C., preferably −78 to 0 ° C., 0 to 20 ° C., or 20 to 40 ° C. The higher the reaction temperature, the faster the reaction proceeds, but it may be set as appropriate according to the reaction scale and the like. Although reaction time is not specifically limited, either, it is 0.5-8 hr, for example, Preferably, it can be set as 0.5-1 hr, 1-4 hr, or 4-8 hr. The longer the reaction time, the more easily the reaction proceeds. However, for example, the reaction may be performed for a necessary time while confirming the progress of the reaction by TLC (thin layer chromatography) or the like. The amount ratio of the reactants, the solvent, etc. is not particularly limited, and may be, for example, a stoichiometric ratio or other ratio, and may be set appropriately.

  Further, the pyrene derivative (IX) is halogenated to obtain a pyrene derivative (II ′) (second halogenation step). X in the chemical formula (II ′) is halogen and is the same as X in the chemical formula (II). The reaction conditions for the second halogenation step are not particularly limited, and may be the same as, for example, the first halogenation step.

Furthermore, substituents R ² and R ³ are introduced into the pyrene derivative by an appropriate method to obtain a pyrene derivative (II). When R ² is a hydrogen atom and the substitution number a of R ³ is 0 (that is, the substituent R ³ does not exist), the pyrene derivative (II ′) and the pyrene derivative (II) are the same. The step of introducing the substituents R ² and R ³ can be omitted.

  More specifically, the scheme 3 can also be performed as in the following examples, for example. The production of the pyrene derivative may be difficult from the viewpoints of the solubility of the raw materials, the reactivity, etc., but according to the methods such as the above-mentioned schemes 1 to 3 or the examples described later, A pyrene derivative (II) can also be easily synthesized.

<2-3. Fourth to ninth manufacturing methods>
As described above, the fourth production method of the present invention is as follows.
The pyrene derivative represented by the chemical formula (I) is a pyrene derivative represented by the chemical formula (V),
In the chemical formula (V), R ⁴ is a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ ;
A metalation step of producing a pyrene derivative represented by the chemical formula (IV) by metallizing the halogenated pyrene derivative represented by the chemical formula (II); and
Said formula is reacted with a cation of the pyrene derivative and R ⁴ of formula (IV) by introducing a substituent R ^4, including substituents introduction step of producing a pyrene derivative represented by the formula (V),
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

  That is, the fourth production method of the present invention is a production method that includes the metallization step and the substituent introduction step in the second production method of the present invention and does not include the cross coupling step. As described above, the pyrene derivative represented by the chemical formula (V) can be used as an intermediate in the second production method of the present invention. However, the use of the pyrene derivative represented by the chemical formula (V) is not limited to this, and any use may be used.

As described above, the fifth production method of the present invention is as follows.
The pyrene derivative represented by the chemical formula (I) is a pyrene derivative represented by the chemical formula (V ″),
A silylpyrene derivative production process for producing a silylpyrene derivative represented by the chemical formula (I ′) by the third production method of the present invention, and
A halogenation step of producing a halogenated pyrene derivative represented by the chemical formula (V ″) by reacting the silylpyrene derivative represented by the chemical formula (I ′) with a halogenating agent,
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

  That is, the fifth manufacturing method of the present invention is a manufacturing method that includes the silylpyrene derivative manufacturing step and the halogenation step in the third manufacturing method of the present invention, and does not include the second cross-coupling step. As described above, the pyrene derivative represented by the chemical formula (V ″) can be used as an intermediate in the third production method of the present invention. However, the use of the pyrene derivative represented by the chemical formula (V ″) is not limited to this, and any use may be used.

Next, the sixth production method of the present invention comprises:
In the first, second, third or fifth manufacturing method of the present invention,
In the cross-coupling step, a substituted or unsubstituted saturated or unsaturated non-aromatic heterocyclic compound, a substituted or unsubstituted alcohol, substituted or unsubstituted, instead of the arylboronic acid represented by the chemical formula (III) Using substituted phenol, arylamine, diarylamine, alkylamine, dialkylamine, or bis (trialkylsilyl) amine,
In the cross-coupling step, Ar introduced into the pyrene derivative (I ′) is substituted or unsubstituted aryl group or substituted or unsubstituted heteroaryl group, substituted or unsubstituted saturated or unsaturated non-aromatic An aromatic heterocycle, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, an arylamino group, a diarylamino group, an alkylamino group, a dialkylamino group, or a bis (trialkylsilyl) amino group,
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

The seventh manufacturing method of the present invention comprises:
In the third or sixth production method of the present invention,
In the second cross-coupling step, in place of the arylboronic acid represented by the chemical formula (III), a substituted or unsubstituted saturated or unsaturated non-aromatic heterocyclic compound, a substituted or unsubstituted alcohol, a substituted Or using unsubstituted phenol, arylamine, diarylamine, alkylamine, dialkylamine, or bis (trialkylsilyl) amine,
In the second cross-coupling step, Ar introduced into the pyrene derivative (I) is substituted or unsubstituted aryl group or substituted or unsubstituted heteroaryl group, substituted or unsubstituted saturated or unsaturated non-substituted An aromatic heterocycle, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, an arylamino group, a diarylamino group, an alkylamino group, a dialkylamino group, or a bis (trialkylsilyl) amino group ,
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

In the sixth or seventh production method of the present invention, the cross coupling step or the second cross coupling step is not particularly limited. For example, in the coexistence of a palladium catalyst, a ligand (ligand), and a base. You can go there. Such a reaction may be referred to as, for example, a Backward-Hartwig cross coupling reaction. A general backwald-Hartwig cross coupling reaction can be illustrated as shown in the following scheme B1 or B2, for example. However, the following schemes B1 and B2 are merely examples and do not limit the present invention. In the following schemes B1 and B2, Ar ^a is an arbitrary aryl group, and X is halogen. In the case where the following scheme B1 or B2 is applied to the sixth or seventh production method of the present invention, the pyrene ring corresponds to Ar ^a in the following schemes B1 and B2. Further, in the following scheme B1, each R is a hydrogen atom or an arbitrary substituent, and may be the same or different, and two Rs may be combined to form a ring together with the nitrogen atom to which they are bonded. It may be formed. Moreover, R in the following scheme B2 is a hydrogen atom or an arbitrary substituent.

In the sixth or seventh production method of the present invention, the reaction conditions for the Backward-Hartwig cross coupling reaction are not particularly limited. The reaction conditions may be appropriately set with reference to, for example, known reaction conditions for the Backward-Hartwig cross coupling reaction. For example, the palladium catalyst is not particularly limited, but Pd ₂ (dba) ₃ .CHCl ₃ (chloroform complex of tris (dibenzylideneacetone) dipalladium (0)), PdCl ₂ (palladium chloride), Pd (OAc) ₂ (palladium acetate). Examples of the ligand include BINAP (2,2′-bis (diphenylphosphino) -1,1′-binaphthyl), DPPF (1,1′-bis (diphenylphosphino) ferrocene), X-Phos (2 -Dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl) and the like. Examples of the base include alkali metal alkoxides and alkali metal salts. More specifically, for example, NaO ^t Bu (sodium tertiary butoxide), K ₃ PO ₄ (potassium phosphate), Examples include Cs ₂ CO ₃ (cesium carbonate). The reaction solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as toluene, halogenated solvents such as methylene chloride, ether solvents such as tetrahydrofuran, and the like. The reaction temperature is not particularly limited, but may be, for example, 25 to 150 ° C, preferably 30 to 110 ° C, more preferably 40 to 80 ° C. Although the reaction time is not particularly limited, it can be, for example, 1 to 48 hr, preferably 3 to 20 hr, more preferably 8 to 15 hr. The amount ratio of the reactants, the solvent, etc. is not particularly limited, and may be, for example, a stoichiometric ratio or other ratio, and may be set appropriately.

Next, an eighth production method of the present invention is as follows.
In the first, second, third or fifth manufacturing method of the present invention,
In the cross-coupling step, substituted or unsubstituted acetylene is used instead of the arylboronic acid represented by the chemical formula (III),
Ar introduced into the pyrene derivative (I ′) in the cross-coupling step is a substituted or unsubstituted ethynylene group instead of a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

The ninth production method of the present invention comprises:
In the third, sixth or eighth manufacturing method of the present invention,
In the second cross-coupling step, substituted or unsubstituted acetylene is used instead of the arylboronic acid represented by the chemical formula (III),
Ar introduced into the pyrene derivative (I) in the second cross-coupling step is a substituted or unsubstituted ethynylene group instead of a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
This is a method for producing the pyrene derivative of the present invention, its tautomer, geometric isomer or stereoisomer, or a salt thereof.

In the eighth or ninth production method of the present invention, the cross coupling step or the second cross coupling step is not particularly limited. For example, the cross coupling step or the second cross coupling step may be performed in the presence of a palladium catalyst, a copper catalyst, and an amine. good. Such a reaction is sometimes called, for example, a Sonogashira cross-coupling reaction. A general Sonogashira cross coupling reaction can be illustrated as shown in the following scheme S, for example. However, the following scheme S is merely an example and does not limit the present invention. In the following scheme S, Ar ^a is an arbitrary aryl group, and X is halogen. In the case where the following scheme S is applied to the eighth or ninth production method of the present invention, the pyrene ring corresponds to Ar ^a in the following scheme S. Moreover, in the following scheme B1, R is a hydrogen atom or an arbitrary substituent.

In the 8th or 9th manufacturing method of this invention, the reaction conditions of the said Sonogashira cross coupling reaction are not specifically limited. The reaction conditions may be set as appropriate with reference to, for example, the known Sonogashira cross-coupling reaction conditions. For example, as the reagent for introducing the substituted or unsubstituted ethynylene group, the corresponding substituted or unsubstituted acetylene can be used. The substituted or unsubstituted acetylene is not particularly limited, and examples thereof include 1- (trimethylsilyl) acetylene and 1- (triethylsilyl) acetylene. Examples of the palladium catalyst is not particularly _{limited, PdCl 2 (PPh 3) 2} , Pd 2 (dba) 3 · CHCl 3 , and the like. The copper catalyst is not particularly limited, and examples thereof include copper (I) iodide and copper (I) chloride. Examples of the amine include triethylamine, methylamine, and diethylamine. The reaction solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as toluene and benzene, halogenated solvents such as methylene chloride, ether solvents such as tetrahydrofuran, and the like. Although reaction temperature is not specifically limited, either, for example, 25-155 degreeC, Preferably it is 30-130 degreeC, More preferably, it can be set as 60-110 degreeC. Although the reaction time is not particularly limited, it can be, for example, 1 to 48 hr, preferably 5 to 24 hr, more preferably 8 to 12 hr. The amount ratio of the reactants, the solvent, etc. is not particularly limited, and may be, for example, a stoichiometric ratio or other ratio, and may be set appropriately.

  The 1st-9th manufacturing method of this invention is not limited to the above description, A change is possible suitably. For example, the reaction may be carried out by appropriately coexisting other substances in addition to the respective reactants, catalysts and the like. Moreover, a catalyst, a solvent, etc. may be used independently or may be used together. The 1st-9th manufacturing method of this invention can also be performed with reference to the reaction conditions etc. of the Example mentioned later, for example.

<3. Complexes and products containing pyrene derivatives>
The use of the pyrene derivative of the present invention is not particularly limited, and can be arbitrarily used. For example, it can be used for the complex, catalyst, electronic material, luminescent material, or dye of the present invention.

  As described above, the complex of the present invention is a complex containing the pyrene derivative of the present invention, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof as a ligand. The structure of the complex of the present invention is not particularly limited. For example, a structure in which a molecule or atom as a guest is trapped in the π electron space formed by the pyrene derivative of the present invention may be used. In the present invention, “molecules” and “atoms” are not limited to being electrically neutral, but also include cases in an ionic state.

  As described above, the complex of the present invention is a catalyst comprising the pyrene derivative of the present invention, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof, or the complex of the present invention. The catalyst of the present invention can realize, for example, reactivity different from that of the conventional catalyst by incorporating a substrate into the π-electron space formed by the pyrene derivative of the present invention. For example, since the pyrene derivative of the present invention includes a pyrene ring as described above and can form a wide π-electron space, it can be applied to a substrate having a large molecular size. However, these are examples, and the catalyst of the present invention is not limited by these explanations. The application of the catalyst of the present invention is not particularly limited, and can be used for an appropriate reaction. For example, if the pyrene derivative of the present invention has optical activity, it can be used as an asymmetric synthesis catalyst using it as a ligand.

  In the present invention, the π electron space formed by the pyrene derivative of the present invention is sometimes referred to as “π chemical space”, focusing on chemical phenomena such as chemical reactions occurring there. Examples of the utilization method of the π chemical space include the catalyst of the present invention. In addition to this, examples of the method of using the π electron space or π chemical space include molecular recognition. The “molecule recognition” includes not only molecules but also atom recognition. In the molecular recognition, for example, a molecule or atom that is a guest may be recognized by the π electron space or π chemical space based on characteristics such as size and charge. In the molecular recognition, only one of these characteristics or a plurality of these characteristics may be recognized.

Furthermore, the pyrene derivative or complex of the present invention can also be used for the electronic material or light-emitting material of the present invention as described above. For example, it is excellent as an electronic material or a light-emitting material when the π electrons of the pyrene ring and the aryl group (Ar) are conjugated on the same plane, or do not exist on the same plane and are not conjugated, or by switching between the two. May exhibit the same properties. In addition, as described above, the pyrene derivative of the present invention is stable because all of the 1-position, 3-position, 6-position, and 8-position having the highest activity in the pyrene ring are substituted with Ar and R ^1. It can have the property of high durability. Thereby, for example, it is possible to obtain a stable electronic material or light-emitting material having high durability against water, oxygen, heat, or the like. However, these descriptions are also examples, and the electronic material and the light emitting material of the present invention are not limited at all.

  The electronic material of the present invention is not particularly limited, and examples thereof include organic EL materials and semiconductors. The light emitting material of the present invention is not particularly limited, and examples thereof include fluorescent materials and dyes. The light emitting material of the present invention can also obtain different light emission wavelengths by changing the conjugate length of π electrons derived from the difference in structure.

  Furthermore, the use of the pyrene derivative or complex of the present invention is not limited thereto, and for example, it may be used for the same use as known pyrene or a derivative thereof, or may be used for any other use.

  Examples of the present invention will be described below. However, the present invention is not limited to the following examples.

<Equipment, reagents, etc.>
¹ H and ¹³ C NMR spectra were recorded at 400 MHz and 100 MHz using a BRUKER-SPECTROSPIN-400 (trade name) and a 5 mm QNP probe, respectively. The chemical shift value was recorded in parts per million (ppm) by directly referring to the external tetramethylsilane (TMS) using the resonance of a small amount of monoprotic solvent as an internal standard. The abbreviation s represents a single line (singlet), d represents a double line (doublet), t represents a triple line (triplet), q represents a quadruple line (quartet), m is Represents a multiple line. Elemental analysis was performed using Yanaco MT-5 CHN-Corder (trade name). Unless otherwise specified, “Anal.” Represents an elemental analysis value. Regarding the elemental analysis value, “Calcd. For” represents a calculated value, and “Found” represents an actual measurement value. Mass spectra were measured using JEOL GC-mate II (trade name) in FAB mode. Column chromatography was performed using silica gel (Kanto Chemical Co., Inc., trade name Silica Gel 60N). Thin layer chromatographic analysis was performed using Merck silica gel 60 F ₂₅₄ (trade name). The reaction was carried out under an argon atmosphere unless otherwise specified. Reagents were purchased from Kanto Chemical Co., Inc., Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., and Acros Organics. All reagents were used without further purification. Anhydrous THF solvent was purchased from Kanto Chemical Industry Co., Ltd.

First, in Examples 1 to 8, the pyrene derivatives (101) to (108) were prepared using a pyrene derivative (1,6-dibutyl-3,8-dibromopyrene) represented by Compound No. 1 in the following Scheme 4 as a raw material. Synthesized. In addition, Ar in the following scheme 4 is an aryl group. 1,6-dibutyl-3,8-dibromopyrene was synthesized according to the following reference example.

前記ピレン誘導体（１０１）〜（１０８）を前記スキーム４にしたがって合成するに先立ち、まず、スキーム４の出発原料である化合物１（１，６−ジブチル−３，８−ジブロモピレン）を合成した。その合成は、上記スキーム５にしたがって行った。なお、上記スキーム５は、大きく３段階に分けることができるため、以下、スキーム５−１〜５−３に分けて具体的に説明する。なお、上記スキーム５中において、数字の直後の「eq」は、原料のピレン誘導体に対する当量を表す。以下においても、特に断らない限り、同様である。 <Reference Example: Synthesis of 1,6-dibutyl-3,8-dibromopyrene>

Prior to the synthesis of the pyrene derivatives (101) to (108) according to the scheme 4, the compound 1 (1,6-dibutyl-3,8-dibromopyrene), which is the starting material of the scheme 4, was first synthesized. The synthesis was performed according to Scheme 5 above. In addition, since the said scheme 5 can be divided roughly into 3 steps, it divides into schemes 5-1 to 5-3 below and demonstrates concretely. In Scheme 5 above, “eq” immediately after the number represents the equivalent to the starting pyrene derivative. The same applies to the following unless otherwise specified.

上記スキーム５−１に従い、１，６−ジブロモピレン（化合物２）を合成した。すなわち、まず、１Ｌの二口フラスコに、ピレン(18.2g， 90mmol)を入れ、さらに四塩化炭素CCl₄(405mL)を加えて室温で撹拌した。それにより得られた淡黄色溶液に、臭素Br₂(9.6mL, 190mmol)のCCl₄(60mL)溶液を、３時間かけて滴下した。さらに室温で２時間撹拌すると、反応混合物は、白色懸濁液となった。それを濾過して得られた濾取物を、メタノール(300mL)およびトルエン(約500mL)で洗浄し、濾過することで、粗生成物を淡褐色固体として得た。その粗生成物を、トルエン(約600-250=350mL)で再結晶し、目的物である１，６−ジブロモピレン（化合物２）を、白色固体として得た（収量10.0g, 収率31%)。なお、副生成物である１，８−ジブロモピレンは、前述した１回の再結晶操作で除去することができた。以下に、１，６−ジブロモピレン（化合物２）の¹H NMR分析値を示す。併せて、図１に、１，６−ジブロモピレン（化合物２）の¹H NMRチャートを示す。 <Scheme 5-1: Synthesis of 1,6-dibromopyrene (Compound 2)>

1,6-Dibromopyrene (Compound 2) was synthesized according to Scheme 5-1 above. That is, first, pyrene (18.2 g, 90 mmol) was put into a 1 L two-necked flask, carbon tetrachloride CCl ₄ (405 mL) was further added, and the mixture was stirred at room temperature. A CCl ₄ (60 mL) solution of bromine Br ₂ (9.6 mL, 190 mmol) was added dropwise to the resulting pale yellow solution over 3 hours. After further stirring at room temperature for 2 hours, the reaction mixture became a white suspension. The filtered product obtained by filtering it was washed with methanol (300 mL) and toluene (about 500 mL) and filtered to obtain a crude product as a light brown solid. The crude product was recrystallized from toluene (about 600-250 = 350 mL) to obtain 1,6-dibromopyrene (compound 2) as a target product as a white solid (yield 10.0 g, yield 31%). ). The by-product 1,8-dibromopyrene could be removed by one recrystallization operation as described above. The ¹ H NMR analysis value of 1,6-dibromopyrene (Compound 2) is shown below. In addition, FIG. 1 shows a ¹ H NMR chart of 1,6-dibromopyrene (compound 2).

¹ H NMR analysis value of 1,6-dibromopyrene (compound 2):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.49 (d, 2H, J = 9.2Hz), 8.30 (d, 2H, J = 8.2Hz), 8.15 (d, 2H, J = 9.2Hz), 8.09 (d, (2H, J = 8.2Hz).

化合物２すなわち１，６−ジブロモピレン(2.86g, 7.5mmol）の無水THF(36mL)溶液を、−78℃に冷やし、ノルマルブチルリチウムn-BuLi(18mmol, 1.67Mヘキサン溶液)を、7分間かけて滴下した。それにより得られた懸濁液を、さらに40分間撹拌すると、黄色の懸濁液になった。そこに、求電子剤である１−ブロモブタン(1.95mL, 18mmol)を、5分間かけてゆっくりと加えた。その混合物の温度を室温まで上げ、さらに2時間撹拌した。その後、0℃でメタノール(30mL)を加えて反応を停止させ、温度を、再び室温まで上昇させた。これを除媒濃縮後、クロロホルム(250mL)に溶かし、その溶液を、分液漏斗に移した。有機相を、水(250mL)および飽和食塩水(250mL)で洗浄し、Na₂SO₄で乾燥し、濾過し、除媒濃縮して、粗生成物を得た。なお、「除媒濃縮」は、溶液等から溶媒を減圧留去等により除去して濃縮することをいう。この粗生成物をTLC（薄層クロマトグラフィー）で展開したところ、４スポットが確認された。この粗生成物を、クロロホルムを溶離剤とした濾過カラムクロマトグラフィーにより精製し、追って、ヘキサンを溶離剤とした濾過カラムクロマトグラフィーにより、さらに精製した。その生成物を、クロロホルム/メタノール(3.5mL/21mL)で再沈殿させ、目的物である化合物３すなわち１，６−ジブチルピレンを、白色固体として得た(収量1.11g, 収率47%)。以下に、１，６−ジブチルピレン（化合物３）の¹H NMR分析値を示す。また、図２に、１，６−ジブチルピレン（化合物３）の¹H NMRチャートを示す。 <Scheme 5-2: Synthesis of 1,6-dibutylpyrene (Compound 3)>

Compound 2, ie 1,6-dibromopyrene (2.86 g, 7.5 mmol) in anhydrous THF (36 mL) was cooled to −78 ° C. and normal butyl lithium n-BuLi (18 mmol, 1.67 M in hexane) was added over 7 minutes. And dripped. The resulting suspension was stirred for an additional 40 minutes and became a yellow suspension. Thereto, 1-bromobutane (1.95 mL, 18 mmol) as an electrophile was slowly added over 5 minutes. The temperature of the mixture was raised to room temperature and further stirred for 2 hours. Thereafter, methanol (30 mL) was added at 0 ° C. to stop the reaction, and the temperature was raised again to room temperature. After removing the solvent, this was dissolved in chloroform (250 mL), and the solution was transferred to a separatory funnel. The organic phase was washed with water (250 mL) and saturated brine (250 mL), dried over Na ₂ SO ₄ , filtered, and concentrated to remove the solvent to give a crude product. Note that “concentration of solvent removal” refers to concentration by removing a solvent from a solution or the like by distillation under reduced pressure or the like. When this crude product was developed by TLC (Thin Layer Chromatography), 4 spots were confirmed. The crude product was purified by filtration column chromatography using chloroform as an eluent, and further purified by filtration column chromatography using hexane as an eluent. The product was reprecipitated with chloroform / methanol (3.5 mL / 21 mL) to obtain the target compound 3, ie, 1,6-dibutylpyrene, as a white solid (yield 1.11 g, yield 47%). The ¹ H NMR analysis value of 1,6-dibutylpyrene (Compound 3) is shown below. FIG. 2 shows a ¹ H NMR chart of 1,6-dibutylpyrene (Compound 3).

¹ H NMR analysis value of 1,6-dibutylpyrene (compound 3):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.22 (d, J = 9.2Hz, 2H), 8.08 (d, J = 7.7Hz, 2H), 8.05 (d, J = 9.2Hz, 2H), 7.85 (d, J = 7.7Hz, 2H), 3.34 (t, J = 7.7Hz, 4H), 1.84 (tt, J = 7.7Hz, 7.7Hz, 4H), 1.51 (tq, J = 7.3Hz, 7.7Hz, 4H), 1.00 (t, J = 7.3Hz, 6H).

１Ｌの二口フラスコに、化合物３すなわち１，６−ジブチルピレン(17.4g, 55.4mmol)を入れ、さらに、四塩化炭素CCl₄(336mL)を加えて室温で撹拌した。それにより得られた淡黄色の懸濁液に、臭素Br₂(5.9mL, 116mmol)を、7分間かけて滴下した。それを室温で30分間撹拌した。その後、0℃で、メタノール(290mL)を加えて反応を停止させ、温度を室温まで上昇させた。それにより得られた沈殿物を、濾過し、メタノール(約200mL)で洗浄することで、粗生成物を、淡赤色固体として得た。その粗生成物を、ベンゼン(650-325=325mL)で再結晶し、目的物である１，３−ジブチル−３，８−ジブロモピレン（化合物１）を、白色固体として得た(収率72%, 収量18.6g)。以下に、１，３−ジブチル−３，８−ジブロモピレン（化合物１）の¹H NMR分析値を示す。併せて、図３に、１，３−ジブチル−３，８−ジブロモピレン（化合物１）の¹H NMRチャートを示す。 <Scheme 5-3: Synthesis of 1,6-dibutyl-3,8-dibromopyrene (Compound 1)>

Compound 3, that is, 1,6-dibutylpyrene (17.4 g, 55.4 mmol), was added to a 1 L two-necked flask, carbon tetrachloride CCl ₄ (336 mL) was further added, and the mixture was stirred at room temperature. Bromine Br ₂ (5.9 mL, 116 mmol) was added dropwise to the resulting pale yellow suspension over 7 minutes. It was stirred at room temperature for 30 minutes. Thereafter, at 0 ° C., methanol (290 mL) was added to stop the reaction, and the temperature was raised to room temperature. The resulting precipitate was filtered and washed with methanol (ca. 200 mL) to give the crude product as a pale red solid. The crude product was recrystallized from benzene (650-325 = 325 mL) to obtain the desired 1,3-dibutyl-3,8-dibromopyrene (Compound 1) as a white solid (yield 72). %, Yield 18.6 g). The ¹ H NMR analysis value of 1,3-dibutyl-3,8-dibromopyrene (Compound 1) is shown below. In addition, FIG. 3 shows a ¹ H NMR chart of 1,3-dibutyl-3,8-dibromopyrene (Compound 1).

¹ H NMR analysis value of 1,3-dibutyl-3,8-dibromopyrene (compound 1):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.41 (d, J = 9.5Hz, 2H), 8.23 (d, J = 9.5Hz, 2H), 8.12 (s, 2H), 3.28 (t, J = 7.8Hz, 4H), 1.82 (tt, J = 7.8Hz, 7.8Hz, 4H), 1.51 (tq, J = 7.8Hz, 7.3Hz, 4H), 1.00 (t, J = 7.3Hz, 6H).

<Examples 1 to 8: Synthesis of arylated pyrene derivative>
According to Scheme 4 (reproduced below), a Suzuki-Miyaura cross-coupling reaction between 1,6-dibutyl-3,8-dibromopyrene (Compound 1) and boronic acid was performed. The pyrene derivatives (101) to (107) could be produced (synthesized) by changing the boronic acid in various ways. Table 2 below shows the reaction conditions and yield. As shown in Table 2, the target pyrene derivative could be obtained in a high yield of 70% or more in any of the examples. The pyrene derivative (108) could be obtained by reacting the pyrene derivative (107) with phenyl lithium, as will be described later. In addition, “quant.” In the following Table 2 represents that the yield was quantitative (that is, almost 100%). The same applies to the following.

化合物１すなわち１，６−ジブチル−３，８−ジブロモピレン(235mg, 0.5mmol)、K₃PO₄・nH₂O(318mg, 1.5mmol)、２−メトキシフェニルボロン酸(228mg, 1.5mmol)、Pd₂(dba)₃・CHCl₃(20.7mg, 4mol%)およびPCy₃(11.2mg, 8mol%)を無水トルエン(12mL)中に加えて得られた懸濁液を110℃で加熱し、ワインのような暗赤色の懸濁液を得た。その懸濁液を、さらに、前記温度で2時間40分加熱撹拌し、黒色の懸濁液を得た。なお、Pd₂(dba)₃・CHCl₃は、トリス(ジベンジリデンアセトン)ジパラジウム(0)のクロロホルム付加体を意味し、PCy₃は、トリシクロヘキシルホスフィンを意味する（以下同じ）。その後、加熱を終了して反応を停止させ、反応混合物を静置して室温まで冷却した。その反応混合物をセライト（商品名）で濾過して不要な沈殿を除き、水(10mL×2)および飽和食塩水(10mL)で洗浄し、Na₂SO₄で乾燥後、濾過し、減圧濃縮して、粗生成物を、橙色の粘状物として得た。その粗生成物を、ヘキサン/ジクロロメタン=4/1の混合溶媒を溶離剤としたカラムクロマトグラフィーにより、精製した。このようにして、目的生成物である１，６−ジブチル−３，８−ビス（２−メトキシフェニル）ピレン（化合物（１０１））を、黄色の粘状物として得た（収率98%, 収量259mg）。それを、プロピオニトリルEtCN(7mL)により再結晶し、純粋な１，６−ジブチル−３，８−ビス（２−メトキシフェニル）ピレン（化合物（１０１））を、淡黄色固体として得た(収率81%, 収量214mg)。以下に、１，６−ジブチル−３，８−ビス（２−メトキシフェニル）ピレン（化合物（１０１））の機器分析値を示す。併せて、図４および５に、１，６−ジブチル−３，８−ビス（２−メトキシフェニル）ピレン（化合物（１０１））の¹H NMRチャートおよび¹³C NMRチャートを示す。 <Example 1: 1,6-dibutyl-3,8-bis (2-methoxyphenyl) pyrene (compound (101))>

Compound 1, namely 1,6-dibutyl-3,8-dibromopyrene (235 mg, 0.5 mmol), K ₃ PO ₄ .nH ₂ O (318 mg, 1.5 mmol), 2-methoxyphenylboronic acid (228 mg, 1.5 mmol), The suspension obtained by adding Pd ₂ (dba) ₃ · CHCl ₃ (20.7 mg, 4 mol%) and PCy ₃ (11.2 mg, 8 mol%) in anhydrous toluene (12 mL) was heated at 110 ° C. A dark red suspension was obtained. The suspension was further heated and stirred at the above temperature for 2 hours and 40 minutes to obtain a black suspension. Pd ₂ (dba) ₃ · CHCl ₃ means a chloroform adduct of tris (dibenzylideneacetone) dipalladium (0), and PCy ₃ means tricyclohexylphosphine (the same applies hereinafter). Thereafter, the heating was terminated to stop the reaction, and the reaction mixture was left to cool to room temperature. The reaction mixture was filtered through Celite (trade name) to remove unnecessary precipitates, washed with water (10 mL × 2) and saturated brine (10 mL), dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure. The crude product was obtained as an orange sticky product. The crude product was purified by column chromatography using a mixed solvent of hexane / dichloromethane = 4/1 as an eluent. In this way, 1,6-dibutyl-3,8-bis (2-methoxyphenyl) pyrene (compound (101)), which was the target product, was obtained as a yellow viscous product (yield 98%, Yield 259 mg). It was recrystallized from propionitrile EtCN (7 mL) to give pure 1,6-dibutyl-3,8-bis (2-methoxyphenyl) pyrene (compound (101)) as a pale yellow solid ( Yield 81%, Yield 214 mg). The instrumental analysis value of 1,6-dibutyl-3,8-bis (2-methoxyphenyl) pyrene (compound (101)) is shown below. In addition, FIGS. 4 and 5 show a ¹ H NMR chart and a ¹³ C NMR chart of 1,6-dibutyl-3,8-bis (2-methoxyphenyl) pyrene (compound (101)).

Instrumental analysis of 1,6-dibutyl-3,8-bis (2-methoxyphenyl) pyrene (compound (101)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.14 (d, J = 9.5Hz, 2H), 7.84 (dd, J = 9.5Hz, 6.3Hz, 2H), 7.79 (d, J = 1.3Hz, 2H), 3.71 -3.72 (s, 6H), 3.38-3.26 (m, 4H), 1.84 (tt, J = 7.8Hz, 7.8Hz, 4H), 1.49 (tq, J = 7.8Hz 7.4Hz, 4H), 0.97 (d, ^{J = 7.4Hz, 6H). 13} C NMR (100MHz, CDCl 3) δ 157.8, 136.3, 133.9, 132.7, 130.8, 129.7, 129.2, 128.6, 128.2, 126.1, 125.8, 122.5, 120.9, 55.9, 34.2, 33.8, 23.2, 14.4. Anal. Calcd. For C ₃₈ H ₃₈ O ₂ : C, 86.65; H, 7.27. Found: C, 86.70; H, 7.23.

化合物１すなわち１，６−ジブチル−３，８−ジブロモピレン(235mg, 0.5mmol)、K₃PO₄・nH₂O(318mg, 1.5mmol)、ｏ−トリルボロン酸(204mg, 1.5mmol)、Pd₂(dba)₃・CHCl₃(20.7mg, 4mol%)およびPCy₃(11.2mg, 8mol%)を無水トルエン(12mL)中に加えて得られた懸濁液を110℃で加熱し、ワインのような暗赤色の懸濁液を得た。その懸濁液を、さらに、前記温度で4時間加熱撹拌し、黒色の懸濁液を得た。その後、加熱を終了して反応を停止させ、反応混合物を静置して室温まで冷却した。その反応混合物をセライト（商品名）で濾過して不要な沈殿を除き、水(10mL×2)および飽和食塩水(10mL)で洗浄し、Na₂SO₄で乾燥後、濾過し、減圧濃縮して、粗生成物を、橙色の粘状物として得た。その粗生成物を、ヘキサンを溶離剤としたカラムクロマトグラフィーにより、精製した。このようにして、目的生成物である１，６−ジブチル−３，８−ビス（ｏ−トリル）ピレン（化合物（１０２））を、白色固体として得た（定量的、収量251mg）。それを、ヘキサン(14-8=6mL)により再結晶し、純粋な１，６−ジブチル−３，８−ビス（ｏ−トリル）ピレン（化合物（１０２））を、白色固体として得た(収率55%, 収量137mg)。以下に、１，６−ジブチル−３，８−ビス（ｏ−トリル）ピレン（化合物（１０２））の機器分析値を示す。併せて、図６および７に、１，６−ジブチル−３，８−ビス（ｏ−トリル）ピレン（化合物（１０２））の¹H NMRチャートおよび¹³C NMRチャートを示す。 <Example 2: 1,6-dibutyl-3,8-bis (o-tolyl) pyrene (compound (102))>

Compound 1, namely 1,6-dibutyl-3,8-dibromopyrene (235 mg, 0.5 mmol), K ₃ PO ₄ .nH ₂ O (318 mg, 1.5 mmol), o-tolylboronic acid (204 mg, 1.5 mmol), Pd ₂ The suspension obtained by adding (dba) ₃・ CHCl ₃ (20.7 mg, 4 mol%) and PCy ₃ (11.2 mg, 8 mol%) in anhydrous toluene (12 mL) was heated at 110 ° C. A dark red suspension was obtained. The suspension was further heated and stirred at the above temperature for 4 hours to obtain a black suspension. Thereafter, the heating was terminated to stop the reaction, and the reaction mixture was left to cool to room temperature. The reaction mixture was filtered through Celite (trade name) to remove unnecessary precipitates, washed with water (10 mL × 2) and saturated brine (10 mL), dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure. The crude product was obtained as an orange sticky product. The crude product was purified by column chromatography eluting with hexane. In this manner, 1,6-dibutyl-3,8-bis (o-tolyl) pyrene (compound (102)), which was the target product, was obtained as a white solid (quantitative, yield 251 mg). It was recrystallized from hexane (14-8 = 6 mL) to obtain pure 1,6-dibutyl-3,8-bis (o-tolyl) pyrene (compound (102)) as a white solid (yield). Rate 55%, yield 137 mg). The instrumental analysis values of 1,6-dibutyl-3,8-bis (o-tolyl) pyrene (compound (102)) are shown below. In addition, FIGS. 6 and 7 show a ¹ H NMR chart and a ¹³ C NMR chart of 1,6-dibutyl-3,8-bis (o-tolyl) pyrene (compound (102)).

Instrumental analysis of 1,6-dibutyl-3,8-bis (o-tolyl) pyrene (compound (102)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.10 (d, J = 9.4Hz, 2H), 7.73 (d, J = 9.4Hz, 2H), 7.73 (s, 2H), 7.42-7.34 (m, 8H), 3.36-3.27 (m, 4H), 2.08-2.10 (s, 6H), 1.83 (tt, J = 7.7Hz, 7.7Hz, 4H), 1.47 (tq, J = 7.3Hz 7.7Hz, 4H), 0.96 (t , J = 7.3Hz, 6H). 13 C NMR (100MHz, CDCl 3) δ 141.4, 137.4, 137.1, 136.7, 131.1, 131.0, 130.3, 129.1, 128.5, 127.9, 126.2, 125.9, 125.4, 122.9, 34.3, 33.7 Anal.Calcd.For C ₃₈ H ₃₈ : C, 92.26; H, 7.74. Found: C, 92.24; H, 7.62.

化合物１すなわち１，６−ジブチル−３，８−ジブロモピレン(235mg, 0.5mmol)、K₃PO₄・nH₂O(425mg, 2mmol)、２−ホルミルフェニルボロン酸(225mg, 1.5mmol)、Pd₂(dba)₃・CHCl₃(20.7mg, 4mol%)およびPCy₃(16.8mg, 12mol%)を無水トルエン(12mL)中に加えて得られた懸濁液を110℃で加熱し、ワインのような暗赤色の懸濁液を得た。その懸濁液を、さらに、前記温度で15時間加熱撹拌し、黒色の懸濁液を得た。その後、加熱を終了して反応を停止させ、反応混合物を静置して室温まで冷却した。その反応混合物をセライト（商品名）で濾過して不要な沈殿を除き、水(10mL×2)および飽和食塩水(10mL)で洗浄し、Na₂SO₄で乾燥後、濾過し、減圧濃縮して、粗生成物を、暗黄色固体として得た。その粗生成物を、ヘキサン/ジクロロメタン=1/1の混合溶媒を溶離剤としたカラムクロマトグラフィーにより、精製した。このようにして、目的生成物である２，２’−（３，８−ジブチルピレン−１，６−ジイル）ジベンズアルデヒド（化合物（１０３））を、橙色固体として得た（収率90％, 収量235mg）。それを、プロピオニトリルEtCN(8mL)により再結晶し、純粋な２，２’−（３，８−ジブチルピレン−１，６−ジイル）ジベンズアルデヒド（化合物（１０３））を、黄色固体として得た(収率63%, 収量165mg)。以下に、２，２’−（３，８−ジブチルピレン−１，６−ジイル）ジベンズアルデヒド（化合物（１０３））の機器分析値を示す。併せて、図８および９に、２，２’−（３，８−ジブチルピレン−１，６−ジイル）ジベンズアルデヒド（化合物（１０３））の¹H NMRチャートおよび¹³C NMRチャートを示す。 <Example 3: 2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (103))>

Compound 1, namely 1,6-dibutyl-3,8-dibromopyrene (235 mg, 0.5 mmol), K ₃ PO ₄ .nH ₂ O (425 mg, 2 mmol), 2-formylphenylboronic acid (225 mg, 1.5 mmol), Pd ₂ (dba) ₃ · CHCl ₃ (20.7 mg, 4 mol%) and PCy ₃ (16.8 mg, 12 mol%) were added to anhydrous toluene (12 mL), and the resulting suspension was heated at 110 ° C. A dark red suspension was obtained. The suspension was further heated and stirred at the above temperature for 15 hours to obtain a black suspension. Thereafter, the heating was terminated to stop the reaction, and the reaction mixture was left to cool to room temperature. The reaction mixture was filtered through Celite (trade name) to remove unnecessary precipitates, washed with water (10 mL × 2) and saturated brine (10 mL), dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure. The crude product was obtained as a dark yellow solid. The crude product was purified by column chromatography using a mixed solvent of hexane / dichloromethane = 1/1 as an eluent. Thus, 2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (103)), which was the target product, was obtained as an orange solid (yield 90%, Yield 235 mg). It is recrystallized from propionitrile EtCN (8 mL) to obtain pure 2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (103)) as a yellow solid. (Yield 63%, Yield 165 mg). The instrumental analysis values of 2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (103)) are shown below. In addition, FIGS. 8 and 9 show a ¹ H NMR chart and a ¹³ C NMR chart of 2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (103)).

Instrumental analysis of 2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (103)):
¹ H NMR (400MHz, CDCl ₃ ) δ 9.68-9.67 (m, 2H), 8.24-8.21 (m, 2H), 8.20-8.18 (m, 2H), 7.83 (s, 2H), 7.81-7.76 (m, 4H), 7.68-7.59 (m, 4H), 3.33 (t, J = 7.8Hz, 4H), 1.83 (tt, J = 7.8Hz, 7.5Hz, 4H), 1.48 (tq, J = 7.5Hz 7.4Hz, 4H), 0.97 (t, J = 7.4Hz, 6H). 13 CNMR (100MHz, CDCl 3) δ 192.3, 145.2, 137.1, 137.1, 135.3, 133.9, 132.9, 132.5, 130.3, 129.1, 128.9, 128.5, 127.5, 127.5, 125.8, 123.7, 34.3, 33.7, 23.2, 14.3. Anal.Calcd.For C ₃₈ H ₃₄ O ₂ : C, 87.32; H, 6.56. Found: C, 87.33; H, 6.56.

化合物１すなわち１，６−ジブチル−３，８−ジブロモピレン(235mg, 0.5mmol)、K₃PO₄・nH₂O(318mg, 1.5mmol)、２−ホルミルフェニルボロン酸(228mg, 1.5mmol)、Pd₂(dba)₃・CHCl₃(20.7mg, 4mol%)およびPCy₃(14.0mg, 10mol%)を無水トルエン(12mL)中に加えて得られた懸濁液を110℃で加熱し、橙色の懸濁液を得た。その懸濁液を、さらに、前記温度で13時間20分加熱撹拌し、黒色の懸濁液を得た。その後、加熱を終了して反応を停止させ、反応混合物を静置して室温まで冷却した。その反応混合物をセライト（商品名）で濾過して不要な沈殿を除き、水(10mL×2)および飽和食塩水(10mL)で洗浄し、Na₂SO₄で乾燥後、濾過し、減圧濃縮して、粗生成物を、黄色固体として得た。その粗生成物を、ヘキサン/クロロホルム=1/1の混合溶媒を溶離剤とした濾過カラムクロマトグラフィーにより、精製した。このようにして、目的生成物である｛２，２’−（３，８−ジブチルピレン−１，６−ジイル）ビス（２，１−フェニレン）｝ビス（メチルスルファン）（化合物（１０４））を、黄色粘状物として得た（収率76％, 収量213mg）。それを、プロピオニトリルEtCN(240-180=60mL)により再結晶し、純粋な｛２，２’−（３，８−ジブチルピレン−１，６−ジイル）ビス（２，１−フェニレン）｝ビス（メチルスルファン）（化合物（１０４））を、淡黄色固体として得た(収率51%, 収量142mg)。以下に、｛２，２’−（３，８−ジブチルピレン−１，６−ジイル）ビス（２，１−フェニレン）｝ビス（メチルスルファン）（化合物（１０４））の機器分析値を示す。併せて、図１０および１１に、｛２，２’−（３，８−ジブチルピレン−１，６−ジイル）ビス（２，１−フェニレン）｝ビス（メチルスルファン）（化合物（１０４））の¹H NMRチャートおよび¹³C NMRチャートを示す。 <Example 4: {2,2 '-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (methylsulfane) (compound (104))>

Compound 1, ie 1,6-dibutyl-3,8-dibromopyrene (235 mg, 0.5 mmol), K ₃ PO ₄ .nH ₂ O (318 mg, 1.5 mmol), 2-formylphenylboronic acid (228 mg, 1.5 mmol), The suspension obtained by adding Pd ₂ (dba) ₃ · CHCl ₃ (20.7 mg, 4 mol%) and PCy ₃ (14.0 mg, 10 mol%) in anhydrous toluene (12 mL) was heated at 110 ° C. A suspension of was obtained. The suspension was further heated and stirred at the above temperature for 13 hours and 20 minutes to obtain a black suspension. Thereafter, the heating was terminated to stop the reaction, and the reaction mixture was left to cool to room temperature. The reaction mixture was filtered through Celite (trade name) to remove unnecessary precipitates, washed with water (10 mL × 2) and saturated brine (10 mL), dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure. The crude product was obtained as a yellow solid. The crude product was purified by filtration column chromatography using a mixed solvent of hexane / chloroform = 1/1 as an eluent. Thus, the desired product {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (methylsulfane) (compound (104) ) Was obtained as a yellow gum (yield 76%, yield 213 mg). It is recrystallized from propionitrile EtCN (240-180 = 60 mL) and pure {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} Bis (methylsulfane) (compound (104)) was obtained as a pale yellow solid (51% yield, 142 mg yield). The instrumental analysis values of {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (methylsulfane) (compound (104)) are shown below. . In addition, FIGS. 10 and 11 show {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (methylsulfane) (compound (104)). ¹ H NMR chart and ¹³ C NMR chart are shown.

Instrumental analysis of {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (methylsulfane) (compound (104)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.18 (d, J = 9.5Hz, 2H), 7.77 (s, 2H), 7.76 (d, J = 9.5Hz, 2H), 7.51-7.30 (m, 8H), 3.36-3.27 (m, 4H), 2.32-2.33 (s, 6H), 1.84 (tt, J = 7.5Hz, 7.4Hz, 4H), 1.48 (tq, J = 7.4Hz 7.3Hz, 4H), 0.96 (t , J = 7.3Hz, 6H). 13 C NMR (100MHz, CDCl 3) δ 140.0, 139.3, 136.8, 135.3, 131.45, 131.44, 129.3, 129.0, 128.5, 128.0, 126.2, 125.4, 125.0, 124.7, 123.0, 34.2 , 33.8, 23.2, 16.0, 14.4. Anal.Calcd.For C ₃₈ H ₃₈ O ₂ : C, 81.67; H, 6.85. Found: C, 81.51; H, 6.78.

化合物１すなわち１，６−ジブチル−３，８−ジブロモピレン(235mg, 0.5mmol)、K₃PO₄・nH₂O(425mg, 2mmol)、メシチルボロン酸(328mg, 2mmol)、Pd₂(dba)₃・CHCl₃(41.4mg, 8mol%)およびPCy₃(33.7mg, 24mol%)を無水トルエン(12mL)中に加えて得られた懸濁液を110℃で加熱し、赤ワインのような暗赤色の懸濁液を得た。その懸濁液を、さらに、前記温度で18時間加熱撹拌し、暗褐色の懸濁液を得た。その後、加熱を終了して反応を停止させ、反応混合物を静置して室温まで冷却した。その反応混合物をセライト（商品名）で濾過して不要な沈殿を除き、水(10mL×2)および飽和食塩水(10mL)で洗浄し、Na₂SO₄で乾燥後、濾過し、減圧濃縮して、粗生成物を、橙色粘状物として得た。その粗生成物を、ヘキサン/ジクロロメタン=1/1の混合溶媒を溶離剤とした濾過カラムクロマトグラフィーにより、精製し、さらに、追って、ヘキサンを溶離剤とした濾過カラムクロマトグラフィーにより精製した。このようにして、目的生成物である１，６−ジブチル−３，８−ジメシチルピレン（化合物（１０５））を、白色固体として得た（収率74％, 収量203mg）。それを、プロピオニトリルEtCN(18-7.5=10.5mL)により再結晶し、純粋な１，６−ジブチル−３，８−ジメシチルピレン（化合物（１０５））を、白色固体として得た(収率62%, 収量171mg)。以下に、１，６−ジブチル−３，８−ジメシチルピレン（化合物（１０５））の機器分析値を示す。併せて、図１２および１３に、１，６−ジブチル−３，８−ジメシチルピレン（化合物（１０５））の¹H NMRチャートおよび¹³C NMRチャートを示す。 <Example 5: 1,6-dibutyl-3,8-dimesitylpyrene (compound (105))>

Compound 1, namely 1,6-dibutyl-3,8-dibromopyrene (235 mg, 0.5 mmol), K ₃ PO ₄ .nH ₂ O (425 mg, 2 mmol), mesitylboronic acid (328 mg, 2 mmol), Pd ₂ (dba) ₃ A suspension obtained by adding CHCl ₃ (41.4 mg, 8 mol%) and PCy ₃ (33.7 mg, 24 mol%) in anhydrous toluene (12 mL) was heated at 110 ° C. to obtain a dark red color like red wine. A suspension was obtained. The suspension was further heated and stirred at the above temperature for 18 hours to obtain a dark brown suspension. Thereafter, the heating was terminated to stop the reaction, and the reaction mixture was left to cool to room temperature. The reaction mixture was filtered through Celite (trade name) to remove unnecessary precipitates, washed with water (10 mL × 2) and saturated brine (10 mL), dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure. The crude product was obtained as an orange sticky product. The crude product was purified by filtration column chromatography using a mixed solvent of hexane / dichloromethane = 1/1 as an eluent, and further purified by filtration column chromatography using hexane as an eluent. Thus, 1,6-dibutyl-3,8-dimesitylpyrene (compound (105)), which was the target product, was obtained as a white solid (yield 74%, yield 203 mg). It was recrystallized from propionitrile EtCN (18-7.5 = 10.5 mL) to give pure 1,6-dibutyl-3,8-dimesitylpyrene (compound (105)) as a white solid (yield 62 %, Yield 171 mg). The instrumental analysis values of 1,6-dibutyl-3,8-dimesitylpyrene (compound (105)) are shown below. In addition, FIGS. 12 and 13 show a ¹ H NMR chart and a ¹³ C NMR chart of 1,6-dibutyl-3,8-dimesitylpyrene (compound (105)).

Instrumental analysis value of 1,6-dibutyl-3,8-dimesitylpyrene (compound (105)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.31 (d, J = 9.4Hz, 2H), 7.64 (s, 2H), 7.61 (d, J = 9.4Hz, 2H), 7.08 (s, 2H), 3.31 ( t, J = 7.5Hz, 4H), 2.45 (s, 6H), 1.92 (s, 12H), 1.82 (tt, J = 7.5Hz, 7.5Hz, 4H), 1.44 (tq, J = 7.5Hz 7.4Hz, 4H), 0.95 (t, J = 7.4Hz, 6H). 13 C NMR (100MHz, CDCl 3) δ 137.9, 137.4, 137.2, 137.0, 136.1, 129.1, 128.5, 128.4, 127.9, 126.5, 124.8, 123.0, 34.2 , 33.6, 23.0, 21.5, 21.0, 14.4. Anal.Calcd.For C ₄₂ H ₄₆ : C, 91.58; H, 8.42. Found: C, 91.58; H, 8.42.

化合物１すなわち１，６−ジブチル−３，８−ジブロモピレン(235mg, 0.5mmol)、K₃PO₄・nH₂O(425mg, 2mmol)、１−ナフチルボロン酸(344mg, 2mmol)、Pd₂(dba)₃・CHCl₃(41.4mg, 8mol%)およびPCy₃(33.7mg, 24mol%)を無水トルエン(12mL)中に加えて得られた懸濁液を110℃で加熱し、赤色の懸濁液を得た。その懸濁液を、さらに、前記温度で5時間20分加熱撹拌し、黒色の懸濁液を得た。その後、加熱を終了して反応を停止させ、反応混合物を静置して室温まで冷却した。その反応混合物をセライト（商品名）で濾過して不要な沈殿を除き、水(10mL×2)および飽和食塩水(10mL)で洗浄し、Na₂SO₄で乾燥後、濾過し、減圧濃縮して、粗生成物を、黄色固体として得た。その粗生成物を、ヘキサン/トルエン=1/1の混合溶媒を溶離剤とした濾過カラムクロマトグラフィーにより精製した。このようにして、目的生成物である１，６−ジブチル−３，８−ビス（１−ナフチル）ピレン（または１，６−ジブチル−３，８−ビス（ナフタレン−１−イル）ピレン、化合物（１０６））を、淡黄色固体として得た（定量的、 収量312mg）。それを、プロピオニトリルEtCN(600-530=70mL)により再結晶し、純粋な１，６−ジブチル−３，８−ビス（１−ナフチル）ピレン（化合物（１０６））を、白色固体として得た(収率79%, 収量224mg)。以下に、１，６−ジブチル−３，８−ビス（１−ナフチル）ピレン（化合物（１０６））の機器分析値を示す。併せて、図１４および１５に、１，６−ジブチル−３，８−ビス（１−ナフチル）ピレン（化合物（１０６））の¹H NMRチャートおよび¹³C NMRチャートを示す。 <Example 6: 1,6-dibutyl-3,8-bis (1-naphthyl) pyrene (compound (106))>

Compound 1, ie 1,6-dibutyl-3,8-dibromopyrene (235 mg, 0.5 mmol), K ₃ PO ₄ .nH ₂ O (425 mg, 2 mmol), 1-naphthylboronic acid (344 mg, 2 mmol), Pd ₂ ( dba) ₃ · CHCl ₃ (41.4 mg, 8 mol%) and PCy ₃ (33.7 mg, 24 mol%) in anhydrous toluene (12 mL) were added and the resulting suspension was heated at 110 ° C to give a red suspension A liquid was obtained. The suspension was further heated and stirred at the above temperature for 5 hours and 20 minutes to obtain a black suspension. Thereafter, the heating was terminated to stop the reaction, and the reaction mixture was left to cool to room temperature. The reaction mixture was filtered through Celite (trade name) to remove unnecessary precipitates, washed with water (10 mL × 2) and saturated brine (10 mL), dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure. The crude product was obtained as a yellow solid. The crude product was purified by filtration column chromatography using a mixed solvent of hexane / toluene = 1/1 as an eluent. Thus, the desired product 1,6-dibutyl-3,8-bis (1-naphthyl) pyrene (or 1,6-dibutyl-3,8-bis (naphthalen-1-yl) pyrene, compound (106)) was obtained as a pale yellow solid (quantitative, yield 312 mg). It is recrystallized from propionitrile EtCN (600-530 = 70 mL) to obtain pure 1,6-dibutyl-3,8-bis (1-naphthyl) pyrene (compound (106)) as a white solid. (Yield 79%, yield 224 mg). The instrumental analysis values of 1,6-dibutyl-3,8-bis (1-naphthyl) pyrene (compound (106)) are shown below. In addition, FIGS. 14 and 15 show a ¹ H NMR chart and a ¹³ C NMR chart of 1,6-dibutyl-3,8-bis (1-naphthyl) pyrene (compound (106)).

Instrumental analysis of 1,6-dibutyl-3,8-bis (1-naphthyl) pyrene (compound (106)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.12 (d, J = 9.5Hz, 2H), 8.03-8.00 (m, 4H), 7.89 (s, 2H), 7.72-7.63 (m, 6H), 7.53-7.43 (m, 4H), 7.32-7.39 (m, 2H), 3.30 (t, J = 7.7Hz, 4H), 1.82 (tt, J = 7.7Hz, 7.5Hz, 4H), 1.46 (tq, J = 7.5Hz 7.4Hz, 4H), 0.93 (t , J = 7.4Hz, 6H). 13 C NMR (100MHz, CDCl 3) δ 139.6, 136.9, 135.7, 134.0, 133.5, 130.2, 128.9, 128.8, 128.7, 128.6, 128.2, 127.2, 126.4, 126.2, 126.1, 125.9, 125.8, 123.0, 34.3, 33.8, 23.2, 14.3. Anal.Calcd. For C ₄₄ H ₃₈ : C, 93.24; H, 6.76. Found: C, 93.26; H, 9.81.

化合物１すなわち１，６−ジブチル−３，８−ジブロモピレン(235mg, 0.5mmol)、K₃PO₄・nH₂O(425mg, 2mmol)、ｏ−（メトキシカルボニル）フェニルボロン酸(270mg, 1.5mmol)、Pd₂(dba)₃・CHCl₃(20.7mg, 4mol%)およびPCy₃(16.8mg, 12mol%)を無水トルエン(12mL)中に加えて得られた懸濁液を110℃で加熱し、赤ワインのような暗赤色の懸濁液を得た。その懸濁液を、さらに、前記温度で18.5時間加熱撹拌し、黒色の懸濁液を得た。その後、加熱を終了して反応を停止させ、反応混合物を静置して室温まで冷却した。その反応混合物をセライト（商品名）で濾過して不要な沈殿を除き、水(10mL×2)および飽和食塩水(10mL)で洗浄し、Na₂SO₄で乾燥後、濾過し、減圧濃縮して、粗生成物を、橙色固体として得た。その粗生成物を、ヘキサン/クロロホルム=1/1の混合溶媒を溶離剤としたカラムクロマトグラフィーにより精製した。このようにして、目的生成物であるジメチル−２，２’−（３，８−ジブチルピレン−１，６−ジイル）ジベンゾエート（化合物（１０７））を、淡黄色固体として得た（収率99％, 収量288mg）。それを、プロピオニトリルEtCN(25-18=7mL)により再結晶し、純粋なジメチル−２，２’−（３，８−ジブチルピレン−１，６−ジイル）ジベンゾエート（化合物（１０７））を、橙色固体として得た(収率80%, 収量233mg)。以下に、ジメチル−２，２’−（３，８−ジブチルピレン−１，６−ジイル）ジベンゾエート（化合物（１０７））の機器分析値を示す。併せて、図１６および１７に、ジメチル−２，２’−（３，８−ジブチルピレン−１，６−ジイル）ジベンゾエート（化合物（１０７））の¹H NMRチャートおよび¹³C NMRチャートを示す。 <Example 7: Dimethyl-2,2 '-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (Compound (107))>

Compound 1, namely 1,6-dibutyl-3,8-dibromopyrene (235 mg, 0.5 mmol), K ₃ PO ₄ .nH ₂ O (425 mg, 2 mmol), o- (methoxycarbonyl) phenylboronic acid (270 mg, 1.5 mmol) ), Pd ₂ (dba) ₃ · CHCl ₃ (20.7 mg, 4 mol%) and PCy ₃ (16.8 mg, 12 mol%) in anhydrous toluene (12 mL) were heated at 110 ° C. A dark red suspension like red wine was obtained. The suspension was further heated and stirred at the above temperature for 18.5 hours to obtain a black suspension. Thereafter, the heating was terminated to stop the reaction, and the reaction mixture was left to cool to room temperature. The reaction mixture was filtered through Celite (trade name) to remove unnecessary precipitates, washed with water (10 mL × 2) and saturated brine (10 mL), dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure. The crude product was obtained as an orange solid. The crude product was purified by column chromatography using a mixed solvent of hexane / chloroform = 1/1 as an eluent. Thus, the target product dimethyl-2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (107)) was obtained as a pale yellow solid (yield) 99%, yield 288 mg). It was recrystallized from propionitrile EtCN (25-18 = 7 mL) to give pure dimethyl-2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (107)). Was obtained as an orange solid (80% yield, 233 mg yield). The instrumental analysis value of dimethyl-2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (107)) is shown below. In addition, FIGS. 16 and 17 show a ¹ H NMR chart and a ¹³ C NMR chart of dimethyl-2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (107)). .

Instrumental analysis of dimethyl-2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (107)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.15-8.07 (m, 4H), 8.79-7.48 (m, 10H), 3.40 (s, 3H), 3.31 (s, 3H), 3.29-3.25 (m, 4H) , 1.81 (tt, J = 7.2Hz, 4H), 1.46 (tq, J = 7.2Hz 7.4Hz, 4H), 0.95 (t, J = 7.4Hz, 6H). ¹³ C NMR (100MHz, CDCl ₃ ) δ 164.60 (19), 164.55 (19), 138.4 (5), 138.3 (5), 132.7 (10), 132.7 (10), 132.4 (13), 132.3 (13), 128.86 (15), 128.75 (15), 128.2 (6), 128.1 (6), 127.7 (17), 127.6 (17), 126.4 (8), 124.53 (18), 124.52 (18), 124.47 (7), 122.1 (12), 122.0 (12), 120.90 (9), 120.87 (9), 119.0 (11), 48.2 (20), 48.1 (20), 30.31 (4), 30.29 (4), 29.7 (3), 19.1 (2), 10.4 (1).

化合物（１０７）すなわちジメチル−２，２’−（３，８−ジブチルピレン−１，６−ジイル）ジベンゾエート(291mg, 0.5mmol)、の無水トルエン(30mL)の溶液を、−20℃に冷やし、フェニルリチウムPhLi(3mmol, 1.9Mジブチルエーテル溶液)を、9分間かけて滴下した。それを−20℃に保ったまま1時間攪拌した。1時間後、1規定（1mol/L）の塩酸（10ｍL）を加え反応を停止し、その溶液を、分液漏斗に移した。水相を、クロロホルム(30mL×2)で抽出し、合わせた有機相を飽和食塩水(20mL)で洗浄し、Na₂SO₄で乾燥後、濾過し、減圧濃縮して、粗生成物を、淡黄色固体として得た。この粗生成物をTLC（薄層クロマトグラフィー）で展開したところ、２スポットが確認された。この粗生成物を、ヘキサン/クロロホルム=2/1の混合溶媒を溶離剤としたカラムクロマトグラフィーにより単離精製し、追って、ヘキサン/塩化メチレン=2/1の混合溶媒を溶離剤としたカラムクロマトグラフィーにより、さらに精製した。このようにして、目的生成物である｛２，２’−（３，８−ジブチルピレン−１，６−ジイル）ビス（２，１−フェニレン）｝ビス（ジフェニルメタノール）（化合物（１０８））を白黄色固体として得た。｛２，２’−（３，８−ジブチルピレン−１，６−ジイル）ビス（２，１−フェニレン）｝ビス（ジフェニルメタノール）（化合物（１０８））のトランス体は、収率46％, 収量192mgであり、シス体は、収率36％, 収量150mgであった。トランス体のみ、プロピオニトリルEtCN(90-72=18mL)により再結晶し、純品な｛２，２’−（３，８−ジブチルピレン−１，６−ジイル）ビス（２，１−フェニレン）｝ビス（ジフェニルメタノール）（化合物（１０８））を、白黄色固体として得た(収量75mg, 収率18%)。以下に、｛２，２’−（３，８−ジブチルピレン−１，６−ジイル）ビス（２，１−フェニレン）｝ビス（ジフェニルメタノール）（化合物（１０８））のトランス体およびシス体の機器分析値を、それぞれ示す。 <Example 8: {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (diphenylmethanol) (Compound (108))>

A solution of compound (107), dimethyl-2,2 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (291 mg, 0.5 mmol), in anhydrous toluene (30 mL) was cooled to −20 ° C. Phenyllithium PhLi (3 mmol, 1.9 M dibutyl ether solution) was added dropwise over 9 minutes. It was stirred for 1 hour while keeping at -20 ° C. After 1 hour, 1N (1 mol / L) hydrochloric acid (10 mL) was added to stop the reaction, and the solution was transferred to a separatory funnel. The aqueous phase was extracted with chloroform (30 mL × 2), and the combined organic phases were washed with saturated brine (20 mL), dried over Na ₂ SO ₄ , filtered, and concentrated under reduced pressure. Obtained as a pale yellow solid. When this crude product was developed by TLC (thin layer chromatography), two spots were confirmed. This crude product was isolated and purified by column chromatography using a mixed solvent of hexane / chloroform = 2/1 as an eluent, followed by column chromatography using a mixed solvent of hexane / methylene chloride = 2/1 as an eluent. Further purification by chromatography. Thus, the desired product {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (diphenylmethanol) (compound (108)) Was obtained as a white yellow solid. The trans isomer of {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (diphenylmethanol) (compound (108)) has a yield of 46%, The yield was 192 mg, and the cis-isomer was 36% yield and 150 mg yield. Only the trans isomer was recrystallized from propionitrile EtCN (90-72 = 18 mL) to produce pure {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene) )} Bis (diphenylmethanol) (compound (108)) was obtained as a white yellow solid (yield 75 mg, 18% yield). The trans and cis forms of {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (diphenylmethanol) (compound (108)) are shown below. The instrumental analysis values are shown respectively.

Instrumental analysis of {2,2 ′-(3,8-dibutylpyrene-1,6-diyl) bis (2,1-phenylene)} bis (diphenylmethanol) (compound (108)):
Trans body
Rf value 0.36 (hexane / methylene chloride = 2/1)
¹ H NMR (400MHz, CDCl ₃ ) δ 8.05 (d, J = 9.4Hz, 2H), 7.78 (d, J = 9.4Hz, 2H), 7.42-7.14 (m, 26H), 6.95 (s, 2H), 6.933-6.931 (m, 2H), 2.93-2.64 (m, 4H), 2.64 (s, 2H), 1.51-1.41 (m, 4H), 1.33 (tq, J = 7.2Hz, 4H), 0.94 (t, ^{J = 7.2Hz, 6H). 13} C NMR (100MHz, CDCl 3) δ 148.4, 147.3, 146.4, 139.6, 136.6, 136.2, 134.0, 131.0, 129.8, 128.8 128.7, 128.4, 128.2, 127.9, 127.5, 127.4, 127.1 , 127.0, 126.1, 125.8, 123.1, 84.0, 33.8, 33.5, 23.3, 14.3. FAB-MS m / z: 832 ([M + 2H] ⁺ ).
Cis body
Rf value 0.17 (hexane / methylene chloride = 2/1)
¹ H NMR (400MHz, CDCl ₃ ) δ 8.05 (d, J = 9.4Hz, 2H), 7.78 (d, J = 9.4Hz, 2H), 7.42-7.14 (m, 26H), 6.96-6.94 (m, 2H ), 6.93 (s, 2H), 2.96-2.76 (m, 4H), 2.61 (s, 2H), 1.52-1.54 (m, 4H), 1.34 (tq, J = 7.2Hz, 4H), 0.94 (t, ^{J = 7.2Hz, 6H). 13} C NMR (100MHz, CDCl 3) δ 148.3, 147.3, 146.6, 139.7, 136.5, 136.2, 133.8, 130.9, 129.8, 128.8 128.7, 128.4, 128.23, 128.20, 127.9, 127.5, 127.4 , 127.1, 127.0, 126.1, 125.7, 123.1, 84.0, 33.8, 33.5, 31.9, 23.3 23.0, 14.5, 14.3.FAB-MS m / z: 833 ([M + 2H] ⁺ ).

  As described above, according to Examples 1 to 8, it was possible to easily synthesize pyrene derivatives rich in π electrons in which two benzene rings were directly covalently bonded to the pyrene ring. These pyrene derivatives can be used for an appropriate application as described above, for example, utilizing the property that a wide π-electron space can be formed.

<Examples 9 to 34: Synthesis of various asymmetric pyrene derivatives>
In Examples 9 to 34, various asymmetric pyrene derivatives were synthesized using any one of the second to ninth production methods of the present invention. All of these are included in the pyrene derivative of the present invention represented by the chemical formula (I). More specifically, first, in Example 9, (6-bromo-3,8-dibutylpyren-1-yl) tetramethylsilane (1001) showing high solubility in various organic solvents was synthesized. . Furthermore, in Examples 10 to 34, various asymmetric pyrene derivatives were synthesized using (6-bromo-3,8-dibutylpyren-1-yl) tetramethylsilane (1001) as shown in the following scheme. In addition, although it is guessed that the compound (1001) has improved the solubility with respect to an organic solvent by introduce | transducing TMS (trimethylsilyl), it is not necessarily clear. The bromide (1001) served as an effective substrate in the Suzuki-Miyaura cross-coupling reaction, the Sonogashira cross-coupling reaction, and the Backwald-Hartwig cross-coupling reaction, and coupling bodies for each reaction were obtained. Subsequently, the TMS group was converted to bromine. As a substrate for the reaction, a pyrene derivative (1002) having an ester group, a pyrene derivative (1005) having a formyl group, and a pyrene derivative (1007) having a methoxy group were used. Again for the bromides (1014), (1015) and (1016) obtained by desilylation, Suzuki-Miyaura cross-coupling reaction, Sonogami cross-coupling reaction, or Backwald-Hartwig cross-coupling reaction. Went.

  1,6-Dibromo-3,8-dibutylpyrene used as a starting material for the compound (1001) was synthesized according to the above Reference Example. Thereafter, 1,6-dibromo-3,8-dibutylpyrene was lithiated, and the lithiated product was reacted with chlorotrimethylsilane. As a result, the compound (1001) was obtained with a yield of about 70%. This synthesis was repeated several times to prepare about 25 g of the total amount of the compound (1001). The lithiation proceeded smoothly by adding THF as an additive. In addition, it was confirmed that the compound (1001) quickly dissolved in chloroform, methylene chloride, benzene, toluene, THF, ethyl acetate, acetonitrile, propionitrile, acetone, or hexane.

^a反応は、(a) Mizushima, T.; Yoshida, A.; Harada, A.; Yoneda, Y.; Minatani, T.; Murata, S. Org. Biomol. Chem., 2006, 4, 4336-4344. または(b) Yoshida, A.; Harada, A.; Mizushima, T.; Murata, S. Chem. Lett. 2003, 32, 68-69.を参考にして、後述の実施例１３〜２４のいずれかに記載のとおり行った。
^bパラジウムブラックの形成が完了し、および／またはTLCによる追跡で原料消失を確認したところで、反応を終了させた。
^c反応は、トルエン中、110℃で、5mol% Pd₂(dba)₃, 15mol% PCy₃,およびK₃PO₄(2eq)の共存下で行った。
^d化合物（１００１）(0.25mmol)およびTMSアセチレン(0.75mmol)を、Et₃N(1.5mL)および(1.5mL)の共存下、70℃で反応させた。触媒系として、PdCl₂(PPh₃)₂(0.0125mmol)およびPPh₃(0.025mmol)、ならびにCuI(0.025mmol)を用いた。
^e化合物（１００１）(0.25mmol), ピロリジン(0.75mmol)およびNaO^tBu(0.75mmol)を、トルエン(2mL)中で反応させた。触媒系としては、Pd₂(dba)₃(0.0125mmol)およびBINAP(0.025mmol)を用いた。 <Cross coupling reaction using (6-bromo-3,8-dibutylpyren-1-yl) tetramethylsilane (1001)>
In Examples 13 to 24, (6-8-butylpyrene-6 was obtained by cross-coupling reaction between (6-bromo-3,8-dibutylpyren-1-yl) tetramethylsilane (1001) and various reactants. -Deyl) trimethylsilane derivatives (1002) to (1013) were synthesized. The results are summarized in Table 3 below. Examples 13 to 22 are examples of the Suzuki-Miyaura cross-coupling reaction. The reaction conditions were (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane 0.5 mmol (233 mg), 10 mol%. It was set to 105 ° C. in Pd (PPh ₃ ) ₄ , K ₂ CO ₃ ( ₂ eq), DMF (2 mL). In Examples 13 to 18, it was confirmed by TLC monitoring that the reaction was controlled. In Examples 13-18, as shown in Table 3, the target product was obtained in a high yield of about 80-90%. In Example 19, as a result of using Pd ₂ (dba) ₃ and PCy ₃ as the palladium catalyst, the reaction was completed within 8 hours, and the target product was obtained in 93% yield. In Examples 20 to 22, compound (1001) was reacted with an aryl boronic acid containing a bromine atom, a nitrogen atom and the like. As a result, bromide (1009), benzamide derivative (1010), and pyrrolidine derivative (1011) could be obtained in yields of 90%, 95%, and 47%, respectively. In Example 23, the Sonogashira cross-coupling reaction was performed using trimethylsilylacetylene, and the compound (1012) was obtained in 91% yield. In Example 24, the backwald-Hartwig cross-coupling reaction was performed using pyrrolidine, and the compound (1013) was obtained in 70% yield.

^a reaction is (a) Mizushima, T .; Yoshida, A .; Harada, A .; Yoneda, Y .; Minatani, T .; Murata, S. Org. Biomol. Chem., 2006, 4, 4336-4344 Or (b) Yoshida, A .; Harada, A .; Mizushima, T .; Murata, S. Chem. Lett. 2003, 32, 68-69. As described in the above.
^{b When} the formation of palladium black was completed and / or disappearance of raw materials was confirmed by TLC tracking, the reaction was terminated.
^{The c} reaction was performed in toluene at 110 ° C. in the presence of 5 mol% Pd ₂ (dba) ₃ , 15 mol% PCy ₃ , and K ₃ PO ₄ (2 eq).
^d Compound (1001) (0.25mmol) and TMS acetylene (0.75 mmol), the presence of Et ₃ N (1.5mL) and (1.5 mL), and reacted at 70 ° C.. As the catalyst system, PdCl ₂ (PPh ₃ ) ₂ (0.0125 mmol) and PPh ₃ (0.025 mmol) and CuI (0.025 mmol) were used.
^e Compound (1001) (0.25 mmol), pyrrolidine (0.75 mmol) and NaO ^t Bu (0.75 mmol) were reacted in toluene (2 mL). As the catalyst system, Pd ₂ (dba) ₃ (0.0125 mmol) and BINAP (0.025 mmol) were used.

<Desilylation of 1-substituted (3,8-dibutylpyren-6-yl) trimethylsilane>
In Examples 10 to 12, desilylation reaction of monofunctionalized (3,8-dibutylpyren-6-yl) trimethylsilane was performed. In this reaction, by using bromine, the tetramethylsilyl group is eliminated and the compound (1002), (1005) or (1007) is converted into bromide (1014), (1015) or (1016), respectively. (Scheme below). As a desilylation (bromination) agent, a 1M carbon tetrachloride solution of bromine was used. As a result, the compound (1002) could be converted to (1014) in 91% yield. The same reaction was performed using the compound (1005) or (1007), and the compound (1015) (95% yield) or (1016) (93% yield) could be converted, respectively.

<Preparation of Asymmetric Pyrene Compound from Compounds (1014), (1015) and (1016)>
In Examples 25-34, asymmetrically functionalized pyrene compounds (1017)-(1026) can be synthesized using bromide compounds (1014), (1015) and (1016) in the cross-coupling reaction. did it. The results are summarized in Table 4 below. Bromide (1016) slowly proceeded with the cross-coupling reaction with arylboronic acid (including methyl ester group, formyl group, or pyridine group) (Examples 25 to 27). Further, bromide (1016) was subjected to Sonogashira cross-coupling reaction with trimethylsilylacetylene to obtain 71% yield of the desired product (1020) (Example 28). Furthermore, in the Backwald-Hartwig cross-coupling reaction using pyrrolidine, the target product (1021) was obtained in an 80% yield (Example 29).

^aパラジウムブラックの形成が完了し、および／またはTLCによる追跡で原料消失を確認したところで、反応を終了させた。
^bブロマイド（１０１４）、（１０１５）または（１０１６）(0.25mmol)およびTMSアセチレン(0.75mmol)を、Et₃N(1.5mL)および(1.5mL)の共存下、70℃で反応させた。触媒系として、PdCl₂(PPh₃)₂(0.0125mmol)およびPPh₃(0.025mmol)、ならびにCuI(0.025mmol)を用いた。
^cブロマイド（１０１４）、（１０１５）または（１０１６）(0.25mmol),ピロリジン(0.75mmol)およびNaO^tBu(0.75mmol)を、トルエン(1.5mL)中で反応させた。触媒系としては、Pd₂(dba)₃(0.0125mmol)およびBINAP(0.025mmol)を用いた。 In Examples 30 to 34, Suzuki-Miyaura cross-coupling reaction or Sonogashira cross-coupling reaction was performed using bromide (1014) or (1015). As a result, as shown in Table 4, the target compounds (1022) to (1026) could be obtained in a high yield of 73 to 97%. For example, in Example 30 (compound (1022)), it was clearly confirmed by ¹ H NMR and ¹³ C NMR that a methyl ester group was present at the ortho and para positions. Similarly in Example 32 (compound (1024)), a formyl group is present at the ortho and para positions. As described above, the functional group could be accurately introduced into the core of the pyrene structure by systematic conversion using the compound (1011).

formation of ^a palladium black is completed, and / or at disappearance of the starting materials was confirmed by tracking by TLC, the reaction was terminated.
^b bromide (1014), (1015) or (1016) (0.25 mmol) and TMS acetylene (0.75 mmol), the presence of Et ₃ N (1.5 mL) and (1.5 mL), and reacted at 70 ° C.. As the catalyst system, PdCl ₂ (PPh ₃ ) ₂ (0.0125 mmol) and PPh ₃ (0.025 mmol) and CuI (0.025 mmol) were used.
^c bromide (1014), the (1015) or (1016) (0.25 mmol), pyrrolidine (0.75 mmol) and NaO ^t Bu (0.75 mmol), were reacted in toluene (1.5 mL). As the catalyst system, Pd ₂ (dba) ₃ (0.0125 mmol) and BINAP (0.025 mmol) were used.

1,6-ジブロモ-3,8-ジブチルピレン(7.6g, 16mmol)の無水トルエン(600mL)溶液に、室温で、THF(3.2mL, 38mmol)を加え、続いて、n-BuLi(11mL, 1.63Mヘキサン溶液)を、3分間以上かけて滴下した。その溶液を15分間撹拌し、そして、クロロトリメチルシラン(9.5mL, 48mmol)を、1分間以上かけて加えた。それを室温で2時間撹拌した後、水を加えて反応を停止させた。その後、溶媒を完全に減圧留去し、得られた混合物に、CHCl₃を加え、水相を、CHCl₃で抽出した。有機相を合わせ、飽和食塩水(30mL)で洗浄し、Na₂SO₄で乾燥し、濃縮して、粗生成物を得た。この粗生成物をシリカゲルカラムクロマトグラフィー（溶離剤：ヘキサンのみ）で精製し、目的の(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））を、白色固体として得た(収率70%、収量5.2g)。以下に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））の機器分析値を示す。また、図１８に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（１００１）の¹H NMRチャートを示し、図１９に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））の¹³C NMRチャートを示す。 <Example 9: (6-Bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001))>

To a solution of 1,6-dibromo-3,8-dibutylpyrene (7.6 g, 16 mmol) in anhydrous toluene (600 mL) at room temperature was added THF (3.2 mL, 38 mmol), followed by n-BuLi (11 mL, 1.63 M hexane solution) was added dropwise over 3 minutes. The solution was stirred for 15 minutes and chlorotrimethylsilane (9.5 mL, 48 mmol) was added over 1 minute. After stirring at room temperature for 2 hours, water was added to stop the reaction. Thereafter, the solvent was completely distilled off under reduced pressure, CHCl ₃ was added to the resulting mixture, and the aqueous phase was extracted with CHCl ₃ . The organic phases were combined, washed with saturated brine (30 mL), dried over Na ₂ SO ₄ and concentrated to give the crude product. The crude product was purified by silica gel column chromatography (eluent: hexane only), and the desired (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) was converted to a white solid. (Yield 70%, yield 5.2 g). The instrumental analysis values of (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) are shown below. FIG. 18 shows a ¹ H NMR chart of (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (1001), and FIG. 19 shows (6-bromo-3,8-dibutylpyrene). 1 shows a ¹³ C NMR chart of (1-yl) trimethylsilane (compound (1001)).

Instrumental analysis of (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.43 (d, J = 9.5Hz, 1H), 8.37 (d, J = 9.4Hz, 1H), 8.30 (d, J = 9.5Hz, 1H), 8.21 (d, J = 9.4Hz, 1H), 8.10 (s, 1H), 8.04 (s, 1H), 3.35-3.27 (m, 4H), 1.85-1.83 (m, 4H), 1.56-1.49 (m, 4H), 1.0 (t, J = 7.4, 7.4Hz, 6H), 0.60 (s, 9H). 13 C NMR (100MHz, CDCl 3) δ 138.3, 136.6, 136.1, 134.5, 134.3, 131.2, 129.9, 128.33, 128.25, 128.1 , 127.4, 126.4, 125.2, 124.5, 34.6, 34.11, 34.05, 33.5, 23.3, 23.2, 14.42, 14.38, 1.05. MS (FAB) m / z: 466 (M ⁺ ). Anal. Calcd for C ₂₇ H ₃₃ BrSi : C, 69.66; H, 7.14. Found: C, 69.79; H, 7.10.

メチル 4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００２））(1.0g, 2mmol)の無水CCl₄(4mL)溶液を、0℃に冷却した。その混合物に、3mLの臭素(1MのCCl₄貯蔵液)を、20分間以上かけて滴下し、さらに、15分間撹拌した。さらに、室温にまで温度を上げて反応を続けた。室温でさらに1時間撹拌後、水を加えて反応を停止させた。得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=1/3)で精製し、目的化合物であるメチル 4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンゾエート（化合物（１０１４））を、黄色固体として得た(収量91%、収率903mg)。以下に、メチル 4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンゾエート（化合物（１０１４））の機器分析値を示す。また、図２０に、メチル 4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンゾエート（化合物（１０１４））の¹H NMRチャートを示し、図２１に、メチル 4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンゾエート（化合物（１０１４））の¹³C NMRチャートを示す。 <Example 10: Methyl 4- (6-bromo-3,8-dibutylpyren-1-yl) benzoate (compound (1014))>

A solution of methyl 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1002)) (1.0 g, 2 mmol) in anhydrous CCl ₄ (4 mL) was cooled to 0 ° C. To the mixture, 3 mL of bromine (1M CCl ₄ stock solution) was added dropwise over 20 minutes and stirred for an additional 15 minutes. Further, the reaction was continued by raising the temperature to room temperature. After stirring at room temperature for another hour, water was added to stop the reaction. The resulting crude product was purified by column chromatography (hexane / CHCl ₃ = 1/3), and the target compound methyl 4- (6-bromo-3,8-dibutylpyren-1-yl) benzoate ( Compound (1014)) was obtained as a yellow solid (yield 91%, yield 903 mg). The instrumental analysis value of methyl 4- (6-bromo-3,8-dibutylpyren-1-yl) benzoate (compound (1014)) is shown below. 20 shows a ¹ H NMR chart of methyl 4- (6-bromo-3,8-dibutylpyren-1-yl) benzoate (compound (1014)), and FIG. 21 shows methyl 4- (6- The ¹³ C NMR chart of bromo-3,8-dibutylpyren-1-yl) benzoate (compound (1014)) is shown.

Instrumental analysis of methyl 4- (6-bromo-3,8-dibutylpyren-1-yl) benzoate (compound (1014)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.43 (d, J = 9.5 Hz, 1H), 8.30-8.23 (m, 3H), 8.11-8.04 (3H), 7.83 (s, 1H), 7.71 (d, J = 8.8Hz, 2H), 4.02 (s, 1H), 3.22 (t.J = 7.5, 7.5Hz, 2H), 3.19 (t.J = 7.5, 7.5Hz, 2H), 1.89-1.74 (m, 4H) , 1.56-1.43 (m, 4H), 1.01-0.89 (m, 6H). 13 C NMR (100MHz, CDCl 3) δ 167.3, 146.2, 138.1, 137.5, 136.6, 131.5, 130.9, 129.8, 129.4, 129.2, 128.8 , 128.4, 128.3, 127.1, 127.0, 126.2, 125.4, 125.0, 124.2, 122.9, 120.1, 52.5, 34.3, 34.0, 33.7, 33.3, 31.8, 23.2, 23.0, 22.9, 14.4, 14.3, 14.2.MS (FAB) m / z: 526 (M ⁺ ). Anal. Calcd for C ₃₂ H ₃₁ BrO ₂ : C, 72.86; H, 5.92. Found: C, 72.86; H, 5.81.

4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアルデヒド（化合物（１００５））(982mg, 2mmol)の無水CCl₄(4.5mL)溶液を、0℃に冷却した。その混合物に、3mLの臭素(1MのCCl₄貯蔵液)を、20分間以上かけて滴下し、さらに、15分間撹拌した。さらに、室温にまで温度を上げて反応を続けた。室温でさらに1時間撹拌後、水を加えて反応を停止させた。得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=1/3)で精製し、目的物である4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンズアルデヒド（化合物（１０１５））を、黄色固体として得た(収量93%、収率923mg)。以下に、4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンズアルデヒド（化合物（１０１５））の機器分析値を示す。また、図２２に、4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンズアルデヒド（化合物（１０１５））の¹H NMRチャートを示し、図２３に、4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンズアルデヒド（化合物（１０１５））の¹³C NMRチャートを示す。 <Example 11: 4- (6-Bromo-3,8-dibutylpyren-1-yl) benzaldehyde (Compound (1015))>

A solution of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (compound (1005)) (982 mg, 2 mmol) in anhydrous CCl ₄ (4.5 mL) was cooled to 0 ° C. To the mixture, 3 mL of bromine (1M CCl ₄ stock solution) was added dropwise over 20 minutes and stirred for an additional 15 minutes. Further, the reaction was continued by raising the temperature to room temperature. After stirring at room temperature for another hour, water was added to stop the reaction. The obtained crude product was purified by column chromatography (hexane / CHCl ₃ = 1/3), and the desired 4- (6-bromo-3,8-dibutylpyren-1-yl) benzaldehyde (compound (1015)) was obtained as a yellow solid (93% yield, 923 mg yield). The instrumental analysis value of 4- (6-bromo-3,8-dibutylpyren-1-yl) benzaldehyde (compound (1015)) is shown below. FIG. 22 shows a ¹ H NMR chart of 4- (6-bromo-3,8-dibutylpyren-1-yl) benzaldehyde (compound (1015)), and FIG. 23 shows 4- (6-bromo- The ¹³ C NMR chart of 3,8-dibutylpyren-1-yl) benzaldehyde (compound (1015)) is shown.

Instrumental analysis of 4- (6-bromo-3,8-dibutylpyren-1-yl) benzaldehyde (compound (1015)):
¹ H NMR (400MHz, CDCl ₃ ) δ 10.1 (s, 1H), 8.41 (d, J = 9.5Hz, 1H), 8.26 (d, J = 9.5Hz, 1H), 8.06-8.04 (m, 5H), 7.82 (s, 1H), 7.78 (d, J = 8.0Hz, 2H), 3.30 (t. J = 7.5, 7.5Hz, 2H), 3.16 (t. J = 7.5, 7.5Hz, 2H), 1.85-1.56 (m, 4H), 1.54-1.44 ( m, 4H), 1.04-0.97 (m, 6H). 13 C NMR (100MHz, CDCl 3) δ 192.1, 147.8, 138.2, 137.5, 136.2, 135.4, 131.48, 131.45, 129.9, 129.2, 128.9, 128.3, 128.2, 127.0, 126.9, 126.3, 125.4, 124.8, 124.1, 123.1, 120.2, 34.2, 33.9, 33.6, 33.2, 23.1, 23.0, 14.25, 14.19.MS (FAB) m / z: 496 (M ⁺ ). Anal. Calcd for C ₃₁ H ₂₉ BrO: C, 74.85; H, 5.88. Found: C, 74.81; H, 5.94.

(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)トリメチルシラン（化合物（１００７））(985mg, 2mmol)の無水CCl₄(2mL)溶液を、0℃に冷却した。その混合物に、3mLの臭素(1MのCCl₄貯蔵液)を、20分間以上かけて滴下し、さらに、15分間撹拌した。さらに、室温にまで温度を上げて反応を続けた。室温でさらに1時間撹拌後、水を加えて反応を停止させた。得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=1/3)で精製し、目的物である1-ブロモ-3,8-ジブチル-6-(4-メトキシフェニル)ピレン（化合物（１０１６））を、黄色固体として得た(収量98%、収率887mg)。以下に、1-ブロモ-3,8-ジブチル-6-(4-メトキシフェニル)ピレン（化合物（１０１６））の機器分析値を示す。また、図２４に、1-ブロモ-3,8-ジブチル-6-(4-メトキシフェニル)ピレン（化合物（１０１６））の¹H NMRチャートを示し、図２５に、1-ブロモ-3,8-ジブチル-6-(4-メトキシフェニル)ピレン（化合物（１０１６））の¹³C NMRチャートを示す。 <Example 12: 1-bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016))>

A solution of (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1007)) (985 mg, 2 mmol) in anhydrous CCl ₄ (2 mL) was cooled to 0 ° C. To the mixture, 3 mL of bromine (1M CCl ₄ stock solution) was added dropwise over 20 minutes and stirred for an additional 15 minutes. Further, the reaction was continued by raising the temperature to room temperature. After stirring at room temperature for another hour, water was added to stop the reaction. The obtained crude product was purified by column chromatography (hexane / CHCl ₃ = 1/3), and the target 1-bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)) was obtained as a yellow solid (98% yield, 887 mg yield). The instrumental analysis value of 1-bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)) is shown below. FIG. 24 shows a ¹ H NMR chart of ¹ -bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)), and FIG. 25 shows 1-bromo-3,8. The ¹³ C NMR chart of 2-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)) is shown.

Instrumental analysis of 1-bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.43 (d, J = 9.5Hz, 1H), 8.34 (d, J = 9.5Hz, 1H), 8.19 (d, J = 9.5Hz, 1H), 82.1-8.08 ( m, 2H), 7.85 (s, 1H), 7.55 (d, J = 8.7Hz, 2H), 7.10 (d, J = 8.7Hz, 2H), 3.94 (s, 3H), 3.36 (t. J = 7.8 , 7.8Hz, 2H), 3.26 (t.J = 7.8, 7.8Hz, 2H), 1.88-1.79 (m, 4H), 1.53-1.46 (m, 4H), 1.02-0.96 (m, 6H). ¹³ C NMR (100MHz, CDCl ₃ ) δ 159.2, 137.8, 137.7, 137.4, 133.8, 131.9, 131.3, 129.8, 128.6, 128.4, 128.2, 127.30, 127.28, 125.7, 125.6, 124.3, 122.4, 119.7, 114.0, 55.6, 34.3, 34.0, 33.7, 33.3, 23.2, 23.1, 14.3, 14.2. MS (FAB) m / z: 498 (M ⁺ ). Anal.Calcd for C ₃₁ H ₃₁ BrO: C, 74.54; H, 6.26. Found: C, 74.58; H, 6.35.

K₂CO₃(138mg, 1mmol)および4-(メトキシカルボニル)フェニルボロン酸(135mg, 0.75mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(233mg, 0.5mmol)およびPd(PPh₃)₄(58mg, 0.05mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、23時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=2/1)で精製し、目的物であるメチル 4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００２））を、黄色固体として得た(収率87%、収量227mg)。以下に、メチル 4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００２））の機器分析値を示す。また、図２６に、メチル 4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００２））の¹H NMRチャートを示し、図２７に、メチル 4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００２））の¹³C NMRチャートを示す。 <Example 13: Methyl 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1002))>

K ₂ CO ₃ (138 mg, 1 mmol) and 4- (methoxycarbonyl) phenylboronic acid (135 mg, 0.75 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (233 mg, 0.5 mmol) and Pd (PPh ₃ ) ₄ (58 mg, 0.05 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 23 hours under reflux conditions of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 2/1), and the desired product methyl 4- (3,8-dibutyl-6- (trimethylsilyl) pyrene-1- Yl) benzoate (compound (1002)) was obtained as a yellow solid (87% yield, 227 mg yield). The instrumental analysis value of methyl 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1002)) is shown below. FIG. 26 shows a ¹ H NMR chart of methyl 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1002)), and FIG. 27 shows methyl 4- ( A ¹³ C NMR chart of 3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1002)) is shown.

Instrumental analysis of methyl 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1002)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.39 (d, J = 9.4Hz, 1H), 8.30 (d, J = 9.4Hz, 1H), 8.23 (d, J = 8.4Hz, 2H), 8.16 (d, J = 9.4Hz, 1H), 8.09 (d, J = 9.4Hz, 1H), 8.03 (s, 1H), 7.81 (s, 1H), 7.72 (d, J = 8.4Hz, 2H), 4.01 (s, 3H), 3.37 (t, J = 7.7, 7.7Hz, 2H), 3.30 (t, J = 7.7, 7.7Hz, 2H), 1.92-1.78 (m, 4H), 1.59-1.46 (m, 4H), 1.03 -0.98 (m, 6H), 0.61 (s, 9H). 13 C NMR (100MHz, CDCl 3) δ 167.3, 146.7, 137.1, 136.0, 135.5, 134.5, 134.1, 131.0, 129.9, 129.8, 129.1, 128.8, 128.6 , 128.1, 127.1, 126.5, 126.0, 125.2, 123.4, 122.4, 52.4, 34.4, 34.3, 33.9, 33.8, 23.3, 23.2, 14.34, 14.33, 1.0. MS (FAB) m / z: 520 (M ⁺ ). Anal Calcd for C ₃₅ H ₄₀ O ₂ Si: C, 80.72; H, 7.74. Found: C, 80.76; H, 7.55.

K₂CO₃(138mg, 1mmol)および3-(メトキシカルボニル)フェニルボロン酸(135mg, 0.75mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(233mg, 0.5mmol)およびPd(PPh₃)₄(58mg, 0.05mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、21時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=2/1)で精製し、目的物であるメチル 3-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００３））を、淡黄色固体として得た(収率88%、収量228mg)。以下に、メチル 3-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００３））の機器分析値を示す。また、図２８に、メチル 3-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００３））の¹H NMRチャートを示し、図２９に、メチル 3-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００３））の¹³C NMRチャートを示す。 <Example 14: Methyl 3- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (Compound (1003))>

K ₂ CO ₃ (138 mg, 1 mmol) and 3- (methoxycarbonyl) phenylboronic acid (135 mg, 0.75 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (233 mg, 0.5 mmol) and Pd (PPh ₃ ) ₄ (58 mg, 0.05 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 21 hours under reflux conditions of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 2/1), and the target product, methyl 3- (3,8-dibutyl-6- (trimethylsilyl) pyrene-1- Yl) benzoate (compound (1003)) was obtained as a pale yellow solid (yield 88%, yield 228 mg). The instrumental analysis value of methyl 3- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1003)) is shown below. FIG. 28 shows a ¹ H NMR chart of methyl 3- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1003)), and FIG. 29 shows methyl 3- ( A ¹³ C NMR chart of 3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1003)) is shown.

Instrumental analysis of methyl 3- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1003)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.39 (d, J = 9.4Hz, 1H), 8.32-8.29 (m, 2H), 8.17-8.15 (m, 2H), 8.06 (d, J = 9.4Hz, 1H ), 8.02 (s, 1H), 7.83-7.82 (m, 2H), 7.63 (t, J = 7.7Hz, 7.7Hz, 1H), 3.97 (s, 3H), 3.37 (t, J = 7.8Hz, 7.8 Hz, 2H), 3.30 (t, J = 7.8Hz, 7.8Hz, 2H), 1.92-1.78 (m, 4H), 1.59-1.46 (m, 4H), 1.04-0.97 (m, 6H), 0.61 (s ¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.4, 142.2, 137.1, 136.1, 135.9, 135.5, 135.4, 134.5, 134.1, 131.9, 130.6, 129.9, 129.0, 128.61, 128.57, 128.0, 127.2, 126.5 , 126.0, 125.3, 123.4, 122.4, 52.4, 34.5, 34.4, 34.0, 33.8, 23.31, 23.26, 14.4, 1.0.MS (FAB) m / z: 520 (M ⁺ ). Anal. Calcd for C ₃₅ H ₄₀ O ₂ Si: C, 80.72; H, 7.74. Found: C, 80.47; H, 7.56.

K₂CO₃(138mg, 1mmol)および2-(メトキシカルボニル)フェニルボロン酸(135mg, 0.75mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(233mg, 0.5mmol)およびPd(PPh₃)₄(58mg, 0.05mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、18時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=2/1)で精製し、目的物であるメチル 2-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００４））を、淡黄色固体として得た(収率78%、収量202mg)。以下に、メチル 2-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００４））の機器分析値を示す。また、図３０に、メチル 2-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００４））の¹H NMRチャートを示し、図３１に、メチル 2-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンゾエート（化合物（１００４））の¹³C NMRチャートを示す。 <Example 15: Methyl 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1004))>

K ₂ CO ₃ (138 mg, 1 mmol) and 2- (methoxycarbonyl) phenylboronic acid (135 mg, 0.75 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (233 mg, 0.5 mmol) and Pd (PPh ₃ ) ₄ (58 mg, 0.05 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 18 hours under DMF reflux conditions (heated to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 2/1), and the target product, methyl 2- (3,8-dibutyl-6- (trimethylsilyl) pyrene-1- Yl) benzoate (compound (1004)) was obtained as a pale yellow solid (78% yield, 202 mg yield). The instrumental analysis value of methyl 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1004)) is shown below. 30 shows a ¹ H NMR chart of methyl 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1004)), and FIG. 31 shows methyl 2- ( A ¹³ C NMR chart of 3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1004)) is shown.

Instrumental analysis of methyl 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzoate (compound (1004)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.36 (d, J = 9.4Hz, 1H), 8.30 (d, J = 9.4Hz, 1H), 8.10-8.06 (m, 1H), 8.00 (s, 1H), 7.76 (d, J = 9.4Hz, 1H), 7.70 (s, 1H), 7.65 (dt, J = 1.4Hz, 7.5Hz, 9.0Hz, 1H), 7.56 (dt, J = 1.4Hz, 7.5Hz, 9.0 Hz, 1H), 7.50 (dd, J = 1.1Hz, 7.6Hz, 1H), 3.38-3.26 (m, 8H), 1.90-1.75 (m, 4H), 1.54-1.44 (m, 4H), 1.01-0.97 (m, 6H), 0.60 ( s, 9H). 13 C NMR (100MHz, CDCl 3) δ 168.6, 142.3, 136.7, 136.6, 135.9, 135.1, 134.6, 133.9, 132.7, 132.3, 131.6, 130.4, 129.9, 128.4 , 128.2, 127.7, 127.5, 126.1, 126.0, 125.5, 123.0, 122.6, 52.1, 34.5, 34.4, 34.0, 33.7, 23.3, 23.2, 14.5, 14.4, 1.0.MS (FAB) m / z: 520 (M ⁺ ) Anal. Calcd for C ₃₅ H ₄₀ O ₂ Si: C, 80.72; H, 7.74. Found: C, 80.74; H, 7.48.

K₂CO₃(138mg, 1mmol)および4-ホルミルフェニルボロン酸(113mg, 0.75mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(233mg, 0.5mmol)およびPd(PPh₃)₄(58mg, 0.05mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、22時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=4/1)で精製し、目的物である4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアルデヒド（化合物（１００５））を、淡黄色固体として得た(収率93%、収量227mg)。以下に、4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアルデヒド（化合物（１００５））の機器分析値を示す。また、図３２に、4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアルデヒド（化合物（１００５））の¹H NMRチャートを示し、図３３に、4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアルデヒド（化合物（１００５））の¹³C NMRチャートを示す。 <Example 16: 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (compound (1005))>

K ₂ CO ₃ (138 mg, 1 mmol) and 4-formylphenylboronic acid (113 mg, 0.75 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (233 mg, 0.5 mmol) and Pd (PPh ₃ ) ₄ (58 mg, 0.05 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 22 hours under reflux conditions of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 4/1), and the desired product 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl ) Benzaldehyde (compound (1005)) was obtained as a pale yellow solid (yield 93%, yield 227 mg). The instrumental analysis value of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (compound (1005)) is shown below. FIG. 32 shows a ¹ H NMR chart of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (compound (1005)), and FIG. 33 shows 4- (3, A ¹³ C NMR chart of 8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (compound (1005)) is shown.

Instrumental analysis of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (compound (1005)):
¹ H NMR (400MHz, CDCl ₃ ) δ 10.2 (s, 1H), 8.40 (d, J = 9.5Hz, 1H), 8.30 (d, J = 9.5Hz, 1H), 8.18 (d, J = 9.5Hz, 1H), 8.10-8.06 (m, 3H), 8.03 (s, 1H), 7.83-7.81 (m, 3H), 3.37 (t, J = 7.7Hz, 2H), 3.30 (t, J = 7.7Hz, 2 H), 1.93-1.78 (m, 4H), 1.59-1.46 (m, 4H), 1.04-0.98 (m, 6H), 0.62 (s, 9H). 13 C NMR (100MHz, CDCl 3) δ 192.1, 148.2, 137.1, 136.1, 135.7, 135.6, 135.3, 134.5, 134.2, 131.5, 129.84, 129.76, 128.8, 128.7, 128.3, 127.0, 126.5, 125.9, 125.0, 123.5, 122.4, 34.5, 34.3, 33.9, 33.8, 23.3, 23.2, 14.34, 14.33, 1.0. MS (FAB) m / z: 490 (M ⁺ ). Anal. Calcd for C ₃₄ H ₃₈ OSi: C, 83.21; H, 7.80. Found: C, 83.21; H, 7.76.

K₂CO₃(138mg, 1mmol)および2-ホルミルフェニルボロン酸(113mg, 0.75mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(233mg, 0.5mmol)およびPd(PPh₃)₄(58mg, 0.05mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、14時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=4/1)で精製し、目的物である2-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアルデヒド（化合物（１００６））を、淡黄色固体として得た(収率89%、収量219mg)。以下に、を示す。また、図３４に、2-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアルデヒド（化合物（１００６））の¹H NMRチャートを示し、図３５に、2-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアルデヒド（化合物（１００６））の¹³C NMRチャートを示す。 <Example 17: 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (compound (1006))>

K ₂ CO ₃ (138 mg, 1 mmol) and 2-formylphenylboronic acid (113 mg, 0.75 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (233 mg, 0.5 mmol) and Pd (PPh ₃ ) ₄ (58 mg, 0.05 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 14 hours under DMF reflux conditions (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 4/1), and the desired product 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl ) Benzaldehyde (compound (1006)) was obtained as a pale yellow solid (89% yield, 219 mg yield). The following is shown. FIG. 34 shows a ¹ H NMR chart of 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (compound (1006)), and FIG. 35 shows 2- (3, The ¹³ C NMR chart of 8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (compound (1006)) is shown.

Instrumental analysis of 2- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzaldehyde (compound (1006)):
¹ H NMR (400MHz, CDCl ₃ ) δ 9.64 (s, 1H), 8.43 (d, J = 9.4Hz, 1H), 8.32 (d, J = 9.4Hz, 1H), 8.19-8.13 (m, 2H), 8.04 (s, 1H), 7.79 (s, 1H), 7.78-7.73 (m, 2H), 7.65-7.58 (m, 2H), 3.37 (t, J = 7.7, 7.7Hz, 2H), 3.28 (t , J = 7.7, 7.7Hz, 2 H), 1.92-1.75 (m, 4H), 1.57-1.44 (m, 4H), 1.03-0.96 (m, 6H), 0.60 (s, 9H). ¹³ C NMR ( 100MHz, CDCl ₃ ) δ 192.4, 145.5, 136.8, 136.4, 136.0, 135.4, 134.5, 134.3, 133.7, 132.5, 132.2, 129.7, 129.0, 128.7, 128.4, 128.3, 127.3, 126.2, 125.7, 125.2, 124.0, 122.4, 34.5, 34.3, 34.0, 33.7, 23.22, 14.35, 14.32, 1.0. MS (FAB) m / z: 490 (M ⁺ ). Anal. Calcd for C ₃₄ H ₃₈ OSi: C, 83.21; H, 7.80. Found: C, 83.24; H, 7.70.

K₂CO₃(138mg, 1mmol)および4-メトキシフェニルボロン酸(114mg, 0.75mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(233mg, 0.5mmol)およびPd(PPh₃)₄(58mg, 0.05mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、23時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=9/1)で精製し、目的物である(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)トリメチルシラン（化合物（１００７））を、淡黄色固体として得た(収率91%、収量223mg)。以下に、(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)トリメチルシラン（化合物（１００７））の機器分析値を示す。また、図３６に、(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)トリメチルシラン（化合物（１００７））の¹H NMRチャートを示し、図３７に、(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)トリメチルシラン（化合物（１００７））の¹³C NMRチャートを示す。 <Example 18: (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1007))>

K ₂ CO ₃ (138 mg, 1 mmol) and 4-methoxyphenylboronic acid (114 mg, 0.75 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (233 mg, 0.5 mmol) and Pd (PPh ₃ ) ₄ (58 mg, 0.05 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 23 hours under reflux conditions of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 9/1), and the desired product (3,8-dibutyl-6- (4-methoxyphenyl) pyrene-1- Yl) trimethylsilane (compound (1007)) was obtained as a pale yellow solid (91% yield, 223 mg yield). The instrumental analysis values of (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1007)) are shown below. FIG. 36 shows a ¹ H NMR chart of (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1007)), and FIG. The ¹³ C NMR chart of 8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1007)) is shown.

Instrumental analysis of (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1007)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.35 (d, J = 9.5Hz, 1H), 8.28 (d, J = 9.5Hz, 1H), 8.17 (d, J = 9.5Hz, 1H), 8.13 (d, J = 9.5Hz, 1H), 8.00 (s, 1H), 7.81 (s, 1H), 7.56 (d, J = 8.8Hz, 2H), 7.10 (d, J = 8.8Hz, 2H), 3.94 (s, 3H), 3.36 (t, J = 7.8, 7.8Hz, 2H), 3.29 (t, J = 7.8, 7.8Hz, 2H), 1.91-1.77 (m, 4H), 1.58-1.46 (m, 4H), 1.03-0.96 (m, 6H), 0.60 (s, 9H). 13 C NMR (100MHz, CDCl 3) δ 159.2, 137.2, 137.0, 135.7, 135.0, 134.7, 134.2, 134.0, 132.0, 130.0, 129.3, 128.1, 127.7, 127.4, 126.6, 126.2, 126.0, 122.9, 122.5, 114.1, 55.5, 34.5, 34.4, 34.0, 33.8, 23.34, 23.29, 14.42, 14.41, 1.1.MS (FAB) m / z: 492 (M ⁺ ). Anal. Calcd for C ₃₄ H ₄₀ OSi: C, 82.87; H, 8.18. Found: C, 80.88; H, 8.20.

K₂CO₃(138mg, 1mmol)および2-メトキシフェニルボロン酸(114mg, 0.75mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(233mg, 0.5mmol)、Pd₂(dba)₃・CHCl₃(26mg, 0.025mmol)およびPCy₃(21mg, 0.075mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、8時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=9/1)で精製し、目的物である(3,8-ジブチル-6-(2-メトキシフェニル)ピレン-1-イル)トリメチルシラン（化合物（１００８））を、淡黄色固体として得た(収率97%、収量238mg)。以下に、(3,8-ジブチル-6-(2-メトキシフェニル)ピレン-1-イル)トリメチルシラン（化合物（１００８））の機器分析値を示す。また、図３８に、(3,8-ジブチル-6-(2-メトキシフェニル)ピレン-1-イル)トリメチルシラン（化合物（１００８））の¹H NMRチャートを示し、図３９に、(3,8-ジブチル-6-(2-メトキシフェニル)ピレン-1-イル)トリメチルシラン（化合物（１００８））の¹³C NMRチャートを示す。 <Example 19: (3,8-dibutyl-6- (2-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1008))>

K ₂ CO ₃ (138 mg, 1 mmol) and 2-methoxyphenylboronic acid (114 mg, 0.75 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (233 mg, 0.5 mmol), Pd ₂ (dba) ₃ .CHCl ₃ ( 26 mg, 0.025 mmol) and PCy ₃ (21 mg, 0.075 mmol) were added. Further, the inside of the Schlenk flask was replaced with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 8 hours under DMF reflux conditions (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 9/1), and the desired product (3,8-dibutyl-6- (2-methoxyphenyl) pyrene-1- Yl) trimethylsilane (compound (1008)) was obtained as a pale yellow solid (97% yield, 238 mg yield). The instrumental analysis values of (3,8-dibutyl-6- (2-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1008)) are shown below. FIG. 38 shows a ¹ H NMR chart of (3,8-dibutyl-6- (2-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1008)), and FIG. The ¹³ C NMR chart of 8-dibutyl-6- (2-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1008)) is shown.

Instrumental analysis of (3,8-dibutyl-6- (2-methoxyphenyl) pyren-1-yl) trimethylsilane (compound (1008)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.35 (d, J = 9.4Hz, 1H), 8.29 (d, J = 9.4Hz, 1H), 8.09 (d, J = 9.4Hz, 1H), 7.99 (m, 1H), 7.83 (d, J = 9.4Hz, 1H), 7.80 (s, 1H), 7.50-7.39 (m, 2H), 7.16-7.10 (m, 2H), 3.71 (s, 3H), 3.40-3.24 (m, 4H), 1.92-1.76 (m, 4H), 1.58-1.45 (m, 4H), 1.03-0.97 (m, 6H), 0.60 (m, 9H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ 157.7, 136.8, 135.7, 134.9, 134.6, 134.1, 133.9, 132.8, 130.7, 130.1, 129.7, 129.3, 128.4, 128.1, 127.7, 126.5, 126.4, 126.1, 122.6, 120.9, 111.5, 55.8, 34.5, 34.3, 34.1, 33.8, 23.3, 23.30, 14.5, 14.4, 1.1.MS (FAB) m / z: 492 (M ⁺ ). Anal. Calcd for C ₃₄ H ₄₀ OSi: C, 82.87; H, 8.18. Found: C, 82.87; H, 8.20.

K₂CO₃(138mg, 1mmol)および2-ブロモフェニルボロン酸(151mg, 0.75mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(233mg, 0.5mmol)およびPd(PPh₃)₄(58mg, 0.05mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、11時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサンのみ)で精製し、目的物である(6-(2-ブロモフェニル)-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００９））を、黄白色固体として得た(収率90%、収量244mg)。以下に、(6-(2-ブロモフェニル)-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００９））の機器分析値を示す。また、図４０に、(6-(2-ブロモフェニル)-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００９））の¹H NMRチャートを示し、図４１に、(6-(2-ブロモフェニル)-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００９））の¹³C NMRチャートを示す。 <Example 20: (6- (2-bromophenyl) -3,8-dibutylpyren-1-yl) trimethylsilane (compound (1009))>

K ₂ CO ₃ (138 mg, 1 mmol) and 2-bromophenylboronic acid (151 mg, 0.75 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (233 mg, 0.5 mmol) and Pd (PPh ₃ ) ₄ (58 mg, 0.05 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 11 hours under the reflux condition of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane only), and the target product (6- (2-bromophenyl) -3,8-dibutylpyren-1-yl) trimethylsilane (compound) (1009)) as a pale yellow solid (yield 90%, yield 244 mg). The instrumental analysis value of (6- (2-bromophenyl) -3,8-dibutylpyren-1-yl) trimethylsilane (compound (1009)) is shown below. FIG. 40 shows a ¹ H NMR chart of (6- (2-bromophenyl) -3,8-dibutylpyren-1-yl) trimethylsilane (compound (1009)), and FIG. The ¹³ C NMR chart of (2-bromophenyl) -3,8-dibutylpyren-1-yl) trimethylsilane (compound (1009)) is shown.

Instrumental analysis of (6- (2-bromophenyl) -3,8-dibutylpyren-1-yl) trimethylsilane (compound (1009)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.39 (d, J = 9.5Hz, 1H), 8.31 (d, J = 9.5Hz, 1H), 8.14 (d, J = 9.5Hz, 1H), 8.01 (s, 1H), 7.80 (d, J = 8.0Hz, 1H), 7.74 (s, 1H), 7.70 (d, J = 9.5Hz, 1H), 7.48-7.47 (m, 2H), 7.37-7.33 (m, 1H ), 3.41-3.25 (m, 4H), 1.92-1.76 (m, 4H), 1.57-1.45 (m, 4H), 1.02-0.96 (m, 6H), 0.61 (s, 9H). ¹³ C NMR (100 MHz , CDCl ₃ ) δ 142.5, 136.8, 136.14, 136.13, 136.12, 135.4, 134.5, 134.1, 133.1, 132.7, 129.9, 129.3, 128.9, 128.7, 128.1, 127.6, 127.4, 126.2, 125.9, 125.7, 125.1, 123.2, 122.5 , 34.5, 34.3, 34.1, 33.8, 23.3, 23.2, 14.44, 14.39, 1.1.MS (FAB) m / z: 542 (M ⁺ ). Anal. Calcd for C ₃₈ H ₃₇ BrSi: C, 73.18; H, 6.89 Found: C, 73.22; H, 6.89.

K₂CO₃(138mg, 1mmol)および4-カルバモイルフェニルボロン酸(124mg, 0.75mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(233mg, 0.5mmol)およびPd(PPh₃)₄(58mg, 0.05mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、16時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(CH₂Cl₂/MeOH=99/1)で精製し、目的物である4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアミド（化合物（１０１０））を、淡黄色固体として得た(収率95%、収量239mg)。以下に、4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアミド（化合物（１０１０））の機器分析値を示す。また、図４２に、4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアミド（化合物（１０１０））の¹H NMRチャートを示し、図４３に、4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ベンズアミド（化合物（１０１０））の¹³C NMRチャートを示す。 <Example 21: 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzamide (Compound (1010))>

K ₂ CO ₃ (138 mg, 1 mmol) and 4-carbamoylphenylboronic acid (124 mg, 0.75 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (233 mg, 0.5 mmol) and Pd (PPh ₃ ) ₄ (58 mg, 0.05 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 16 hours under reflux conditions of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (CH ₂ Cl ₂ / MeOH = 99/1), and the desired product 4- (3,8-dibutyl-6- (trimethylsilyl) pyrene-1 -Yl) benzamide (compound (1010)) was obtained as a pale yellow solid (95% yield, 239 mg yield). The instrumental analysis values of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzamide (Compound (1010)) are shown below. 42 shows a ¹ H NMR chart of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzamide (compound (1010)), and FIG. 43 shows 4- (3, A ¹³ C NMR chart of 8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzamide (compound (1010)) is shown.

Instrumental analysis of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) benzamide (compound (1010)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.39 (d, J = 9.5Hz, 1H), 8.30 (d, J = 9.5Hz, 1H), 8.16 (d, J = 9.5Hz, 1H), 8.09 (d, J = 9.5Hz, 1H), 8.03 (s, 1H), 8.01 (d, J = 8.3Hz, 2H), 7.80 (s, 1H), 7.73 (d, J = 8.3Hz, 2H), 3.37 (t, J = 7.3Hz, 7.3Hz, 2H), 3.37 (t, J = 7.8Hz, 7.8Hz, 2H), 3.30 (t, J = 7.8Hz, 7.8Hz, 2H), 1.92-1.77 (m, 4H), 1.60-1.46 (m, 4H), 1.03-0.97 (m, 6H), 0.61 (s, 9H). 13 C NMR (100MHz, CDCl 3) δ 170.2, 145.7, 137.1, 136.0, 135.5, 134.5, 134.1, 132.4 , 131.2, 129.79, 129.77, 128.9, 128.8, 128.6, 128.1, 127.8, 127.1, 126.4, 125.9, 125.2, 123.3, 122.4, 34.4, 34.2, 33.9, 33.7, 23.22, 23.19, 14.3, 1.0.MS (FAB) m / z: 505 (M ⁺ ). Anal. Calcd for C ₃₄ H ₃₉ NOSi: C, 80.74; H, 7.77. Found: C, 80.71; H, 7.65.

K₂CO₃(138mg, 1mmol)およびピリジン-4-イルボロン酸(92mg, 0.75mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(233mg, 0.5mmol)およびPd(PPh₃)₄(58mg, 0.05mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、22時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=1/4)で精製し、目的物である4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ピリジン（化合物（１０１１））を、淡黄色固体として得た(収率47%、収量108mg)。以下に、4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ピリジン（化合物（１０１１））の機器分析値を示す。また、図４４に、4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ピリジン（化合物（１０１１））の¹H NMRチャートを示し、図４５に、4-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ピリジン（化合物（１０１１））の¹³C NMRチャートを示す。 <Example 22: 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyridine (compound (1011))>

K ₂ CO ₃ (138 mg, 1 mmol) and pyridin-4-ylboronic acid (92 mg, 0.75 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (233 mg, 0.5 mmol) and Pd (PPh ₃ ) ₄ (58 mg, 0.05 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 22 hours under reflux conditions of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 1/4), and the desired product 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl ) Pyridine (compound (1011)) was obtained as a pale yellow solid (47% yield, 108 mg yield). The instrumental analysis value of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyridine (compound (1011)) is shown below. FIG. 44 shows a ¹ H NMR chart of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyridine (compound (1011)), and FIG. 45 shows 4- (3, A ¹³ C NMR chart of 8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyridine (compound (1011)) is shown.

Instrumental analysis of 4- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyridine (compound (1011)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.79 (d, J = 4.2Hz, 2H), 8.41 (d, J = 9.4Hz, 1H), 8.30 (d, J = 9.4Hz, 1H), 8.20 (d, J = 9.5Hz, 1H), 8.09 (d, J = 9.5Hz, 1H), 8.04 (s, 1H), 7.79 (s, 1H), 7.59-7.58 (m, 2H), 3.37 (t, J = 7.7 , 7.7Hz, 2H), 3.31 (t, J = 7.7, 7.7Hz, 2H), 1.92-1.78 (m, 4H), 1.59-1.47 (m, 4H), 1.04-0.98 (m, 6H), 0.61 ( ¹³ C NMR (100 MHz, CDCl ₃ ) δ 149.9, 149.6, 137.1, 136.2, 135.8, 134.4, 134.1, 133.9, 129.6, 128.9, 128.4, 128.2, 126.7, 126.3, 125.8, 124.6, 123.6, 122.2 , 34.4, 34.1, 33.8, 33.6, 23.2, 23.1, 14.2, 0.9. MS (FAB) m / z: 463 (M ⁺ ). Anal. Calcd for C ₃₂ H ₃₇ NSi: C, 82.88; H, 8.04. Found : C, 82.90; H, 8.00.

(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(116mg, 0.25mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、CuI(4.8mg, 0.025mmol)、PdCl₂(PPh₃)₂(8.8mg, 0.0125mmol)およびPPh₃(6.6mg 0.025mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、トルエンおよびトリエチルアミン(それぞれ1.5mL)を加えた。その反応混合物を、室温で15分間撹拌し、トリメチルシリルアセチレン（74mg, 0.75mmol）を加えた。その後、前記混合物を、70℃で1時間撹拌した。得られた溶液を、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサンのみ)で精製し、目的物である(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)トリメチルシラン（化合物（１０１２））を、黄色固体として得た(収率91%、収量110mg)。以下に、(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)トリメチルシラン（化合物（１０１２））の機器分析値を示す。また、図４６に、(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)トリメチルシラン（化合物（１０１２））の¹H NMRチャートを示し、図４７に、(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)トリメチルシラン（化合物（１０１２））の¹³C NMRチャートを示す。 <Example 23: (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) trimethylsilane (compound (1012))>

(6-Bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (116 mg, 0.25 mmol) was dried by heating in a Schlenk flask under reduced pressure. Next, CuI (4.8 mg, 0.025 mmol), PdCl ₂ (PPh ₃ ) ₂ (8.8 mg, 0.0125 mmol) and PPh ₃ (6.6 mg 0.025 mmol) were added into the Schlenk flask. Further, the inside of the Schlenk flask was replaced with argon three times, and toluene and triethylamine (each 1.5 mL) were added. The reaction mixture was stirred at room temperature for 15 minutes and trimethylsilylacetylene (74 mg, 0.75 mmol) was added. The mixture was then stirred at 70 ° C. for 1 hour. The obtained solution was filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane only), and the desired product (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) trimethylsilane (compound (1012)) was obtained as a yellow solid (91% yield, 110 mg yield). The instrumental analysis values of (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) trimethylsilane (compound (1012)) are shown below. 46 shows a ¹ H NMR chart of (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) trimethylsilane (compound (1012)), and FIG. The ¹³ C NMR chart of 8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) trimethylsilane (compound (1012)) is shown.

Instrumental analysis of (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) trimethylsilane (compound (1012)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.58 (d, J = 9.4Hz, 1H), 8.37 (d, J = 9.4Hz, 1H), 8.31 (d, J = 9.4Hz, 1H), 8.23 (d, J = 9.4Hz, 1H), 8.02 (s, 1H), 8.00 (s, 1H), 3.35-3.27 (m, 4H), 1.87-1.80 (m, 4H), 1.52-1.48 (m, 4H), 1.03 -0.99 (m, 6H), 0.59 (s, 9H), 0.39 (s, 9H). 13 C NMR (100MHz, CDCl 3) δ 136.8, 136.7, 135.9, 134.21, 134.15, 131.1, 131.0, 129.9, 129.3, 128.6, 126.0, 125.8, 125.3, 123.9, 122.3, 117.1, 104.9, 99.9, 34.6, 34.1, 33.5, 23.3, 23.2, 14.3, 1.0, 0.5. MS (FAB) m / z: 482 (M ⁺ ). Anal. Calcd for C ₃₂ H ₄₂ Si ₂ : C, 79.60; H, 8.77. Found: C, 79.66; H, 8.77.

NaO^tBu(72mg, 0.75mmol) を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、Pd₂(dba)₃・CHCl₃(13mg, 0.0125mmol)およびBINAP(16mg, 0.025mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴン置換した。そのシュレンクフラスコ内に、トルエン(2.0mL)を入れ、15分間撹拌した。つぎに、そのシュレンクフラスコ内に、(6-ブロモ-3,8-ジブチルピレン-1-イル)トリメチルシラン（化合物（１００１））(116mg, 0.25mmol)を加え、15分間撹拌した。さらに、前記シュレンクフラスコ内に、ピロリジン(0.06mL, 0.75mmol)を加え、密閉した。その混合物を、1.5時間以上かけて、90℃まで加熱した。さらに90℃で15時間撹拌後、得られた混合物を、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CH₂Cl₂=9/1)で精製し、目的物である1-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ピロリジン（化合物（１０１３））を、褐色固体として得た(収率70%、収量80mg)。以下に、1-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ピロリジン（化合物（１０１３））の機器分析値を示す。また、図４８に、1-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ピロリジン（化合物（１０１３））の¹H NMRチャートを示し、図４９に、1-(3,8-ジブチル-6-(トリメチルシリル)ピレン-1-イル)ピロリジン（化合物（１０１３））の¹³C NMRチャートを示す。 <Example 24: 1- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyrrolidine (Compound (1013))>

NaO ^t Bu (72 mg, 0.75 mmol) was dried by heating in a Schlenk flask under reduced pressure. Next, Pd ₂ (dba) ₃ .CHCl ₃ (13 mg, 0.0125 mmol) and BINAP (16 mg, 0.025 mmol) were added into the Schlenk flask. Further, the inside of the Schlenk flask was replaced with argon. Toluene (2.0 mL) was placed in the Schlenk flask and stirred for 15 minutes. Next, (6-bromo-3,8-dibutylpyren-1-yl) trimethylsilane (compound (1001)) (116 mg, 0.25 mmol) was added to the Schlenk flask and stirred for 15 minutes. Further, pyrrolidine (0.06 mL, 0.75 mmol) was added to the Schlenk flask and sealed. The mixture was heated to 90 ° C. over 1.5 hours. Further, after stirring at 90 ° C. for 15 hours, the resulting mixture was filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CH ₂ Cl ₂ = 9/1), and the target 1- (3,8-dibutyl-6- (trimethylsilyl) pyrene-1 -Yl) pyrrolidine (compound (1013)) was obtained as a brown solid (yield 70%, yield 80 mg). The instrumental analysis values of 1- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyrrolidine (Compound (1013)) are shown below. FIG. 48 shows a ¹ H NMR chart of 1- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyrrolidine (compound (1013)), and FIG. 49 shows 1- (3, A ¹³ C NMR chart of 8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyrrolidine (Compound (1013)) is shown.

Instrumental analysis of 1- (3,8-dibutyl-6- (trimethylsilyl) pyren-1-yl) pyrrolidine (compound (1013)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.41 (d, J = 8.4Hz, 1H), 8.13-7.93 (m, 3H), 7.49 (brs, 1H), 7.26 (s, 1H), 3.58 (brs, 4H ), 3.29 (t, J = 7.7Hz, 7.7Hz, 4H), 2.11 (brs, 4H), 1.88-1.79 (m, 4H), 1.56-1.49 (m, 4H), 1.03-0.99 (m, 6H) , 0.57 (s, 9H). 13 C NMR (100MHz, CDCl 3) δ 14.2, 137.8, 135.0, 134.4, 133.7, 133.4, 130.3, 127.8, 126.3, 125.1, 124.4, 123.5, 122.4, 121.2, 120.7, 116.1, 53.6, 34.4, 34.2, 34.1, 33.9, 25.4, 23.24, 23.23, 14.3, 0.8. MS (FAB) m / z: 455 (M ⁺ ). Anal. Calcd for C ₃₁ H ₄₁ NSi: C, 81.70; H, 9.07; N, 3.07. Found: C, 81.70; H, 9.07; N, 3.22.

K₂CO₃(83mg, 0.6mmol)および4-(メトキシカルボニル)フェニルボロン酸(81mg, 0.45mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、1-ブロモ-3,8-ジブチル-6-(4-メトキシフェニル)ピレン（化合物（１０１６））(149mg, 0.3mmol)およびPd(PPh₃)₄(69mg, 0.06mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、21時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=2/1)で精製し、目的物であるメチル 4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ベンゾエート（化合物（１０１７））を、淡黄色固体として得た(収率81%、収量134mg)。以下に、メチル 4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ベンゾエート（化合物（１０１７））の機器分析値を示す。また、図５０に、メチル 4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ベンゾエート（化合物（１０１７））の¹H NMRチャートを示し、図５１に、メチル 4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ベンゾエート（化合物（１０１７））の¹³C NMRチャートを示す。 <Example 25: Methyl 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzoate (compound (1017))>

K ₂ CO ₃ (83 mg, 0.6 mmol) and 4- (methoxycarbonyl) phenylboronic acid (81 mg, 0.45 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, 1-bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)) (149 mg, 0.3 mmol) and Pd (PPh ₃ ) ₄ (69 mg, 0.06 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 21 hours under reflux conditions of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 2/1), and the target product, methyl 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyrene, was obtained. -1-yl) benzoate (compound (1017)) was obtained as a pale yellow solid (81% yield, 134 mg yield). The instrumental analysis value of methyl 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzoate (compound (1017)) is shown below. FIG. 50 shows a ¹ H NMR chart of methyl 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzoate (compound (1017)), and FIG. A ¹³ C NMR chart of 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzoate (compound (1017)) is shown.

Instrumental analysis of methyl 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzoate (compound (1017)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.24-8.17 (m, 5H), 8.10 (d, J = 9.5Hz, 1H), 7.83 (d, J = 8.4Hz, 2H), 7.73 (d, J = 8.4 Hz, 2H), 7.58 (d, J = 8.7Hz, 2H), 7.11 (d, J = 8.7Hz, 2H), 4.01 (s, 3H), 3.94 (s, 3H), 3.33 (t, J = 7.6 , 7.6Hz, 4H), 1.86-1.81 (m, 4H), 1.54-1.48 (m, 4H), 1.00-0.96 (m, 6H). ¹³ C NMR (100MHz, CDCl ₃ ) δ 167.4, 159.2, 146.7, 137.4, 136.9, 136.6, 135.9, 134.0, 131.9, 131.0, 129.9, 129.5, 129.1, 129.0, 128.2, 127.5, 127.3, 126.42, 126.39, 125.8, 124.6, 123.2, 122.6, 114.1, 55.6, 52.4, 34.3, 34.2, 33.7, 23.2, 14.3. MS (FAB) m / z: 554 (M ⁺ ). Anal. Calcd for C ₃₉ H ₃₈ O ₃ : C, 84.44; H, 6.90. Found: C, 84.46; H, 7.01.

K₂CO₃(83mg, 0.6mmol)および4-ホルミルフェニルボロン酸(68mg, 0.45mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、1-ブロモ-3,8-ジブチル-6-(4-メトキシフェニル)ピレン（化合物（１０１６））(149mg, 0.3mmol)およびPd(PPh₃)₄(69mg, 0.06mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、1.2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、21時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=2/1)で精製し、目的物である4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ベンズアルデヒド（化合物（１０１８））を、淡黄色固体として得た(収率86%、収量136mg)。以下に、4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ベンズアルデヒド（化合物（１０１８））の機器分析値を示す。また、図５２に、4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ベンズアルデヒド（化合物（１０１８））の¹H NMRチャートを示し、図５３に、4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ベンズアルデヒド（化合物（１０１８））の¹³C NMRチャートを示す。 <Example 26: 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzaldehyde (compound (1018))>

K ₂ CO ₃ (83 mg, 0.6 mmol) and 4-formylphenylboronic acid (68 mg, 0.45 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, 1-bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)) (149 mg, 0.3 mmol) and Pd (PPh ₃ ) ₄ (69 mg, 0.06 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 1.2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 21 hours under reflux conditions of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 2/1), and the target 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyrene- 1-yl) benzaldehyde (compound (1018)) was obtained as a pale yellow solid (86% yield, 136 mg yield). The instrumental analysis value of 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzaldehyde (compound (1018)) is shown below. FIG. 52 shows a ¹ H NMR chart of 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzaldehyde (compound (1018)), and FIG. The ¹³ C NMR chart of (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzaldehyde (compound (1018)) is shown.

Instrumental analysis of 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) benzaldehyde (compound (1018)):
¹ H NMR (400MHz, CDCl ₃ ) δ 10.17 (s, 1H), 8.25-8.18 (m, 3H), 8.11-8.07 (m, 3H), 7.84-7.82 (m, 4H), 7.58 (d, J = 8.7Hz, 2H), 7.12 (d, J = 8.7Hz, 2H), 3.95 (s, 3H), 3.56-3.31 (m, 4H), 1.88-1.81 (m, 4H), 1.54-1.46 (m, 4H ), 1.01-0.96 (m, 6H) . 13 C NMR (100MHz, CDCl 3) δ 192.2, 159.2, 148.3, 138.0, 137.5, 137.0, 136.6, 135.5, 135.3, 133.9, 131.9, 131.5, 129.9, 129.6, 129.1 , 128.9, 128.1, 127.5, 127.2, 126.4, 126.3, 125.9, 124.4, 123.4, 122.6, 114.1, 55.58, 55.57, 55.56, 34.3, 34.2, 33.7, 23.3, 23.2, 14.4, 14.3.MS (FAB) m / z : 524 (M ⁺ ). Anal. Calcd for C ₃₈ H ₃₆ O ₂ : C, 86.99; H, 6.92. Found: C, 86.97; H, 6.95.

K₂CO₃(83mg, 0.6mmol)およびピリジン-4-イルボロン酸(55 mg, 0.45 mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、1-ブロモ-3,8-ジブチル-6-(4-メトキシフェニル)ピレン（化合物（１０１６））(149mg, 0.3mmol)およびPd(PPh₃)₄(69mg, 0.06mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、1.2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、22時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(トルエン/酢酸エチル= 19/1)で精製し、目的物である4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ピリジン（化合物（１０１９））を、淡黄色固体として得た(収率67%、収量100mg)。以下に、4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ピリジン（化合物（１０１９））の機器分析値を示す。また、図５４に、4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ピリジン（化合物（１０１９））の¹H NMRチャートを示し、図５５に、4-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ピリジン（化合物（１０１９））の¹³C NMRチャートを示す。 <Example 27: 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyridine (compound (1019))>

K ₂ CO ₃ (83 mg, 0.6 mmol) and pyridin-4-ylboronic acid (55 mg, 0.45 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, 1-bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)) (149 mg, 0.3 mmol) and Pd (PPh ₃ ) ₄ (69 mg, 0.06 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 1.2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 22 hours under reflux conditions of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (toluene / ethyl acetate = 19/1), and the desired product 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyrene- 1-yl) pyridine (compound (1019)) was obtained as a pale yellow solid (67% yield, 100 mg yield). The instrumental analysis value of 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyridine (compound (1019)) is shown below. 54 shows a ¹ H NMR chart of 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyridine (compound (1019)), and FIG. A ¹³ C NMR chart of (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyridine (compound (1019)) is shown.

Instrumental analysis of 4- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyridine (compound (1019)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.80 (d, J = 5.8Hz, 2H), 8.25-8.17 (m, 3H), 8.10 (d, J = 9.5Hz, 1H), 7.85 (s, 1H). 7.79 (s, 1H), 7.61 (d, J = 5.8Hz, 2H), 7.57 (d, J = 8.7Hz, 2H), 7.11 (d, J = 8.7Hz, 2H), 3.95 (s, 3H), 3.34 (t, J = 7.7, 7.7Hz, 4H), 1.88-1.80 (m, 4H), 1.55-1.46 (m, 4H), 1.01-0.97 (m, 6H). ¹³ C NMR (100MHz, CDCl ₃ ) δ 159.3, 150.0, 149.8, 137.7, 137.2, 136.7, 134.0, 133.9, 131.9, 129.7, 129.3, 128.6, 128.1, 127.4, 127.1, 126.4, 126.3, 126.1, 125.9, 124.1, 123.6, 122.5, 114.1, 55.7, 34.3 , 34.2, 33.71, 33.70, 23.2, 14.33, 14.32. MS (FAB) m / z: 497 (M ⁺ ).

1-ブロモ-3,8-ジブチル-6-(4-メトキシフェニル)ピレン（化合物（１０１６））(125mg, 0.25mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、CuI(4.8mg, 0.025mmol)、PdCl₂(PPh₃)₂(8.8mg, 0.0125mmol)およびPPh₃(6.6mg 0.025mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、トルエンおよびトリエチルアミン(それぞれ1.5mL)を加えた。その反応混合物を、室温で15分間撹拌し、トリメチルシリルアセチレン（74mg, 0.75mmol）を加えた。その後、前記混合物を、70℃で21時間撹拌した。これにより得られた溶液を、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去し、粗生成物を得た。得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=9/1)で精製し、目的物である((3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)エチニル)トリメチルシラン（化合物（１０２０））を、淡黄色固体として得た(収率71%、収量92mg)。以下に、((3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)エチニル)トリメチルシラン（化合物（１０２０））の機器分析値を示す。また、図５６に、((3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)エチニル)トリメチルシラン（化合物（１０２０））の¹H NMRチャートを示し、図５７に、((3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)エチニル)トリメチルシラン（化合物（１０２０））の¹³C NMRチャートを示す。 <Example 28: ((3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) ethynyl) trimethylsilane (compound (1020))>

1-Bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)) (125 mg, 0.25 mmol) was dried by heating in a Schlenk flask under reduced pressure. Next, CuI (4.8 mg, 0.025 mmol), PdCl ₂ (PPh ₃ ) ₂ (8.8 mg, 0.0125 mmol) and PPh ₃ (6.6 mg 0.025 mmol) were added into the Schlenk flask. Further, the inside of the Schlenk flask was replaced with argon three times, and toluene and triethylamine (each 1.5 mL) were added. The reaction mixture was stirred at room temperature for 15 minutes and trimethylsilylacetylene (74 mg, 0.75 mmol) was added. The mixture was then stirred at 70 ° C. for 21 hours. The solution thus obtained was filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters, thereby obtaining a crude product. The obtained crude product was purified by column chromatography (hexane / CHCl ₃ = 9/1), and the desired product ((3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl ) Ethynyl) trimethylsilane (compound (1020)) was obtained as a pale yellow solid (71% yield, 92 mg yield). The instrumental analysis values of ((3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) ethynyl) trimethylsilane (compound (1020)) are shown below. FIG. 56 shows a ¹ H NMR chart of ((3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) ethynyl) trimethylsilane (compound (1020)), and FIG. The ¹³ C NMR chart of ((3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) ethynyl) trimethylsilane (compound (1020)) is shown.

Instrumental analysis of ((3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) ethynyl) trimethylsilane (compound (1020)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.58 (d, J = 9.3Hz, 1H), 8.35 (d, J = 9.3Hz, 1H), 8.19 (d, J = 9.5Hz, 1H), 8.11 (d, J = 9.5Hz, 1H), 8.01 (s, 1H), 7.83 (s, 1H), 7.56 (d, J = 6.6Hz, 2H), 7.10 (d, J = 6.6Hz, 2H), 3.94 (s, 3H), 3.36 (t, J = 7.7, 7.7Hz, 2H), 3.25 (t, J = 7.7, 7.7Hz, 2H), 1.90-1.76 (m, 4H), 1.52-1.43 (m, 4H), 1.02 -0.95 (m, 6H), 0.40 (s, 9H). 13 C NMR (100MHz, CDCl 3) δ 159.3, 137.7, 136.4, 133.9, 132.0, 131.4, 131.3, 129.69, 129.67, 128.4, 127.4, 126.4, 125.87 , 125.86, 125.84, 125.4, 123.9, 122.6, 117.1, 114.1, 105.0, 99.9, 55.7, 34.5, 34.1, 33.9, 33.5, 23.3, 23.2, 14.41, 14.38, 0.6.MS (FAB) m / z: 516 (M _{^{+) Anal Calcd for C 36 H}} 40 OSi:.. C, 83.67; H, 7.80; Found: C, 83.65; H, 7.86.

NaO^tBu(72mg, 0.75mmol) を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、Pd₂(dba)₃・CHCl₃(13mg, 0.0125mmol)およびBINAP(16mg, 0.025mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴン置換した。そのシュレンクフラスコ内に、トルエン(2.0mL)を入れ、15分間撹拌した。つぎに、そのシュレンクフラスコ内に、1-ブロモ-3,8-ジブチル-6-(4-メトキシフェニル)ピレン（化合物（１０１６））(125mg, 0.25mmol)を加え、15分間撹拌した。さらに、前記シュレンクフラスコ内に、ピロリジン(0.06mL, 0.75mmol)を加え、密閉した。その混合物を、1.5時間以上かけて、90℃まで加熱した。さらに90℃で25時間撹拌後、得られた混合物を、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CH₂Cl₂=2/1)で精製し、目的物である1-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ピロリジン（化合物（１０２１））を、褐色固体として得た(収率80%、収量98mg)。以下に、1-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ピロリジン（化合物（１０２１））の機器分析値を示す。また、図５８に、1-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ピロリジン（化合物（１０２１））の¹H NMRチャートを示し、図５９に、1-(3,8-ジブチル-6-(4-メトキシフェニル)ピレン-1-イル)ピロリジン（化合物（１０２１））の¹³C NMRチャートを示す。 <Example 29: 1- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyrrolidine (Compound (1021))>

NaO ^t Bu (72 mg, 0.75 mmol) was dried by heating in a Schlenk flask under reduced pressure. Next, Pd ₂ (dba) ₃ .CHCl ₃ (13 mg, 0.0125 mmol) and BINAP (16 mg, 0.025 mmol) were added into the Schlenk flask. Further, the inside of the Schlenk flask was replaced with argon. Toluene (2.0 mL) was placed in the Schlenk flask and stirred for 15 minutes. Next, 1-bromo-3,8-dibutyl-6- (4-methoxyphenyl) pyrene (compound (1016)) (125 mg, 0.25 mmol) was added to the Schlenk flask and stirred for 15 minutes. Further, pyrrolidine (0.06 mL, 0.75 mmol) was added to the Schlenk flask and sealed. The mixture was heated to 90 ° C. over 1.5 hours. After further stirring at 90 ° C. for 25 hours, the resulting mixture was filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CH ₂ Cl ₂ = 2/1), and the target product 1- (3,8-dibutyl-6- (4-methoxyphenyl) Pyren-1-yl) pyrrolidine (compound (1021)) was obtained as a brown solid (yield 80%, yield 98 mg). The instrumental analysis values of 1- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyrrolidine (Compound (1021)) are shown below. 58 shows a ¹ H NMR chart of 1- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyrrolidine (compound (1021)), and FIG. The ¹³ C NMR chart of (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyrrolidine (compound (1021)) is shown.

Instrumental analysis of 1- (3,8-dibutyl-6- (4-methoxyphenyl) pyren-1-yl) pyrrolidine (compound (1021)):
¹ H NMR (400MHz, C ₆ D ₆ ) δ 8.66 (d, J = 9.6Hz, 1H), 8.29 (d, J = 9.4Hz, 1H), 8.25 (d, J = 9.6Hz, 1H), 8.11 ( d, J = 9.4Hz, 1H), 7.88 (s, 1H), 7.59 (d, J = 8.7Hz, 2H), 7.54 (s, 1H), 7.00 (d, J = 8.7Hz, 2H), 3.42- 3.19 (m, 11H), 1.82-1.72 (m, 8H), 1.46-1.39 (m, 4H), 0.94-0.90 (m, 6H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ 159.0, 144.6, 137.4, 136.0, 135.5, 134.5, 131.9, 129.3, 128.7, 127.9, 127.8, 126.8, 124.2, 124.1, 123.7, 122.8, 121.7, 120.9, 116.5, 114.0, 55.6, 53.9, 34.3, 34.2, 34.1, 25.4, 23.3, 23.2, 14.3.MS (FAB) m / z: 489 (M ⁺ ).

K₂CO₃(83mg, 0.6mmol)および2-(メトキシカルボニル)フェニルボロン酸(81mg, 0.45mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、メチル 4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンゾエート（化合物（１０１４））(158mg, 0.3mmol)およびPd(PPh₃)₄(69mg, 0.06mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、1.2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、22時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=1/4)で精製し、目的物であるジメチル 2,4'-(3,8-ジブチルピレン-1,6-ジイル)ジベンゾエート（化合物（１０２２））を、淡黄色固体として得た(収率73%、収量128mg)。以下に、ジメチル 2,4'-(3,8-ジブチルピレン-1,6-ジイル)ジベンゾエート（化合物（１０２２））の機器分析値を示す。また、図６０に、ジメチル 2,4'-(3,8-ジブチルピレン-1,6-ジイル)ジベンゾエート（化合物（１０２２））の¹H NMRチャートを示し、図６１に、ジメチル 2,4'-(3,8-ジブチルピレン-1,6-ジイル)ジベンゾエート（化合物（１０２２））の¹³C NMRチャートを示す。 <Example 30: Synthesis of dimethyl 2,4 '-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (1022))>

K ₂ CO ₃ (83 mg, 0.6 mmol) and 2- (methoxycarbonyl) phenylboronic acid (81 mg, 0.45 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, methyl 4- (6-bromo-3,8-dibutylpyren-1-yl) benzoate (compound (1014)) (158 mg, 0.3 mmol) and Pd (PPh ₃ ) ₄ (69 mg , 0.06 mmol). Further, the inside of the Schlenk flask was replaced with argon three times, and 1.2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 22 hours under reflux conditions of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 1/4), and the target product, dimethyl 2,4 '-(3,8-dibutylpyrene-1,6-diyl, was obtained. ) Dibenzoate (compound (1022)) was obtained as a pale yellow solid (73% yield, 128 mg yield). The instrumental analysis value of dimethyl 2,4 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (1022)) is shown below. FIG. 60 shows a ¹ H NMR chart of dimethyl 2,4 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (1022)), and FIG. 61 shows dimethyl 2,4 A ¹³ C NMR chart of '-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (1022)) is shown.

Instrumental analysis of dimethyl 2,4 '-(3,8-dibutylpyrene-1,6-diyl) dibenzoate (compound (1022)):
¹ H NMR (400 MHz, CDCl ₃ ) δ 8.25-8.20 (m, 3H), 8.15-8.08 (m, 3H), 7.81-7.79 (m, 2H), 7.74-7.72 (m, 3H), 7.68-7.65 ( m, 1H), 7.59-7.51 (m, 2H), 4.01 (s, 3H), 3.31 (s, 7H), 1.87-1.79 (m, 4H), 1.53-1.42 (m, 4H), 0.99-0.95 ( ¹³ C NMR (100 MHz, CDCl ₃ ) δ 168.5, 167.4, 146.7, 142.2, 137.1, 136.9, 136.6, 136.1, 132.7, 132.2, 131.7, 131.0, 130.4, 129.9, 129.1, 129.0, 128.9, 128.7 , 128.4, 127.8, 127.7, 127.3, 126.4, 126.0, 125.4, 124.7, 123.4, 122.8, 52.5, 52.1, 34.31, 34.30, 33.8, 33.7, 23.2, 23.1, 14.4, 14.3.MS (FAB) m / z: 582 (M ⁺ ). Anal. Calcd for C ₄₀ H ₃₈ O ₄ : C, 82.44; H, 6.57. Found: C, 82.45; H, 6.59.

メチル 4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンゾエート（化合物（１０１４））(132mg, 0.25mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、CuI(4.8mg, 0.025mmol)、PdCl₂(PPh₃)₂(8.8mg, 0.0125mmol)およびPPh₃(6.6mg 0.025mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、トルエンおよびトリエチルアミン(それぞれ1.5mL)を加えた。その反応混合物を、室温で15分間撹拌し、トリメチルシリルアセチレン（74mg, 0.75mmol）を加えた。その後、前記混合物を、さらに、70℃で15時間撹拌した。得られた溶液を、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=5/1)で精製し、目的物であるメチル 4-(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)ベンゾエート（化合物（１０２３））を、黄色固体として得た(収率74%、収量101mg)。以下に、メチル 4-(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)ベンゾエート（化合物（１０２３））の機器分析値を示す。また、図６２に、メチル 4-(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)ベンゾエート（化合物（１０２３））の¹H NMRチャートを示し、図６３に、メチル 4-(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)ベンゾエート（化合物（１０２３））の¹³C NMRチャートを示す。 <Example 31: Methyl 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzoate (Compound (1023))>

Methyl 4- (6-bromo-3,8-dibutylpyren-1-yl) benzoate (compound (1014)) (132 mg, 0.25 mmol) was dried by heating in a Schlenk flask under reduced pressure. Next, CuI (4.8 mg, 0.025 mmol), PdCl ₂ (PPh ₃ ) ₂ (8.8 mg, 0.0125 mmol) and PPh ₃ (6.6 mg 0.025 mmol) were added into the Schlenk flask. Further, the inside of the Schlenk flask was replaced with argon three times, and toluene and triethylamine (each 1.5 mL) were added. The reaction mixture was stirred at room temperature for 15 minutes and trimethylsilylacetylene (74 mg, 0.75 mmol) was added. Thereafter, the mixture was further stirred at 70 ° C. for 15 hours. The obtained solution was filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 5/1), and the target product, methyl 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyrene, was obtained. 1-yl) benzoate (compound (1023)) was obtained as a yellow solid (74% yield, 101 mg yield). The instrumental analysis values of methyl 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzoate (compound (1023)) are shown below. FIG. 62 shows a ¹ H NMR chart of methyl 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzoate (compound (1023)), and FIG. A ¹³ C NMR chart of 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzoate (compound (1023)) is shown.

Instrumental analysis of methyl 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzoate (compound (1023)):
¹ H NMR (400MHz, CDCl ₃ ) δ 8.62 (d, J = 9.4Hz, 1H), 8.36 (d, J = 9.4Hz, 1H), 8.23 (d, J = 8.2Hz, 2H), 8.15-8.09 ( m, 2H), 8.03 (s, 1H), 7.83 (s, 1H), 7.71 (d, J = 8.2Hz, 2H), 4.01 (s, 3H), 3.37 (t, J = 7.7Hz, 7.7Hz, 2H), 3.25 (t, J = 7.7Hz, 7.7Hz, 2H), 189-1.77 (m, 4H), 1.57-1.45 (m, 4H), 1.03-0.96 (m, 6H), 0.41 (s, 9H ¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.4, 146.4, 137.8, 136.8, 136.6, 131.5, 131.3, 131.0, 129.9, 129.5, 129.3, 129.2, 129.0, 127.1, 125.9, 125.75, 125.74, 123.8, 123.2, 117.5, 104.7, 100.2, 52.5, 34.5, 34.1, 33.9, 33.5, 23.3, 23.2, 14.4, 14.3, 0.5.MS (FAB) m / z: 544 (M ⁺ ).

K₂CO₃(83mg, 0.6mmol)および2-ホルミルフェニルボロン酸(68mg, 0.45mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンズアルデヒド（化合物（１０１５））(149mg, 0.3mmol)およびPd(PPh₃)₄(69mg, 0.06mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、1.2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、17時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=2/1)で精製し、目的物である2,4'-(3,8-ジブチルピレン-1,6-ジイル)ジベンズアルデヒド（化合物（１０２４））を、淡黄色固体として得た(収率85%、収量137mg)。以下に、2,4'-(3,8-ジブチルピレン-1,6-ジイル)ジベンズアルデヒド（化合物（１０２４））の機器分析値を示す。また、図６４に、2,4'-(3,8-ジブチルピレン-1,6-ジイル)ジベンズアルデヒド（化合物（１０２４））の¹H NMRチャートを示し、図６５に、2,4'-(3,8-ジブチルピレン-1,6-ジイル)ジベンズアルデヒド（化合物（１０２４））の¹³C NMRチャートを示す。 <Example 32: 2,4 '-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (1024))>

K ₂ CO ₃ (83 mg, 0.6 mmol) and 2-formylphenylboronic acid (68 mg, 0.45 mmol) were dried by heating under reduced pressure in a Schlenk flask. Next, in the Schlenk flask, 4- (6-bromo-3,8-dibutylpyren-1-yl) benzaldehyde (compound (1015)) (149 mg, 0.3 mmol) and Pd (PPh ₃ ) ₄ (69 mg, 0.06 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 1.2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 17 hours under DMF reflux conditions (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 2/1), and the desired product 2,4 ′-(3,8-dibutylpyrene-1,6-diyl) Dibenzaldehyde (compound (1024)) was obtained as a pale yellow solid (yield 85%, yield 137 mg). The instrumental analysis values of 2,4 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (1024)) are shown below. FIG. 64 shows a ¹ H NMR chart of 2,4 ′-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (1024)), and FIG. 65 shows 2,4′- A ¹³ C NMR chart of (3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (1024)) is shown.

Instrumental analysis of 2,4 '-(3,8-dibutylpyrene-1,6-diyl) dibenzaldehyde (compound (1024)):
¹ H NMR (400MHz, CDCl ₃ ) δ 10.18 (s, 1H), 9.66 (s, 1H), 8.25 (d, J = 9.6Hz, 1H), 8.21-8.15 (m, 3H), 8.10 (d, J = 8.2Hz, 2H), 7.86-7.76 (m, 6H), 7.67-7.59 (m, 2H), 3.37-3.31 (m, 4H), 1.89-1.79 (m, 4H), 1.52-1.44 (m, 4H ), 1.0-0.96 (m, 6H) . 13 C NMR (100MHz, CDCl 3) δ 192.4, 192.2, 148.0, 145.2, 137.5, 136.9, 136.3, 135.4, 135.3, 133.9, 132.7, 132.5, 131.6, 130.1, 130.0 , 129.3, 129.1, 128.9, 128.8, 128.5, 127.5, 127.2, 126.1, 125.9, 125.3, 125.2, 123.7, 123.4, 34.3, 34.2, 33.7, 33.6, 23.2, 23.1, 14.29, 14.27.MS (FAB) m / z : 522 (M ⁺ ). Anal. Calcd for C ₃₈ H ₃₄ O ₂ : C, 87.32; H, 6.56. Found: C, 87.35; H, 6.68.

K₂CO₃(83mg, 0.6mmol)およびピレン-1-イルボロン酸(111mg, 0.45mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンズアルデヒド（化合物（１０１５））(149mg, 0.3mmol)およびPd(PPh₃)₄(69mg, 0.06mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、1.2mLのDMFを加えた。その反応混合物を、室温で1分間撹拌し、さらに、DMFの還流条件下（オイルバスで105℃に加熱）で、10時間反応させた。反応終了後、得られた混合物を酢酸エチルで希釈し、さらに、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=2/1)で精製し、目的物である4-(3,8-ジブチル-1,11-ビピレン-6-イル)ベンズアルデヒド（化合物（１０２５））を、淡黄色固体として得た(収率97%、収量180mg)。以下に、4-(3,8-ジブチル-1,11-ビピレン-6-イル)ベンズアルデヒド（化合物（１０２５））の機器分析値を示す。また、図６６に、4-(3,8-ジブチル-1,11-ビピレン-6-イル)ベンズアルデヒド（化合物（１０２５））の¹H NMRチャートを示し、図６７に、4-(3,8-ジブチル-1,11-ビピレン-6-イル)ベンズアルデヒド（化合物（１０２５））の¹³C NMRチャートを示す。 <Example 33: 4- (3,8-dibutyl-1,11-bipyrene-6-yl) benzaldehyde (compound (1025))>

K ₂ CO ₃ (83 mg, 0.6 mmol) and pyren-1-ylboronic acid (111 mg, 0.45 mmol) were dried by heating in a Schlenk flask under reduced pressure. Next, in the Schlenk flask, 4- (6-bromo-3,8-dibutylpyren-1-yl) benzaldehyde (compound (1015)) (149 mg, 0.3 mmol) and Pd (PPh ₃ ) ₄ (69 mg, 0.06 mmol) was added. Further, the inside of the Schlenk flask was replaced with argon three times, and 1.2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 minute and further reacted for 10 hours under the reflux condition of DMF (heating to 105 ° C. in an oil bath). After completion of the reaction, the obtained mixture was diluted with ethyl acetate, and further filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 2/1), and the desired product 4- (3,8-dibutyl-1,11-bipyrene-6-yl) was obtained. Benzaldehyde (compound (1025)) was obtained as a pale yellow solid (yield 97%, yield 180 mg). The instrumental analysis value of 4- (3,8-dibutyl-1,11-bipyren-6-yl) benzaldehyde (compound (1025)) is shown below. 66 shows a ¹ H NMR chart of 4- (3,8-dibutyl-1,11-bipyrene-6-yl) benzaldehyde (compound (1025)), and FIG. 67 shows 4- (3,8 ¹³ shows a ¹³ C NMR chart of -dibutyl-1,11-bipyrene-6-yl) benzaldehyde (compound (1025)).

Instrumental analysis of 4- (3,8-dibutyl-1,11-bipyrene-6-yl) benzaldehyde (compound (1025)):
¹ H NMR (400MHz, CDCl ₃ ) δ 10.2 (s, 1H), 8.37-8.32 (m, 2H), 8.27-8.02 (m, 11H), 7.91-7.85 (m, 4H), 7.70 (d, J = 9.5, 9.5Hz, 1H), 7.68 (d, J = 9.5, 9.5Hz, 1H) .3.41 (t, J = 7.6, 7.9Hz, 2H), 3.28 (t, J = 7.6, 7.9Hz, 2H), 1.95-1.76 (m, 4H), 1.54-1.40 (m, 4H), 0.99 (t, J = 7.4, 7.4Hz, 2H), 0.93 (t, J = 7.4, 7.4Hz, 2H). ¹³ C NMR ( 100MHz, CDCl ₃ ) δ 192.3, 148.3, 137.1, 136.9, 136.7, 136.4, 135.9, 135.4, 131.7, 131.6, 131.2, 131.1, 130.8, 130.3, 130.0, 129.14, 129.11, 129.0, 129.0, 128.7, 127.8, 127.7, 127.3, 126.4, 126.3, 126.2, 126.1, 125.5, 125.3, 125.08, 125.06, 124.83, 124.77, 123.6, 122.9, 34.3, 34.2, 33.7, 33.6, 23.2, 23.1, 14.4, 14.3.MS (FAB) m / z: 618 (M ⁺ ).

4-(6-ブロモ-3,8-ジブチルピレン-1-イル)ベンズアルデヒド（化合物（１０１５））(124mg, 0.25mmol)を、シュレンクフラスコ中、減圧下で加熱して乾燥した。つぎに、そのシュレンクフラスコ内に、CuI(4.8mg, 0.025mmol)、PdCl₂(PPh₃)₂(8.8mg, 0.0125mmol)およびPPh₃(6.6mg 0.025mmol)を加えた。さらに、前記シュレンクフラスコ内をアルゴンで３回置換し、トルエンおよびトリエチルアミン(それぞれ1.5mL)を加えた。その反応混合物を、室温で15分間撹拌し、さらに、70℃で15時間撹拌した。得られた溶液を、セライト（商品名）およびフロリジル（商品名）で濾過して不溶物を除去した。これにより得られた粗生成物を、カラムクロマトグラフィー(ヘキサン/CHCl₃=9/1)で精製し、目的物である4-(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)ベンズアルデヒド（化合物（１０２６））を、黄色固体として得た(収率91%、収量117mg)。以下に、4-(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)ベンズアルデヒド（化合物（１０２６））の機器分析値を示す。また、図６８に、4-(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)ベンズアルデヒド（化合物（１０２６））の¹H NMRチャートを示し、図６９に、4-(3,8-ジブチル-6-((トリメチルシリル)エチニル)ピレン-1-イル)ベンズアルデヒド（化合物（１０２６））の¹³C NMRチャートを示す。 <Example 34: 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzaldehyde (compound (1026))>

4- (6-Bromo-3,8-dibutylpyren-1-yl) benzaldehyde (compound (1015)) (124 mg, 0.25 mmol) was dried by heating in a Schlenk flask under reduced pressure. Next, CuI (4.8 mg, 0.025 mmol), PdCl ₂ (PPh ₃ ) ₂ (8.8 mg, 0.0125 mmol) and PPh ₃ (6.6 mg 0.025 mmol) were added into the Schlenk flask. Further, the inside of the Schlenk flask was replaced with argon three times, and toluene and triethylamine (each 1.5 mL) were added. The reaction mixture was stirred at room temperature for 15 minutes and further stirred at 70 ° C. for 15 hours. The obtained solution was filtered through Celite (trade name) and Florisil (trade name) to remove insoluble matters. The crude product thus obtained was purified by column chromatography (hexane / CHCl ₃ = 9/1), and the desired product 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyrene- 1-yl) benzaldehyde (compound (1026)) was obtained as a yellow solid (91% yield, 117 mg yield). The instrumental analysis values of 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzaldehyde (Compound (1026)) are shown below. FIG. 68 shows a ¹ H NMR chart of 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzaldehyde (compound (1026)), and FIG. The ¹³ C NMR chart of (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzaldehyde (compound (1026)) is shown.

Instrumental analysis of 4- (3,8-dibutyl-6-((trimethylsilyl) ethynyl) pyren-1-yl) benzaldehyde (compound (1026)):
¹ H NMR (400MHz, CDCl ₃ ) δ 10.16 (s, 1H), 8.63 (d, J = 9.4Hz, 1H), 8.37 (d, J = 9.4Hz, 1H), 8.17-8.03 (m, 5H), 7.84-7.80 (m, 3H), 3.38 (t, J = 7.7, 7.7Hz, 2H), 3.32 (t, J = 7.7, 7.7Hz, 2H), 1.89-1.78 (m, 4H), 1.53-1.45 ( m, 4H), 1.03-0.97 (m , 6H), 0.40 (s, 9H). 13 C NMR (100MHz, CDCl 3) δ 192.3, 148.1, 137.8, 136.9, 136.2, 135.5, 131.6, 131.5, 131.2, 130.0 , 129.4, 129.20, 129.17, 127.0, 126.1, 125.74, 125.69, 125.5, 123.7, 123.3, 117.7, 104.7, 100.35, 34.4, 34.1, 33.9, 33.5, 23.3, 23.2, 14.4, 14.3, 0.6.MS (FAB) m / z: 514 (M ⁺ ). Anal. Calcd for C ₃₆ H ₃₈ OSi: C, 84.00; H, 7.44. Found: C, 84.02; H, 7.38.

  As described above, according to Examples 10 to 34, starting from (6-bromo-3,8-dibutylpyren-1-yl) tetramethylsilane (1001) synthesized in Example 9, And asymmetric pyrene derivatives (1002) to (1026) into which various functional groups were introduced at the 6-position could be synthesized.

  As described above, according to the present invention, a pyrene derivative having a novel structure and characteristics, a production method capable of easily producing the pyrene derivative, a complex, a catalyst, an electronic material, a light-emitting material, and a dye using the pyrene derivative are obtained. Can be provided. Furthermore, the use of the pyrene derivative of the present invention is not limited to these. For example, it may be used for the same use as known pyrene or a derivative thereof, or may be used for any other use.

Claims (20)

Pyrene derivatives represented by the following chemical formula (I), tautomers, geometric isomers or stereoisomers thereof, or salts thereof.

In the chemical formula (I),
Ar is a hydrogen atom or an arbitrary substituent, and each Ar may be the same or different;
At least one of Ar is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ , a trialkylsilyl group, a substituted or Unsubstituted ethynylene group, trialkylsilylethynylene group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, arylamino group, diarylamino group, alkylamino group, dialkylamino group, bis (trialkyl Silyl) amino group, substituted or unsubstituted saturated or unsaturated alicyclic hydrocarbon group, substituted or unsubstituted saturated or unsaturated non-aromatic heterocyclic ring, substituted or unsubstituted piperidyl group, substituted or unsubstituted A piperazyl group, a substituted or unsubstituted pyrrolidyl group, or a substituted or An unsubstituted morpholino group,
R ¹⁰⁰ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group may be linear, branched or cyclic, saturated or unsaturated, and may have a substituent. Each R ¹⁰⁰ may be the same or different,
R ¹ is a hydrocarbon group, which may be linear, branched, or cyclic, saturated or unsaturated, may or may not have a substituent, and each R ¹ is the same But it can be different,
R ² is a hydrogen atom or an arbitrary substituent, and each R ² may be the same or different,
R ³ is an arbitrary substituent, each R ³ may be the same or different, a is the number of substitutions from 0 to 2, and each a may be the same or different. In the chemical formula (I),
The pyrene derivative according to claim 1, at least one of Ar is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, a tautomer, geometric isomer or stereoisomer thereof, or Their salt. In the chemical formula (I),
The pyrene derivative according to claim 1 or 2, wherein in each Ar, the aryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyrenyl group. , Geometric isomers or stereoisomers, or salts thereof. In the chemical formula (I),
In each Ar, the aryl group is unsubstituted or an alkyl group, an alkoxy group, an alkylthio group, an acyl group, an alkanoyl group, a formyl group, a halocarbonyl group, a chlorocarbonyl group, a carboxy group, an alkoxycarbonyl group, Hydroxyalkyl group, mercaptoalkyl group, hydroxy group, mercapto group, amino group, aminoalkyl group, alkylamino group, dialkylamino group, aryl group, chain hydrocarbon group, alicyclic hydrocarbon group, alkylsilyl group, dialkyl It is substituted with at least one substituent selected from the group consisting of a silyl group, a trialkylsilyl group, and a deuterium atom, and the substituent may be further substituted with a further substituent. The pyrene derivative according to any one of 3 above, a tautomer and a geometric isomer thereof Properly stereoisomers or salts thereof.   The further substituent is an alkyl group, alkoxy group, alkylthio group, acyl group, alkanoyl group, formyl group, halocarbonyl group, chlorocarbonyl group, carboxy group, alkoxycarbonyl group, hydroxyalkyl group, mercaptoalkyl group, hydroxy group, Mercapto group, amino group, aminoalkyl group, alkylamino group, dialkylamino group, aryl group, chain hydrocarbon group, alicyclic hydrocarbon group, alkylsilyl group, dialkylsilyl group, trialkylsilyl group, and deuterium The pyrene derivative according to claim 4, which is at least one selected from the group consisting of atoms, tautomers, geometric isomers or stereoisomers thereof, or salts thereof. In the chemical formula (I),
Each R ¹ is a linear or branched alkyl group having 1 to 20 carbon atoms, the pyrene derivative according to any one of claims 1 to 5, its tautomer, geometric isomer or stereoisomer, Or their salts. The pyrene derivative according to claim 1, wherein the pyrene derivative represented by the chemical formula (I) is a pyrene derivative represented by any one of the following chemical formulas (101) to (108) and (1001) to (1026). Its tautomers, geometric isomers or stereoisomers, or salts thereof.

In the chemical formula (I), Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,
A cross-coupling step in which a halogenated pyrene derivative represented by the following chemical formula (II) and an aryl boronic acid represented by the following chemical formula (III) are subjected to a cross-coupling reaction in the presence of a palladium catalyst. A method for producing a pyrene derivative according to any one of 1 to 7, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof.

In the chemical formula (II),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I),
X is a halogeno group, and each X may be the same or different;
In the chemical formula (III),
Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined in the chemical formula (I) and any one of claims 1 to 5. The pyrene derivative represented by the chemical formula (I) is a pyrene derivative represented by the following chemical formula (I ′),
A metalation step of producing a pyrene derivative represented by the following chemical formula (IV) by metallizing a halogenated pyrene derivative represented by the following chemical formula (II);
Following chemical formula is reacted with a cation of the pyrene derivative and R ⁴ of formula (IV) by introducing a substituent R ⁴ in a substituted group introduction step for producing a pyrene derivative represented by the following formula (V) and,
A cross-coupling step in which a pyrene derivative represented by the following chemical formula (V) and an aryl boronic acid represented by the following chemical formula (III) are subjected to a cross-coupling reaction in the presence of a palladium catalyst,
The method for producing a pyrene derivative according to any one of claims 1 to 7, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof.

In the chemical formula (I ′),
Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined in the chemical formula (I) and any one of claims 1 to 5;
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I),
R ⁴ is an optional substituent other than an aryl group,
In the chemical formulas (II), (IV) and (V),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I ′),
X is a halogeno group, and each X in the chemical formula (II) may be the same or different;
In the chemical formula (IV),
M is a metal,
In the chemical formula (V),
R ⁴ is the same as the chemical formula (I ′),
In the chemical formula (III),
Ar is the same as in the chemical formula (I ′). In the chemical formulas (V) and (I ′),
The production method according to claim 9, wherein R ⁴ is a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ . In the chemical formulas (V) and (I ′),
The production method according to claim 10, wherein R ⁴ is a trialkylsilyl group. In the chemical formula (I), Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,
A silylpyrene derivative production step for producing a silylpyrene derivative represented by the chemical formula (I ′) by the production method according to claim 10 or 11;
A halogenation step of producing a halogenated pyrene derivative represented by the following chemical formula (V ″) by reacting the silylpyrene derivative represented by the chemical formula (I ′) with a halogenating agent; and
A halogenated pyrene derivative represented by the following chemical formula (V ″) and an aryl boronic acid represented by the following chemical formula (III ′) are subjected to a cross-coupling reaction in the presence of a palladium catalyst to obtain the following chemical formula (I): Including a second cross-coupling step to produce the represented pyrene derivative,
The method for producing a pyrene derivative according to any one of claims 1 to 7, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof.

In the chemical formulas (I ′) and (III ′),
Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined in the chemical formula (I) and any one of claims 1 to 5, and each Ar is the same or different. Well,
In the chemical formula (I ′),
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I),
R ⁴ is a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ ;
In the chemical formula (V ″),
Ar is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group defined in the chemical formula (I) and any one of claims 1 to 5;
R ¹ , R ² , R ³ and a are the same as in the chemical formula (I). The pyrene derivative represented by the chemical formula (I) is a pyrene derivative represented by the chemical formula (V) according to claim 9,
In the chemical formula (V), R ⁴ is a substituted or unsubstituted silyl group represented by —Si (R ¹⁰⁰ ) ₃ ;
A metalation step of producing a pyrene derivative represented by the chemical formula (IV) according to claim 9 by metallizing the halogenated pyrene derivative represented by the chemical formula (II) according to claim 9, and
Said formula is reacted with a cation of the pyrene derivative and R ⁴ of formula (IV) by introducing a substituent R ^4, including substituents introduction step of producing a pyrene derivative represented by the formula (V),
The method for producing a pyrene derivative according to any one of claims 1 to 7, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof. The pyrene derivative represented by the chemical formula (I) is a pyrene derivative represented by the chemical formula (V ″) according to claim 12,
A silylpyrene derivative production process for producing a silylpyrene derivative represented by the chemical formula (I ') by the production method according to claim 10 or 11, and
A halogenation step of producing a halogenated pyrene derivative represented by the chemical formula (V ″) by reacting the silylpyrene derivative represented by the chemical formula (I ′) with a halogenating agent,
The method for producing a pyrene derivative according to any one of claims 1 to 7, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof. In the cross-coupling step, a substituted or unsubstituted saturated or unsaturated non-aromatic heterocyclic compound, a substituted or unsubstituted alcohol, substituted or unsubstituted, instead of the arylboronic acid represented by the chemical formula (III) Using substituted phenol, arylamine, diarylamine, alkylamine, dialkylamine, or bis (trialkylsilyl) amine,
In the cross-coupling step, Ar introduced into the pyrene derivative (I ′) is substituted or unsubstituted aryl group or substituted or unsubstituted heteroaryl group, substituted or unsubstituted saturated or unsaturated non-aromatic An aromatic heterocycle, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, arylamino group, diarylamino group, alkylamino group, dialkylamino group, or bis (trialkylsilyl) amino group Item 15. The production method according to any one of Items 8 to 12 and 14. In the second cross-coupling step, in place of the arylboronic acid represented by the chemical formula (III), a substituted or unsubstituted saturated or unsaturated non-aromatic heterocyclic compound, a substituted or unsubstituted alcohol, a substituted Or using unsubstituted phenol, arylamine, diarylamine, alkylamine, dialkylamine, or bis (trialkylsilyl) amine,
In the second cross-coupling step, Ar introduced into the pyrene derivative (I) is substituted or unsubstituted aryl group or substituted or unsubstituted heteroaryl group, substituted or unsubstituted saturated or unsaturated non-substituted An aromatic heterocycle, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, an arylamino group, a diarylamino group, an alkylamino group, a dialkylamino group, or a bis (trialkylsilyl) amino group The manufacturing method according to claim 12 or 15. In the cross-coupling step, substituted or unsubstituted acetylene is used instead of the arylboronic acid represented by the chemical formula (III),
The Ar introduced into the pyrene derivative (I ′) in the cross-coupling step is a substituted or unsubstituted ethynylene group instead of a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. The production method according to any one of 8 to 12 and 14. In the second cross-coupling step, substituted or unsubstituted acetylene is used instead of the arylboronic acid represented by the chemical formula (III),
Ar introduced into the pyrene derivative (I) in the second cross-coupling step is a substituted or unsubstituted ethynylene group instead of a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. Item 18. The production method according to Item 12, 15 or 17.   A complex comprising the pyrene derivative according to any one of claims 1 to 7, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof as a ligand.   A pyrene derivative according to any one of claims 1 to 7, a tautomer, geometric isomer or stereoisomer thereof, or a salt thereof or a complex according to claim 19, comprising a catalyst, an electronic material, Products that are luminescent materials or pigments.

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