JP2011162490A - Highly-conjugated compound, precursor thereof, and method for producing highly-conjugated compound - Google Patents

Abstract

A novel highly conjugated compound is provided.
SOLUTION: Formula (1)

Alternatively, a highly conjugated compound represented by a structure in which the benzene ring is replaced with a pyridine ring. Also provided are heterocyclic compounds as precursors thereof. The target highly conjugated compound can be produced by oxidizing the precursor compound. Such a compound is useful as an organic field effect transistor or a conductive material.
[Selection figure] None

Description

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

  Conventionally, highly conjugated compounds having a large π-electron conjugated system have been of interest as highly functional materials such as organic field effect transistors and sensors. Various studies have been conducted on such highly conjugated compounds. For example, it has been reported that diazines can be obtained by reacting fluorobenzenes with pyrrole and then oxidizing the resulting compound. (For example, Non-Patent Document 1 and Non-Patent Document 2).

M. Lazerges et al., “Mechanism of Pyrrolyl Oxidation in Star-Shaped Compounds”, Journal of Physical Chemistry A, American Chemical Society, 2003, 107, p. 5042-5048 Masayoshi Takase et al., 4 authors, “Annularly Fused Hexapyrrolohexaazakoronenes: An Extended π System with Multiple Interior Nitrogen Atoms Displays Stable Oxidation State), Angewandte Chemie International Edition, German Society of Chemistry, 2007, 46, p.5524-5527

The most serious problem in synthesizing highly conjugated compounds (especially those having high planarity) is the low solubility of raw materials and products. For example, pentacene, which is actively studied as an organic semiconductor material, has very poor solubility, and has been subjected to sublimation purification in order to achieve high purity, and depending on the desired purity, sublimation purification needs to be performed many times. It was very inefficient.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel highly conjugated compound. It is another object of the present invention to provide a precursor useful for efficiently obtaining a highly pure highly conjugated compound and a method for producing the highly conjugated compound.

  It is represented by the formula (1), the formula (2a), or the formula (2b) of the present invention that can solve the above-mentioned problems.

Wherein ^(1), R 1 ~R ⁴ are the same or different, represent a hydrogen atom or a halogenated optionally an aliphatic hydrocarbon group. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of aliphatic hydrocarbon groups which may be halogenated, and these aliphatic hydrocarbon groups which may be halogenated are bonded to each other. Thus, a ring structure may be formed. X represents a hydrogen atom or forms a carbon-carbon bond between adjacent XX. A ^{1 to} A ⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (3). ]

[In formulas (2a) and (2b), R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an optionally halogenated hydrocarbon group. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of hydrocarbon groups which may be halogenated, and these hydrocarbon groups which may be halogenated are bonded to each other to form a ring structure. May be formed. X represents a hydrogen atom or forms a carbon-carbon bond between adjacent XX. A ^{1 to} A ³ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (3). ]

[In Formula (3), R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or a hydrocarbon group which may be halogenated, and may be bonded to each other to form a ring structure. X represents a hydrogen atom or forms a carbon-carbon bond between adjacent XX. * Represents a bonding position. Note that when substituents plurality of A ¹ to A ⁴ is represented by the formula (3), a plurality of R ⁵ may be the same or different, may be different in each of a plurality of R ⁶ are the same. ]

As the compound represented by the formula (1), those in which the skeleton excluding R ^{1 to} R ⁶ corresponds to the formulas (4a) to (4c) are preferable.

[In the formulas (4a) to (4c), ** represents a bonding position of R ^{1 to} R ⁶ . D ¹ and D ² are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6a). ]

[In the formula (6a), ** represents the bonding position of R ⁵ and R ⁶ . * Represents a bonding position. ]

As examples of the formula (2a) or a compound represented by the formula (2b), which skeleton excluding the R ¹ to R ⁶ corresponds to Formula (5a) ~ (5c) are preferred.

[In formulas (5a) to (5c), * represents a bonding position of R ^{1 to} R ⁶ . D ¹ represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6a). ]

In the above formula, the ring structure formed by R ¹ and R ² , R ³ and R ⁴ , or R ⁵ and R ⁶ is preferably the one represented by the formula (7a) or the formula (7b).

[In formulas (7a) and (7b), * indicates a bonding position. ]

  The highly conjugated compound precursor of the present invention is represented by the formula (8), the formula (9a), or the formula (9b).

[In Formula (8), R < ¹ > -R < ⁴ > is the same or different, and represents the aliphatic hydrocarbon group which may be a hydrogen atom or halogenated. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of aliphatic hydrocarbon groups which may be halogenated, and these aliphatic hydrocarbon groups which may be halogenated are bonded to each other. Thus, a ring structure may be formed. F ^{1 to} F ⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6). ]

[In the formulas (9a) and (9b), R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an optionally halogenated hydrocarbon group. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of hydrocarbon groups which may be halogenated, and these hydrocarbon groups which may be halogenated are bonded to each other to form a ring structure. May be formed. F ^{1 to} F ³ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6). ]

[In formula (6), R ⁵ and R ⁶ represent a hydrogen atom or a hydrocarbon group which may be halogenated, and may be bonded to each other to form a ring structure. * Represents a bonding position. Note that when substituents plurality of F ¹ to F ⁴ are represented by the formula (6), a plurality of R ⁵ may be the same or different, may be different in each of a plurality of R ⁶ are the same. ]

  The production method of the highly conjugated compound of the present invention is the compound represented by the formula (10) or the formula (11) and two or more of the compounds represented by the formulas (12a) to (12c) (provided that the formula (12a) A highly conjugated compound precursor represented by formula (8), formula (9a) or formula (9b) is synthesized from the compound represented by formula (12b) and the compound represented by formula (12b). By oxidizing the precursor, a highly conjugated compound represented by formula (1), formula (2a) or formula (2b) is produced.

[In the formulas (10) and (11), E ^{1 to} E ⁶ are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, or a cyano group. ]

[In the formulas (12a) to (12c), R ^{1 to} R ⁶ are the same or different and represent a hydrocarbon group which may be halogenated and may be bonded to each other to form a ring structure. Good. ]

  Moreover, in the said manufacturing method, after refine | purifying a highly conjugated compound precursor, the aspect which oxidizes this highly conjugated compound precursor is preferable.

  According to the present invention, a novel highly conjugated compound is obtained. Moreover, according to the production method of the present invention, a highly conjugated compound having a higher purity can be easily produced.

<Highly conjugated compounds>
The highly conjugated compound of the present invention will be described. The highly conjugated compound of the present invention is represented by the formula (1), the formula (2a) or the formula (2b). That is, the highly conjugated compound of the present invention has benzene or pyridine as a basic skeleton, and two pyrrolyl groups are added so as to be located at ortho positions relative to each other, and these pyrrolyl groups are cyclized. It has a structure, and it is an essential requirement that at least one of the two pyrrolyl groups has a substituent at the 3-position and the 4-position.

  Thus, in the highly conjugated compound of the present invention, two pyrrolyl groups are added and these are cyclized, so that the π-electron conjugated system is expanded and the band gap is reduced. In addition, since the pyrrolyl group has two substituents, the solubility of the highly conjugated compound is easily improved and the purification load can be reduced. Furthermore, depending on the substituent, the π-electron conjugated system of the highly conjugated compound can be further expanded, and the LUMO can be lowered.

Wherein ^(1), R 1 ~R ⁴ are the same or different, represent a hydrogen atom or a halogenated optionally an aliphatic hydrocarbon group. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of aliphatic hydrocarbon groups which may be halogenated, and these aliphatic hydrocarbon groups which may be halogenated are bonded to each other. Thus, a ring structure may be formed. X represents a hydrogen atom or forms a carbon-carbon bond between adjacent XX. A ^{1 to} A ⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (3). ]

[In formulas (2a) and (2b), R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an optionally halogenated hydrocarbon group. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of hydrocarbon groups which may be halogenated, and these hydrocarbon groups which may be halogenated are bonded to each other to form a ring structure. May be formed. X represents a hydrogen atom or forms a carbon-carbon bond between adjacent XX. A ^{1 to} A ³ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (3). ]

[In Formula (3), R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or a hydrocarbon group which may be halogenated, and may be bonded to each other to form a ring structure. X represents a hydrogen atom or forms a carbon-carbon bond between adjacent XX. * Represents a bonding position. Note that when substituents plurality of A ¹ to A ⁴ is represented by the formula (3), a plurality of R ⁵ may be the same or different, may be different in each of a plurality of R ⁶ are the same. ]

Examples of the optionally halogenated hydrocarbon group represented by R ^{1 to} R ⁶ include an optionally substituted aliphatic hydrocarbon group (aliphatic hydrocarbon group and halogenated aliphatic hydrocarbon group), halogen An aromatic hydrocarbon group (aromatic hydrocarbon group and halogenated aromatic hydrocarbon group) which may be converted to an aromatic hydrocarbon group.

The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Specifically, for example, a linear aliphatic hydrocarbon group such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group; 1-methylethyl group (isopropyl Group), 1,1-dimethylethyl group (tert-butyl group), 2,2-dimethylethyl group (sec-butyl group), 1-methylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group Branched aliphatic hydrocarbon groups such as butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group and 1-methylpentyl group; cyclic fats such as cyclopropyl group, cyclobutyl group and cyclopentyl group Group hydrocarbon group and the like.
Examples of the halogenated aliphatic hydrocarbon group include those in which the hydrogen atom of the aliphatic hydrocarbon group is substituted with a halogen atom. Here, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthranyl group, and a biphenyl group.
Examples of the halogenated aromatic hydrocarbon group include those in which the hydrogen atom of the aromatic hydrocarbon group is substituted with a halogen atom. Here, examples of the halogen atom include those described above.

Here, when R ¹ and R ² , R ³ and R ⁴ or R ⁵ and R ⁶ do not form a ring structure, R ^{1 to} R ⁶ preferably have 2 or more carbon atoms, more preferably 3 or more. More preferably, it is 4 or more, preferably 10 or less, more preferably 9 or less, still more preferably 8 or less. These are preferably straight-chain aliphatic hydrocarbon groups. When R ^{1 to} R ⁶ are branched aliphatic hydrocarbon groups, the solubility of the highly conjugated compound is further improved. However, when a highly conjugated compound is used for an organic semiconductor or the like, the interaction between molecules (ππ stacking) may be hindered by the branching of the aliphatic hydrocarbon group.

The halogenated aliphatic hydrocarbon group represented by R ⁵ or R ⁶ preferably has 2 or more carbon atoms, more preferably 3 or more, still more preferably 4 or more, and more preferably 10 or less, more Preferably it is 9 or less, More preferably, it is 8 or less. These are preferably straight-chain halogenated aliphatic hydrocarbon groups. When R ⁵ and R ⁶ are branched aliphatic hydrocarbon groups, the solubility of the highly conjugated compound is further improved. However, when a highly conjugated compound is used for an organic semiconductor or the like, the interaction between molecules (ππ stacking) may be hindered by the branching of the aliphatic hydrocarbon group.

The ring structure formed by R ¹ and R ² , R ³ and R ⁴ , or R ⁵ and R ⁶ is not particularly limited, and may be monocyclic or polycyclic such as a bridged cyclic structure. It may be. The bridged cyclic hydrocarbon group includes those having an unsaturated bond therein. Furthermore, a structure in which a bridge ring is condensed with a monocyclic ring or a polycycle, or a structure in which bridge rings are condensed with each other is also included. Among these, as the ring structure, a ring structure that can be conjugated with the pyrrolyl ring and a ring structure that is a precursor thereof are preferable. If such an interstructure is formed, the π-electron conjugated system of the highly conjugated compound is further expanded, and the band gap becomes smaller.

Specific examples of the ring structure formed by R ¹ and R ² , R ³ and R ⁴ , or R ⁵ and R ⁶ include those represented by formulas (7a) to (7f).

[In formulas (7a) to (7f), * indicates a bonding position. ]

Among the ring structures, as the ring structure formed by R ¹ and R ² , R ³ and R ⁴ , or R ⁵ and R ⁶ , those represented by formula (7a) or formula (7b) are preferable. . In the case of the ring structure represented by formulas (7b) and (7f), it can be easily changed to the ring structure represented by formulas (7c) and (7d) by heat treatment.

A ^{1 to} A ⁶ represent a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (3). Among these, those having electron-withdrawing properties such as a fluorine atom and a cyano group Is preferred. Due to the presence of the substituent having electroattractive properties, the energy level of electrons as a whole is lowered in the highly conjugated compound, and the LUMO (Lowest Unoccupied Molecular Orbital) can be reduced.

X represents a hydrogen atom, or a carbon-carbon bond is formed between adjacent XX. Here, “form a carbon-carbon bond between adjacent XX” means any one of A ^{1 to} A ⁶ (provided that at least A ¹ in formula (1) and at least in formula (2a) When A ¹ or A ³ or at least A ³ in formula (2b) is a substituent represented by (3) (pyrrolyl group or substituted pyrrolyl group), the adjacent pyrrolyl group or substituted pyrrolyl group is cyclized. It points to that.

That is, in the formula (1), as an aspect in which a carbon-carbon bond is formed between adjacent XX, a skeleton excluding R ^{1 to} R ⁶ corresponds to the formulas (4a) to (4k). Things.

[In the formulas (4a) to (4k), ** represents a bonding position of R ^{1 to} R ⁶ . D ^{1 to} D ⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6a). ]

[In the formula (6a), ** represents the bonding position of R ⁵ and R ⁶ . * Represents a bonding position. ]

Among these, as the compound represented by the formula (1), those in which the skeleton excluding R ^{1 to} R ⁶ corresponds to the formulas (4a) to (4c) are preferable.

In the formula (2a) or (2b), as an aspect in which a carbon-carbon bond is formed between adjacent XX, the skeleton excluding R ^{1 to} R ⁶ is represented by the formulas (5a) to (5i). ).

[In the formulas (5a) to (5i), ** represents the bonding position of R ^{1 to} R ⁶ . D ^{1 to} D ³ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6a). ]

Among these, as the compound represented by the formula (2a) or the formula (2b), those in which the skeleton excluding R ^{1 to} R ⁵ corresponds to the formulas (5a) to (5c) are preferable.

<High conjugated compound precursor>
Next, the highly conjugated compound precursor of the present invention will be described. The highly conjugated compound precursor of the present invention is represented by the formula (8), the formula (9a) or the formula (9b). That is, the highly conjugated compound precursor of the present invention has benzene or pyridine as a basic skeleton, and two pyrrolyl groups are added to the basic skeleton so as to be located in ortho positions relative to each other. It is an essential requirement that at least one has a substituent at the 3-position and the 4-position. The highly conjugated compound precursor having such a structure can easily form the highly conjugated compound by being oxidized. The highly conjugated compound precursor has high solubility because the adjacent pyrrolyl group is not cyclized. Therefore, since the purification using a solvent can be performed, the purification can be easily performed. Therefore, a highly conjugated compound with higher purity can be easily obtained.

[In Formula (8), R < ¹ > -R < ⁴ > is the same or different, and represents the aliphatic hydrocarbon group which may be a hydrogen atom or halogenated. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of aliphatic hydrocarbon groups which may be halogenated, and these aliphatic hydrocarbon groups which may be halogenated are bonded to each other. Thus, a ring structure may be formed. F ^{1 to} F ⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6). ]

[In the formulas (9a) and (9b), R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an optionally halogenated hydrocarbon group. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of hydrocarbon groups which may be halogenated, and these hydrocarbon groups which may be halogenated are bonded to each other to form a ring structure. May be formed. F ^{1 to} F ³ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6). ]

[In formula (6), R ⁵ and R ⁶ represent a hydrogen atom or a hydrocarbon group which may be halogenated, and may be bonded to each other to form a ring structure. * Represents a bonding position. Note that when substituents plurality of F ¹ to F ⁴ are represented by the formula (6), a plurality of R ⁵ may be the same or different, may be different in each of a plurality of R ⁶ are the same. ]

<Method for producing highly conjugated compound>
Next, the manufacturing method of the highly conjugated compound of this invention is demonstrated.
The production method of the highly conjugated compound of the present invention is the compound represented by the formula (10) or the formula (11) and two or more of the compounds represented by the formulas (12a) to (12c) (provided that the formula (12a) A highly conjugated compound precursor represented by formula (8), formula (9a) or formula (9b) is synthesized from the compound represented by formula (12b) and the compound represented by formula (12b). By oxidizing the precursor, a highly conjugated compound represented by formula (1), formula (2a) or formula (2b) is produced.

Hereinafter, a manufacturing method is demonstrated for every process.
In the production method of the present invention, first, a compound represented by the formula (10) or the formula (11) and two or more of the compounds represented by the formulas (12a) to (12c) (however, represented by the formula (12a)). From the compound and the compound represented by the formula (12b), a highly conjugated compound precursor represented by the formula (8), the formula (9a) or the formula (9b) is synthesized.

[In the formulas (10) and (11), E ^{1 to} E ⁶ represent a hydrogen atom, a fluorine atom, a chlorine atom, or a cyano group. ]

[In formulas (12a) to (12c), R ^{1 to} R ⁶ represent a hydrogen atom or a hydrocarbon group which may be halogenated, and may be bonded to each other to form a ring structure. ]

  The method for reacting the compound represented by the formula (10) or the formula (11) and the compound represented by the formulas (12a) to (12c) is not particularly limited, and these are mixed, heated and stirred. It can be carried out. What is necessary is just to adjust reaction temperature and reaction time suitably.

Examples of the reaction solvent include ketones such as acetone; amides such as dimethylformamide (DMF) and dimethylacetamide (DMAc); nitriles such as acetonitrile; ethers such as tetrahydrofuran (THF), diethyl ether and diisopropyl ether; Ureas such as tetramethylurea and dimethylpropyleneurea can be used. As the reaction catalyst, carbonates such as cesium carbonate (Cs ₂ CO _3), potassium carbonate (K ₂ CO _3), sodium carbonate (Na ₂ CO _3), lithium carbonate (Li ₂ CO _3); potassium fluoride Fluorides such as (KF) and sodium fluoride (NaF); potassium-tert-butoxide, normal butyl lithium (n-BuLi), sodium hydride (NaH), potassium hydride (KH), and the like can be used.

  The highly conjugated compound precursor represented by the formula (8), formula (9a) or formula (9b) obtained as described above has high solubility and can be easily purified as described above. Therefore, in the production method of the present invention, it is preferable to purify the highly conjugated compound precursor. By increasing the purity of the high conjugated compound precursor, the purity of the finally obtained high conjugated compound can also be easily increased.

  The purification method of the highly conjugated compound precursor is not particularly limited, and silica gel chromatography, alumina column chromatography, sublimation purification, recrystallization, crystallization, and the like can be used. From the viewpoint of simplicity of work, recrystallization, crystallization, silica gel chromatography, and alumina column chromatography are preferable.

  Next, the high conjugated compound precursor obtained above is oxidized. By oxidizing the highly conjugated compound precursor, the adjacent pyrrolyl group or substituted pyrrolyl group of the precursor is cyclized, and the highly conjugated compound represented by formula (1), formula (2a) or formula (2b) Is obtained. This oxidation reaction is difficult for the by-products to react. Therefore, if the purity is increased at the stage of the highly conjugated compound precursor, a decrease in the purity can be suppressed as much as possible to produce a highly conjugated compound.

The method for oxidizing the highly conjugated compound precursor is not particularly limited as long as the adjacent pyrrolyl group or substituted pyrrolyl group of the precursor can be cyclized.
Examples of the oxidation reaction method include chemical oxidation and electrolytic oxidation. When employing chemical oxidation, examples of the oxidizing agent used include oxygen, hydrogen peroxide; tetrachloro-1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, and the like. Quinones; Halogens such as iodine, bromine and chlorine; Metal chlorides such as iron (III) chloride and copper (II) chloride; Metal oxides such as manganese dioxide, lead dioxide and osmium tetroxide; Nitric acid and chloric acid Oxo acid; oxo acid salts such as potassium chlorate, sodium hypochlorite, sodium bromate, potassium bromate, potassium permanganate, potassium dichromate, sodium persulfate, potassium persulfate, ammonium persulfate; It is done. Among these oxidizing agents, halogen and metal chloride are preferable. Only 1 type may be used for an oxidizing agent or it may use 2 or more types together. When chemical oxidation is employed, UV irradiation or the like may be performed depending on the oxidizing agent used.

  When employing electrolytic oxidation, there is no limitation on the reaction apparatus used, and a reaction apparatus used in the production of polypyrrole, polythiophene, or the like by electrolytic oxidation can be used. Examples of the electrolyte include ammonium salts such as tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium fluoride, tetraethylammonium tetrafluoroborate, tetra-n-butylammonium hexafluorophosphate, and tetra-n-butylammonium hexafluoroantimony. Phosphonium salts such as tetraphenylphosphonium bromide and tetraphenylphosphonium chloride; lithium salts such as lithium perchlorate and lithium hexafluoroborate; sulfonates such as potassium benzenesulfonate and sodium toluenesulfonate; sulfuric acid, hydrochloric acid and trifluoroacetic acid And the like. These electrolytes may be used alone or in combination of two or more.

  Moreover, you may refine | purify the obtained highly conjugated compound as needed. Examples of the purification method include the same methods as those for the highly conjugated compound precursor.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented within a range that can meet the purpose described above and below. All of which are within the scope of the present invention.

In addition, the following apparatus was used for the analysis about the compound synthesize | combined.
Melting point: Model “EXSTAR6000 / TG / DTA6200” manufactured by Seiko Instruments
Ultraviolet-visible absorption spectrum: model “U-2810” manufactured by Hitachi High-Technologies Corporation, model “v-570 model” manufactured by JASCO Corporation
Infrared absorption spectrum: HORIBA, Ltd. Model “FT-720”
NMR spectrum: “JNM-AL400” manufactured by JEOL Ltd., “JNM-EX400” manufactured by JEOL Ltd., “Mercury 2000” manufactured by Varian Technologies, Inc.
Mass spectrum: manufactured by JEOL Ltd. Model “JMS-MS 700”
(MALDI-TOF) mass spectrum; manufactured by Applied Biosystems, model “Voyager-DE ^™ -PRO”

1. Synthesis of Precursor Synthesis Example 1-1 (2,5-Py-3,6-DF-TPN)

A 200 ml three-necked reaction vessel equipped with a dropping funnel and a reflux condenser was charged with 5.00 g (24.99 mmol) of tetrafluoroterephthalonitrile and 8.14 g (24.99 mmol) of cesium carbonate, and the inside of the reaction vessel was purged with nitrogen. After that, 50 ml of acetone was added.
A dropping funnel was charged with 1.68 g (25.04 mmol) of pyrrole and 17 ml of acetone, slowly dropped, heated to 60 ° C. and heated for 24 hours after completion of the dropping.
Subsequently, 12.20 g (37.44 mmol) of cesium carbonate was added to the reaction vessel, and then 1.68 g (25.04 mmol) of pyrrole and 17 ml of acetone were charged into the dropping funnel and slowly dropped, followed by 48 hours at 60 ° C. Heated.
Thereafter, the reaction solution was cooled, filtered to remove inorganic salts, and concentrated using an evaporator. After adding 100 ml of methanol to the concentrate and stirring for about 10 minutes, 10 ml of water was further added and filtered. The residue was washed again with methanol and water, and the obtained residue was vacuum-dried at 60 ° C., whereby a compound represented by the formula (a1) (hereinafter, “2,5-Py-3,6- DF-TPN ") 3.66 g (12.44 mmol, yield 50 mol% from tetrafluoroterephthalonitrile) was obtained.

The analytical data of the obtained 2,5-Py-3,6-DF-TPN are as follows.
¹ H-NMR ((CD ₃ ) ₂ CO, 400 MHz): δ = 6.46-6.47 (m, 4H), 7.20-7.22 (m, 4H).
¹⁹ F-NMR ((CD ₃ ) ₂ CO, 400 MHz) (hexafluorobenzene standard): δ = 45.80 (s, 2F)

  Synthesis Example 1-2 (2,5-Py-3,6-TFII-TPN)

A 30 ml two-necked reaction vessel was charged with 0.67 g (3.54 mmol) of tetrafluoroisoindole and purged with nitrogen. Then, 8.2 ml of tetrahydrofuran (hereinafter, “THF”) was added, and then cooled to −78 ° C. After cooling, 2.3 ml of n-BuLi / n-hexane solution (n-BuLi content 3.82 mmol) was slowly added with a syringe and stirred as it was for 1 hour.
In a separate 50 ml two-necked reaction vessel, 0.5 g (1.70 mmol) of 2,5-Py-3,6-DF-TPN was weighed and purged with nitrogen, then 14 ml of THF was added and dissolved, and cooled to -78 ° C. did.
The previously prepared tetrafluoroisoindole solution was withdrawn with a syringe and slowly added to the reaction solution prepared later.
After the addition was completed, the mixture was stirred for 1 hour under cooling, and then the cooling bath was removed and the mixture was stirred for 12 hours.
Thereafter, ethyl acetate was added to the reaction solution, and hexane was further added to precipitate the reaction product, followed by filtration. The filtrate was further recrystallized with ethyl acetate / hexane to give 0.50 g of a compound represented by the formula (8-1) (hereinafter, “2,5-Py-3,6-TFII-TPN”). (0.79 mmol, yield of 47 mol% from 2,5-Py-3,6-DF-TPN).

The analytical data of 2,5-Py-3,6-TFII-TPN obtained are as follows.
¹ H-NMR ((CD ₃ ) ₂ CO: δ = 6.21-6.23 (m, 4H), 6.85-6.86 (m, 4H), 7.73 (s, 4H).
¹⁹ F-NMR ((CD ₃ ) ₂ CO, 400 MHz) (hexafluorobenzene standard): δ = −1.69—1.64 (m, 4F), 13.23-13.27 (m, 4F) .
UV-bis (CHCl ₃ ): λmax, 365 nm

  Synthesis Example 1-3 (2,3,5,6-TFII-TPN)

A 50 ml two-necked reaction vessel was charged with 1.85 g (9.78 mmol) of tetrafluoroisoindole and purged with nitrogen, and then 22 ml of THF was added and cooled to -78 ° C. After cooling, 6.2 ml (n-BuLi content 10.11 mmol) of n-BuLi / n-hexane solution was slowly added with a syringe and stirred as it was for 1 hour.
In another 100 ml two-necked reaction vessel, 0.92 g (4.60 mmol) of tetrafluoroterephthalonitrile was weighed and purged with nitrogen, and then 30 ml of THF was added and dissolved, and the mixture was cooled to -78 ° C.
The previously prepared tetrafluoroisoindole solution was withdrawn with a syringe and slowly added to the reaction solution prepared later.
After the addition was completed, the mixture was stirred for 1 hour under cooling, and then the cooling bath was removed and the mixture was stirred for 12 hours.
Then, after adding water and quenching reaction, the reaction solution was moved to the separating funnel, ethyl acetate was added, and water washing was performed 3 times. The ethyl acetate solution was dried with mirabilite, concentrated, and purified by silica gel column chromatography (ethyl acetate / hexane) to obtain a compound represented by the formula (8-2) (hereinafter “2, 3, 5, 6”). -TFII-TPN ") was obtained 0.58 g (0.66 mmol, 27 mol% yield from tetrafluoroisoindole).

The analytical data of 2,3,5,6-TFII-TPN obtained are as follows.
¹ H-NMR ((CD ₃ ) ₂ CO, 400 MHz): δ = (t, J = 1.2 Hz, 8H).
¹⁹ F-NMR ((CD ₃ ) ₂ CO, 400 MHz) (hexafluorobenzene standard): δ = −0.67−0.69 (m, 8F), 13.57-13.61 (m, 8F) .
UV-bis (CHCl ₃ ): λmax, 359 nm

  Synthesis Example 1-4 (2,5-Py-3,6- (n-Pen) Py-TPN)

1.00 g (3.40 mmol) of 2,5-Py-3,6-DF-TPN and 3.32 g (10.19 mmol) of cesium carbonate in a 50 ml three-necked reaction vessel equipped with a dropping funnel and a reflux condenser The reaction vessel was purged with nitrogen and 35 ml of dimethylacetamide was added.
A dropping funnel was charged with 1.6 g (7.72 mmol) of 3,4-di-n-pentylpyrrole and 7 ml of dimethylacetamide, slowly dropped, heated to 60 ° C. and heated for 12 hours after completion of the dropping.
Thereafter, the reaction solution was cooled, filtered to remove inorganic salts, and then concentrated. Then, it refine | purifies by silica gel column chromatography (ethyl acetate / hexane), and the compound (henceforth "2,5-Py-3,6- (n-Pen) Py-TPN" represented by Formula (8-3). 0.92 g (1.38 mmol, 40 mol% yield from 2,5-Py-3,6-DF-TPN).

The analysis data of the obtained 2,5-Py-3,6- (n-Pen) Py-TPN are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 0.88-0.91 (m, 12H), 1.29-1.36 (m, 16H), 1.36-1.52 (m, 8H) ), 2.33 (t, J = 3.6 Hz, 8H), 6.23-6.24 (m, 4H), 6.40 (s, 4H), 6.74-6.75 (m, 4H) ).
UV-bis (CHCl ₃ ): λmax, 412 nm

Synthesis Example 1-5 (2,5-Py-3,6-BCPy-TPN)

A 30 ml two-necked reaction vessel was charged with 0.31 g (2.13 mmol) of bicyclopyrrole and purged with nitrogen, and then 4 ml of THF was added and cooled to -78 ° C. After cooling, 1.4 ml of n-BuLi / n-hexane solution (content of n-BuLi 2.24 mmol) was slowly added with a syringe and stirred as it was for 1 hour.
In a separate 50 ml two-necked reaction vessel, 0.30 g (1.02 mmol) of 2,5-Py-3,6-DF-TPN was weighed and purged with nitrogen, then 12 ml of THF was added and dissolved, and cooled to -78 ° C. did.
The previously prepared bicyclopyrrole solution was withdrawn with a syringe and slowly added to the reaction solution prepared later.
After the addition was completed, the mixture was stirred for 1 hour under cooling, and then the cooling bath was removed and the mixture was stirred for 12 hours.
Then, after adding water and quenching reaction, the reaction solution was moved to the separating funnel, ethyl acetate was added, and water washing was performed 3 times. The ethyl acetate solution was dried with mirabilite and concentrated, then purified by silica gel column chromatography (ethyl acetate / hexane), and recrystallized with chloroform to obtain a compound represented by the formula (8-4) (hereinafter, “2, 5-Py-3,6-BCPy-TPN ") was obtained 0.16 g (0.29 mmol, 29 mol% yield from 2,5-Py-3,6-DF-TPN).

The analytical data of the obtained 2,5-Py-3,6-BCPy-TPN are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.45-1.54 (m, 8H), 3.71 (s, 4H), 6.12 (s, 4H), 6.24-6. 25 (m, 4H), 6.41 (dd, J = 3.2, 4.8 Hz, 4H), 6.47-6.48 (m, 4H).
UV-bis (CHCl ₃ ): λmax, 415 nm

  Synthesis Example 1-6 (2,3,4,5-BCPy-TPN)

Bicyclopyrrole 0.587 g (4.00 mmol) was placed in the reaction vessel, purged with nitrogen, protected from light, and dissolved in 20.0 ml of dry dimethylformamide. After cooling to 0 ° C. and adding 0.213 g of NaH mineral oil dispersion (NaH content 5.33 mmol) and stirring for 30 minutes, 0.200 g of tetrafluoroterephthalonitrile dissolved in 20.0 ml of dry dimethylformamide ( 1.00 mmol) was added and the mixture was stirred at 60 ° C. for 2 hours. The mixture was returned to room temperature, quenched with water, extracted with chloroform, washed with water, saturated multilayered water, and saturated brine, dried over dried sodium sulfate, and concentrated under reduced pressure.
Thereafter, the product was purified by silica gel chromatography (50% chloroform / hexane solution, Rf = 0.2), and the compound represented by formula (8-5) (hereinafter, “2,3,4,5-BCPy-TPN”) 0.4681 g (0.669 mmol, yield 67 mol%) was obtained.

The analytical data of the obtained 2,3,4,5-BCPy-TPN are as follows.
m. p: 220-230 ° C. (decomp.)
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.47-1.53 (m, 16H), 3.68 (s, 8H), 6.02 (s, 8H), 6.41-6. 43 (m, 8H,)
¹³ C-NMR (CDCl ₃ , 100 MHz): δ = 27.21, 32.86, 111.20, 112.88, 113.17, 132.75, 135.31, 139.09.
_{UV-vis (CH 2 Cl 2} ): λmax, nm (logε), 427nm (3.9851), 291nm (4.4287), 229nm, (4.5466).
IR (KBr) vmax / cm < ^-1 >: 1481.06, 2233.16, 2859.92, 2933.20, 2954.41, 3045.05.
MS (MALDI-TOF) m / z = 701.0905
(Calculated value: exact mass = 700.3314, molecular weight = 700.8714)
Anal. _{calcd for C 48 H 40 N 6} : C, 82.26; H, 5.75; N, 11.99;
Anal. _{calcd for C 48 H 40 N 6} · 0.25CHCl 3: C, 79.31; H, 5.55; N, 11.50;
Found: C, 79.48; H, 5.67; N, 11.48;

  Synthesis Example 1-7 (4,5-Py-3,6-DF-PN)

A 200 ml three-necked reaction vessel equipped with a dropping funnel and a reflux condenser was charged with 8.01 g (40.03 mmol) of tetrafluorophthalonitrile and 6.51 g (19.98 mmol) of cesium carbonate, and the reaction vessel was purged with nitrogen. Thereafter, 80 ml of acetonitrile was added.
A dropping funnel was charged with 2.68 g (39.95 mmol) of pyrrole and 25 ml of acetonitrile, slowly dropped, heated to 60 ° C. after the completion of dropping, and heated for 12 hours.
Subsequently, 6.52 g (20.01 mmol) of cesium carbonate was added to the reaction vessel, and then 2.68 g (39.95 mmol) of pyrrole and 25 ml of acetonitrile were charged into the dropping funnel, and slowly dropped, and continued at 60 ° C. for 24 hours. Heated.
Thereafter, the reaction solution was cooled, filtered to remove inorganic salts, and concentrated using an evaporator. The concentrate was purified by silica gel column chromatography (ethyl acetate / hexane) and recrystallization, and the compound represented by the formula (a2) (hereinafter, “4,5-Py-3,6-DF-PN”) 3 .29 g (11.18 mmol, 28 mol% yield from tetrafluoroterephthalonitrile) was obtained.

The analytical data of the obtained 4,5-Py-3,6-DF-PN are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 6.32-6.33 (m, 4H), 6.44-6.46 (m, 4H).
¹⁹ F-NMR (CDCl ₃ , 400 MHz) (hexafluorobenzene standard): δ = 48.75 (s, 2F)

  Synthesis Example 1-8 (4,5-Py-3,6-TFII-PN)

0.10 g (0.34 mmol) of 4,5-Py-3,6-DF-PN and 0.24 g (0.74 mmol) of cesium carbonate in a 10 ml two-necked reaction vessel equipped with a dropping funnel and a reflux condenser The reaction vessel was purged with nitrogen and 1.5 ml of dimethylacetamide was added.
A dropping funnel was charged with 0.15 g (0.79 mmol) of tetrafluoroisoindole and 2.1 ml of dimethylacetamide, slowly dropped, heated to 60 ° C. and heated for 12 hours after completion of the dropping.
Thereafter, the reaction solution was cooled and concentrated using an evaporator. After concentration, chloroform and water were added to wash the organic layer. Further, the organic layer was washed twice with water. Subsequently, the product was purified by silica gel column chromatography (chloroform / hexane), and 0.07 g of a compound represented by the formula (8-6) (hereinafter, “4,5-Py-3,6-TFII-PN”) was obtained. (0.11 mmol, 33 mol% yield from 4,5-Py-3,6-DF-PN, yellow solid).

The analysis data of the obtained 4,5-Py-3,6-TFII-PN are as follows.
¹ H-NMR ((CD ₃ ) ₂ CO, 400 MHz): δ = 5.98-5.99 (m, 4H), 6.35-6.36 (m, 4H), 7.72 (t, J = 1.2 Hz, 4H).
¹⁹ F-NMR ((CD ₃ ) ₂ CO, 400 MHz) (hexafluorobenzene standard): δ = −1.54−1.50 (m, 4F), 12.49-12.52 (m, 4F)

  Synthesis Example 1-9 (2,3,5,6-BCPy-1,4-DF-BN)

1.165 g (8.02 mmol) of bicyclopyrrole was placed in a reaction vessel, purged with nitrogen, protected from light, dissolved in 20.0 ml of dry dimethylformamide, and 0.5123 g of NaH mineral oil dispersion (NaH content of 12.81 mmol) was added. The mixture was further stirred for 15 minutes, 230 μl (2.0 mmol) of hexafluorobenzene was added, and the mixture was stirred at 60 ° C. for 3 hours. The mixture was returned to room temperature, quenched with water, extracted with chloroform, washed with water, saturated multistory water and saturated brine, dried over dry sodium sulfate, and concentrated under reduced pressure.
Thereafter, 0.995 g of a compound represented by the formula (8-7) (hereinafter, “2,3,5,6-BCPy-1,4-DF-BN”) was washed with ether and hexane. 1.45 mmol, 72 mol% yield from hexafluorobenzene).

The analytical data of 2,3,5,6-BCPy-1,4-DF-BN obtained are as follows.
m. p: 220-230 ° C. (decomp.)
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.49-1.55 (m, 16H,), 3.69 (s, 8H), 6.00 (s, 8H), 6.43-6 .45 (m, 8H)
¹³ C-NMR (CDCl ₃ , 400 MHz): δ = 27.49, 32.96, 57.12, 111.62, 124.81, 131.27, 135.60, 146.55. ;
¹⁹ F-NMR (CDCl ₃ , 400 MHz): δ = −134.66
_{UV-bis (CH 2 Cl 2} ): λmax, nm (logε), 307 (4.396), 272 (4.669).
IR (KBr) vmax / cm < ^-1 >: 1112.73, 1498.42, 1533.13, 1670.05, 2863.77, 2960.20, 3045.05.
MS (MALDI-TOF) m / z = 6877.2156
(Calculated value: exact mass = 6866.3221, molecular weight = 6866.8334)
Anal. _{calcd for C 46 H 40 F 2} N 4: C, 80.44; H, 5.87; F, 5.53; N, 8.16;
Anal. _{calcd for C 46 H 40 F 2} N 4 · 0.5H 2 O: C, 79.63; H, 5.67; F, 5.48; N, 8.08; O, 1.15
Found: C, 79.20; H, 5.86; N, 8.08.

  Synthesis Example 1-10 (2,3,4,5,6-BCPy-F-BN)

377.6 mg (2.60 mmol) of bicyclopyrrole was placed in a reaction vessel, protected from light, dissolved in 20.0 ml of dry dimethylformamide, 120.4 mg of NaH mineral oil dispersion (NaH content 3.01 mmol) was added, and 15 After stirring for 6 minutes, 60.0 μl (0.52 mmol) of hexafluorobenzene was added, and the mixture was stirred at 70 ° C. for 8 hours. The mixture was returned to room temperature, quenched with water, extracted with chloroform, washed with water, saturated multistory water and saturated brine, dried over dry sodium sulfate, and concentrated under reduced pressure.
Thereafter, the product was purified by silica gel chromatography (50% chloroform / hexane solution, Rf = 0.5), and the compound represented by the formula (8-8) (hereinafter, “2,3,4,5,6-BCPy-F”). -BN ") was obtained 51.5 mg (0.063 mmol, 14 mol% yield from hexafluorobenzene).

The analytical data of 2,3,4,5,6-BCPy-F-BN obtained are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.32-1.51 (m, 20H), 3.51 (m, 6H), 3.67 (s, 4H) 5.54 (s, 2H) ), 5.61 (s, 2H), 6.02 (s, 4H), 6.31-6.34 (m, 6H), 6.41-6.43 (m, 4H).
¹⁹ F-NMR (CDCl ₃ , 400 MHz): δ = −134.25 (s, 2H).
MS (FAB) m / z = 812
(Calculated value: exact mass = 811.41, molecular weight = 812.03)

  Synthesis Example 1-11 (6BCPy-BN)

A reaction vessel was charged with 873.7 mg (6.02 mmol) of bicyclopyrrole, purged with nitrogen, protected from light, dissolved in 25.0 ml of dry dimethylacetamide, and 380.2 mg of NaH mineral oil dispersion (NaH content: 9.51 mmol). The mixture was stirred for 15 minutes, 0.115 ml (1.0 mmol) of hexafluorobenzene was added, and the mixture was stirred at 85 ° C. for 8 hours. The mixture was returned to room temperature, quenched with water, extracted with chloroform, washed with water, saturated multistory water and saturated brine, dried over dry sodium sulfate, and concentrated under reduced pressure.
Thereafter, the resultant was washed with chloroform and hexane to obtain 0.8200 mg (0.875 mmol, 85 mol% yield from 0.86 mmol) of the compound represented by the formula (8-9) (hereinafter “6BCPy-BN”).

The analysis data of the obtained 6BCPy-BN are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.30-1.32 (m, 8H), 1.42-1.56 (m, 8H), 3.51 (s, 8H), 5. 61 (s, 8H), 6.32-6.348 (m, 8H)
¹³ C-NMR (CDCl ₃ , 400 MHz): δ = 27.71, 32.87, 110.72, 130.80, 133.42, 135.52.
_{UV-bis (CH 2 Cl 2} ): λmax, nm (logε), 284 (4.704)
IR (KBr) vmax / cm < ^-1 >: 1112.73, 1496.49, 2861.84, 2954.41, 3045.05.
MS (MALDI-TOF) m / z = 9355.4024
(Calculated value: exact mass = 936.4879, molecular weight = 937.2228)
Anal. _{calcd for C 66 H 60 N 6} : C, 84.58; H, 6.45; N, 8.97;
Anal. _{calcd for C 66 H 60 N 6} · H 2 O: C, 82.99; H, 6.54; N, 8.80; O, 1.67.
Found: C, 83.08; H, 6.26; N, 9.01.

  Synthesis Example 1-12 (6 (n-Hex) Py-BN)

Di-n-hexylpyrrole (1.33 g, 5.65 mmol) was placed in a reaction vessel, purged with nitrogen, protected from light, and dissolved in 47 ml of dry dimethylformamide. After cooling to 0 ° C. and adding 0.38 g of NaH mineral oil dispersion (NaH content 9.5 mmol) and stirring for 30 minutes, 0.15 g of hexafluorobenzene dissolved in 4.5 ml of dry dimethylformamide (0. 81 mmol) was added, and the mixture was stirred at 60 ° C. for 2 hours. The mixture was returned to room temperature, quenched with water, extracted with chloroform, washed with water, saturated multilayered water, and saturated brine, dried over dried sodium sulfate, and concentrated under reduced pressure.
Thereafter, the resultant was purified by silica gel chromatography (chloroform / hexane solution), and 0.82 g (0.55 mmol) of a compound represented by the formula (8-10) (hereinafter, “6 (n-Hex) Py-BN”)) was obtained. The yield was 69 mol% from hexafluorobenzene).

Analytical data of the obtained 6 (n-Hex) Py-BN are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 0.86-0.90 (m, 36H), 1.24-1.28 (m, 96H), 2.13-2.16 (m, 24H) ), 5.70 (s, 12H).
¹³ C-NMR (CDCl ₃ , 100 MHz): δ = 14.18, 22.69, 25.10, 30.36, 31.90, 117.49, 124.53, 132.73

  Synthesis Example 1-13 (1,2,4,5-BCPy-BN)

1.79 g (12.33 mmol) of bicyclopyrrole was placed in a reaction vessel, purged with nitrogen, protected from light, and dissolved in 116 ml of dry dimethylformamide. After cooling to 0 ° C. and adding 0.13 g of NaH mineral oil dispersion (NaH content 3.25 mmol) and stirring for 30 minutes, 1,2,4,5-tetrafluorobenzene dissolved in 12 ml of dry dimethylformamide 0.4 g (2.67 mmol) was added, and the mixture was stirred at 60 ° C. for 2 hours. The mixture was returned to room temperature, quenched with water, extracted with chloroform, washed with water, saturated multilayered water, and saturated brine, dried over dried sodium sulfate, and concentrated under reduced pressure.
Thereafter, the product was purified by silica gel chromatography (chloroform / hexane solution), and 0.72 g (1.... Compound represented by formula (8-11) (hereinafter, “1,2,4,5-BCPy-BN”)) 11 mmol, 42 mol% yield from 1,2,4,5-tetrafluorobenzene).

The analytical data of 1,2,4,5-BCPy-BN obtained are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.48-1.57 (m, 16H), 3.73 (s, 8H), 6.06 (s, 8H), 6.46-6. 47 (m, 8H), 7.32 (s, 2H)
¹³ C-NMR (CDCl ₃ , 100 MHz): δ = 27.60, 33.02, 111.12, 123.30, 131.23, 133.66, 135.89

  Synthesis Example 1-14 (2,4,6-Py-3,5-DF-pyridine)

After charging 5.00 g (29.58 mmol) of pentafluoropyridine and 34.25 g (105.12 mmol) of pentafluoropyridine and 34.25 g (105.12 mmol) of cesium carbonate in a 200 ml three-neck reaction vessel equipped with a dropping funnel and a reflux condenser, the reaction vessel was purged with nitrogen. 50 ml of acetonitrile was added.
A dropping funnel was charged with 6.78 g (101.06 mmol) of pyrrole and 35 ml of dimethylacetamide, slowly dropped, heated to 60 ° C. after the dropping, and heated for 48 hours.
Thereafter, the reaction solution was cooled, filtered to remove inorganic salts, and concentrated using an evaporator. 100 ml of methanol was added to the concentrate and stirred for washing for about 10 minutes, followed by filtration. By recrystallizing the filtrate (ethyl acetate / hexane), 3.60 g of a compound represented by the formula (b1) (hereinafter, “2,4,6-Py-3,5-DF-pyridine”) (11 .60 mmol, yield 39 mol% from pentafluoropyridine).

The analytical data of 2,4,6-Py-3,5-DF-pyridine obtained are as follows.
¹ H-NMR ((CD ₃ ) ₂ CO, 400 MHz): δ = 6.38-6.39 (m, 4H), 6.44-6.46 (m, 2H), 7.28-7.30 (M, 2H), 7.61-7.62 (m, 4H).
¹⁹ F-NMR ((CD ₃ ) ₂ CO, 400 MHz) (hexafluorobenzene standard): δ = 2.86 (s, 2F).

  Synthesis Example 1-15 (2,4,6-Py-3,5- (n-Pen) Py-pyridine)

In a 100 ml three-necked reaction vessel equipped with a dropping funnel and a reflux condenser, 0.70 g (2.26 mmol) of 2,4,6-Py-3,5-DF-pyridine and 3,4-dipentylpyrrole 08 g (5.21 mmol) and 3.72 g (11.42 mmol) of cesium carbonate were charged, and the atmosphere in the reaction vessel was replaced with nitrogen, 33 ml of acetonitrile was added, and the mixture was heated to 60 ° C. and heated for 48 hours.
Thereafter, the reaction solution was cooled, filtered to remove inorganic salts, and concentrated using an evaporator. By purifying the concentrate by silica gel chromatography (chloroform / hexane), a compound represented by the formula (9-1) (hereinafter referred to as “2,4,6-Py-3,5- (n-Pen) Py”). -Pyridine ”) was obtained in an amount of 0.55 g (0.80 mmol, 36 mol% yield from 2,4,6-Py-3,5-DF-pyridine).

Analytical data of the obtained 2,4,6-Py-3,5- (n-Pen) Py-pyridine are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 0.88 (t, J = 7.2 Hz, 12H), 1.20-1.31 (m, 16H), 1.37-1.44 (m 8H), 2.31 (t, J = 7.2 Hz, 8H), 5.98-5.99 (m, 2H), 6.03-6.04 (m, 4H), 6.11-6 .12 (m, 2H), 6.73 (t, J = 2.4 Hz, 4H).

  Synthesis Example 1-16 (2,4,6-Py-3,5-BCPy-pyridine)

A 30 ml two-necked reaction vessel was charged with 0.52 g (3.58 mmol) of bicyclopyrrole and purged with nitrogen, then 15 ml of THF was added, and then cooled to -78 ° C. After cooling, 2.4 ml of n-BuLi / n-hexane solution (n-BuLi content 3.82 mmol) was slowly added with a syringe and stirred as it was for 1 hour.
In a separate 50 ml two-necked reaction vessel, 0.54 g (1.61 mmol) of 2,4,6-Py-3,5-DF-pyridine was weighed and purged with nitrogen, and then 20 ml of THF was added and dissolved. Cooled down. The previously prepared solution was extracted with a syringe and slowly added to the reaction solution of 2,4,6-Py-3,5-DF-pyridine.
After the addition was completed, the mixture was stirred for 1 hour under cooling, and then the cooling bath was removed and the mixture was stirred for 12 hours.
Then, after adding water and quenching reaction, the reaction solution was moved to the separating funnel, ethyl acetate was added, and water washing was performed 3 times. The ethyl acetate solution was dried and concentrated with sodium sulfate, purified by silica gel column chromatography (chloroform / hexane), and recrystallized with chloroform to obtain a compound represented by the formula (9-2) (hereinafter “2, 4”). , 6-Py-3,5-BCPy-pyridine ") was obtained in an amount of 0.03 g (0.05 mmol, yield of 3 mol% from 2,4,6-Py-3,5-DF-pyridine).

Analytical data of the obtained 2,4,6-Py-3,5-BCPy-pyridine are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.4-1.46 (m, 2H), 1.51-1.54 (m, 2H), 3.73 (s, 2H), 5. 94-5.95 (m, 2H), 6.00 (S, 4H), 6.06-6.07 (m, 2H), 6.14-6.15 (m, 4H), 6.41- 6.43 (m, 4H), 6.69-6.71 (m, 4H).

  Synthesis Example 1-17 (2,6-Py-3,5-DF-pyridine)

A 200 ml three-necked reaction vessel equipped with a dropping funnel and a reflux condenser was charged with 5.00 g (33.10 mmol) of 2,3,5,6-tetrafluoropyridine and 29.60 g (90.85 mmol) of cesium carbonate, After purging the reaction vessel with nitrogen, 50 ml of acetonitrile was added.
The dropping funnel was charged with 4.44 g (66.18 mmol) of pyrrole and 22 ml of dimethylacetamide, slowly dropped, heated to 60 ° C. after the completion of dropping, and heated for 48 hours.
After completion of the reaction, the reaction solution was cooled, filtered to remove inorganic salts, and concentrated using an evaporator. The concentrate was purified by silica gel column chromatography (ethyl acetate / hexane), and further purified by recrystallization (hexane), whereby a compound represented by the formula (b2) (hereinafter, “2,6-Py-3, 5-DF-pyridine ") was obtained (4.13 g, 16.84 mmol, 51 mol% yield from 2,3,5,6-tetrafluoropyridine, white solid).

Analytical data of the obtained 2,6-Py-3,5-DF-pyridine are as follows.
¹ H-NMR ((CD ₃ ) ₂ CO, 400 MHz): δ = 6.35-6.37 (m, 4H), 7.59 (brs, 4H).
¹⁹ F-NMR ((CD ₃ ) ₂ CO, 400 MHz) (hexafluorobenzene standard): 32.28 (s, 2F)

  Synthesis Example 1-18 (2,6-Py-3,5-TFII-pyridine)

0.10 g (0.41 mmol) of 2,6-Py-3,5-DF-pyridine and 0.34 g (1.04 mmol) of cesium carbonate in a 10 ml two-necked reaction vessel equipped with a dropping funnel and a reflux condenser The reaction vessel was purged with nitrogen and 1.5 ml of dimethylacetamide was added.
A dropping funnel was charged with 0.18 g (0.95 mmol) of tetrafluoroisoindole and 1.7 ml of dimethylacetamide, slowly dropped, heated to 60 ° C. and heated for 12 hours after completion of the dropping.
Thereafter, the reaction solution was cooled and filtered, and then the filtrate was concentrated using an evaporator. After concentration, chloroform and water were added to wash the organic layer. Further, the organic layer was washed twice with water. Subsequently, it was purified by silica gel column chromatography (chloroform / hexane), and 0.09 g of a compound represented by the formula (9-3) (hereinafter, “2,6-Py-3,5-TFII-pyridine”) was obtained. (0.15 mmol, 2,6-Py-3,5-DF-pyridine yield 38 mol%).

  Synthesis Example 1-19 (2,3,5,6-BCPy-pyridine)

A 200 ml two-necked reaction vessel was charged with 1.02 g of NaH mineral oil dispersion (NaH content 25.5 mmol), the inside of the reaction vessel was purged with nitrogen, 70 ml of dimethylformamide was added, and the mixture was heated to 40 ° C. A solution prepared by dissolving 1.45 g (9.99 mmol) of bicyclopyrrole in 20 ml of dimethylformamide was slowly added using a syringe and stirred for 10 minutes.
Subsequently, a solution prepared by dissolving 0.32 g (2.12 mmol) of 2,3,5,6-tetrafluoropyridine in 10 ml of dimethylformamide was slowly added to the reaction vessel using a syringe.
After stirring for 10 minutes, the reaction temperature was raised to 65 ° C. and reacted for 4 hours.
Thereafter, a small amount of water was added to the reaction vessel to quench the reaction, and the reaction solution was filtered to remove insoluble matters. After the reaction solution was concentrated once, chloroform was added to dissolve the concentrate, and the mixture was washed 3 times with water. The organic layer was dried over anhydrous sodium sulfate, concentrated and then purified by silica gel column chromatography (chloroform / hexane) to obtain a compound represented by the formula (9-4) (hereinafter “2, 3, 5, 6”). -BCPy-pyridine ") was obtained 1.07 g (1.64 mmol, 77 mol% yield from 2,3,5,6-tetrafluoropyridine).

Analytical data of the obtained 2,3,5,6-BCPy-pyridine are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.49-1.63 (m, 16H), 3.66 (s, 4H), 3.83 (s, 4H), 6.24 (s, 4H), 6.30 (s, 4H), 6.44 (dd, J = 2.8, 4.4 Hz, 4H), 6.51 (dd, J = 2.8, 4.4 Hz, 4H), 7.60 (s, 1H).

2. Synthesis of High Conjugated Compound Synthesis Example 2-1 (2,5-Py-3,6-TFII-TPN-OX)

In a 100 ml reaction vessel, 0.15 g (0.24 mmol) of 2,5-Py-3,6-TFII-TPN and 76 g of dichloromethane were weighed and stirred to obtain a uniform solution. To this reaction solution, a dichloromethane solution of iodine (0.13 g (0.51 mmol) of iodine (I ₂ ) dissolved in 5 g of dichloromethane) was added with stirring, and then irradiated with light with a UV lamp for 10 hours.
After irradiation, the reaction was quenched with an aqueous sodium hydrogen sulfite solution, and the reaction solution was filtered to remove insoluble matters. The filtrate was washed with water three times, and the dichloromethane layer was dried with sodium sulfate and concentrated with an evaporator. Subsequently, the concentrate was purified by silica gel column chromatography (chloroform / hexane), vacuum-dried at 60 ° C., and the compound represented by the formula (1-1) (hereinafter “2,5-Py-3,6- TFII-TPN-OX ") was obtained in 0.03 g (0.05 mmol, yield 21 mol%).
The analytical data of the obtained 2,5-Py-3,6-TFII-TPN-OX are as follows.
UV-bis (CHCl ₃ ): λmax, 472 nm

  Synthesis Example 2-2 (2,5-Py-3,6- (n-Pen) Py-TPN-OX)

In a 100 ml reaction vessel, 0.46 g (0.69 mmol) of 2,5-Py-3,6- (n-Pen) Py-TPN and 5 g of dichloromethane were weighed and stirred to obtain a uniform solution. To this reaction solution, a dichloromethane solution of iodine <0.70 g (2.76 mmol) of iodine (I ₂ ) dissolved in 67 g of dichloromethane> was added with stirring, and then irradiated with light from a UV lamp for 10 hours.
After irradiation, the reaction was quenched with an aqueous sodium hydrogen sulfite solution, and the reaction solution was filtered to remove insoluble matters. The filtrate was washed with water three times, and the dichloromethane layer was dried with sodium sulfate and concentrated with an evaporator. Subsequently, the concentrate was purified by silica gel column chromatography (chloroform / hexane) and recrystallization (chloroform / methanol) to obtain a compound represented by the formula (1-2) (hereinafter referred to as “2,5-Py-3, 6- (n-Pen) Py-TPN-OX ") was obtained in 0.26 g (0.39 mmol, yield 56 mol%).

The analysis data of the obtained 2,5-Py-3,6- (n-Pen) Py-TPN-OX are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 0.92-0.95 (m, 6H), 1.39-1.45 (m, 8H), 1.57-1.61 (m, 2H) ), 1.67-1.70 (m, 2H), 2.55 (t, J = 8.0 Hz, 2H), 2.65 (t, J = 8.0 Hz, 2H), 6.51 (dd , J = 1.2, 3.6 Hz, 1H), 6.65-6.67 (m, 1H), 8.11 (s, 1H), 8.40 (dd, J = 1.2, 3.H. 6 Hz, 1 H).
UV-bis (CHCl ₃ ): λmax, 510 nm

  Synthesis Example 2-3 (2,5-Py-3,6-BCPy-TPN-OX)

In a 100 ml reaction vessel, 0.15 g (0.28 mmol) of 2,5-Py-3,6-BCPy-TPN and 1.5 g of dichloromethane were weighed and stirred to obtain a uniform solution. To this reaction solution, a dichloromethane solution of iodine <0.21 g (0.83 mmol) of iodine (I ₂ ) dissolved in 10 g of dichloromethane> was added with stirring, and then irradiated with light from a UV lamp for 10 hours.
After irradiation, the reaction was quenched with an aqueous sodium hydrogen sulfite solution, and the reaction solution was filtered to remove insoluble matters. The filtrate was washed with water three times, and the dichloromethane layer was dried with sodium sulfate and concentrated with an evaporator. Subsequently, the concentrate was purified by silica gel column chromatography (chloroform / hexane) and recrystallization (chloroform / hexane) to obtain a compound represented by the formula (1-3) (hereinafter referred to as “2,5-Py-3, 6-BCPy-TPN-OX ") was obtained in 0.07 g (0.13 mmol, yield 46 mol%).

The analytical data of the obtained 2,5-Py-3,6-BCPy-TPN-OX are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.58-1.72 (m, 8H), 3.98-4.00 (m, 2H), 4.21-4.22 (m, 2H) ), 6.54-6.60 (m, 2H), 6.65 (t, J = 3.6 Hz, 2H), 8.07 (s, 2H), 8.34 (dd, J = 1.2 3.6 Hz, 2H).
UV-bis (CHCl ₃ ): λmax, 511 nm

  Synthesis Example 2-4 (2,3,4,5-BCPy-TPN-OX)

351.9 mg (0.503 mmol) of 2,3,4,5-BCPy-TPN was placed in a reaction vessel, dissolved in 20.0 ml of dichloromethane, and then 30.0 ml of acetonitrile was added. Iodine (I ₂ ) 0.2800 g (1.1 mmol) was added, and the light was kept on for 3 hours. After the reaction, the reaction mixture was quenched with an aqueous sodium nitrite solution, extracted with chloroform, washed with water, saturated multistory water, and saturated brine, dried over dried sodium sulfate, and concentrated under reduced pressure.
Thereafter, the product is purified by silica gel chromatography (50% chloroform / hexane solution, Rf = 0.7) and recrystallized with a small amount of toluene, whereby the compound represented by the formula (1-4) (hereinafter referred to as “2,3”). , 4, 5-BCPy-TPN-OX ") was obtained (114.8 mg, 0.165 mmol, 33 mol% yield).
Analysis data of the obtained 2,3,4,5-BCPy-TPN-OX are as follows.
m. p: 220-230 ° C. (decomp.)
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.67-1.74 (m, 16H), 3.95 (s, 4H), 4.29 (m, 4H), 6.54-6. 60 (m, 8H), 7.97 (s, 4H).
¹³ C-NMR (CDCl ₃ , 100 MHz): δ = 26.48, 26.51, 26.72, 26.82, 33.13, 33.92, 34.06, 89.24, 107.61, 115 .95, 115.95, 116.00, 118.59, 123.73, 123.82, 126.28, 126.33, 135.07, 135.08, 135.25, 135.37, 135.47 , 135.55, 135.56.
UV-vis (CH ₂ Cl ₂ ): λmax, nm (log ε), 527 nm, (4.3671), 279 nm, (4.8649)
IR (KBr) vmax / cm < ^-1 >: 1236.35,1467.56,2210.02,286377,293.13,3045.05.
MS (MALDI-TOF) m / z = 697.1765
(Calculated value: exact mass = 696.3001, molecular weight = 696.8396)
Anal. _{calcd for C 48 H 36 N 6} : C, 82.73; H, 5.21; N, 12.06;
Anal. _{calcd for C 48 H 36 N 6} · 0.5H 2 O: C, 81.68; H, 5.28; N, 11.91;
Found: C, 81.95; H, 5.53; N, 11.54.

  Synthesis Example 2-5 (4,5-Py-3,6-TFII-PN-OX)

Into a 5 ml reaction vessel, 0.02 g (0.03 mmol) of 4,5-Py-3,6-TFII-PN and 1 g of dichloromethane were weighed and stirred to obtain a homogeneous solution. To this reaction solution, a dichloromethane solution of iodine (0.05 g (0.20 mmol) of iodine (I ₂ ) dissolved in 0.6 g of dichloromethane) was added with stirring, and then irradiated with light from a UV lamp for 10 hours.
After irradiation, the reaction was quenched with an aqueous sodium hydrogen sulfite solution, the reaction solution was filtered, the filtration residue was washed with water, chloroform, and ethanol, dried at 60 ° C. under vacuum, and the compound represented by the formula (1-5) (hereinafter referred to as the formula (1-5)) , “4,5-Py-3,6-TFII-PN-OX”) was obtained in 0.014 g (0.02 mmol, yield 71 mol%, brown solid).

  Synthesis Example 2-6 (2,3,5,6-BCPy-1,4-DF-BN-OX)

995.4 mg (1.45 mmol) of 2,3,5,6-BCPy-1,4-DF-BN was placed in a reaction vessel, dissolved in 140.0 ml of dichloromethane, and then 100.0 ml of acetonitrile was added. Iodine (I ₂ ) 761.4 mg (3.04 mmol) was added, and the light was kept on for 5 hours.
After the reaction, the reaction mixture was quenched with an aqueous sodium nitrite solution, extracted with chloroform, washed with water, saturated multistory water, and saturated brine, dried over dried sodium sulfate, and concentrated under reduced pressure.
Thereafter, the compound represented by the formula (1-6) (hereinafter, “2,3,5,6-BCPy-1,4-DF-BN-OX”) is obtained by washing with ether and hexane 267. 33 mg (0.392 mmol, yield 27 mol%) was obtained.
The analytical data of 2,3,5,6-BCPy-1,4-DF-BN-OX obtained are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.68-1.76 (m, 16H), 3.98 (s, 4H), 4.45-4.50 (m, 4H), 6. 60 (m, 8H), 7.62 (s, 8H).
¹³ C-NMR (CDCl ₃ , 400 MHz): δ = 26.80, 26.93, 27.03, 33.21, 34.24, 34.39, 115.83, 121.57, 135.79, 135 89, 136.01, 155.59.
¹⁹ F-NMR (CDCl ₃ , 400 MHz): δ = −136.06 (s, 2H).
_{UV-bis (CH 2 Cl 2} ): λmax, nm (logε), 359 (4.424), 285 (5.015).
IR (KBr) vmax / cm < ^-1 >: 1508.06, 2618.84, 2931.27, 3041.19.
MS (MALDI-TOF) m / z = 684.2003
(Calculated value: exact mass = 682.908, molecular weight = 682.8016)
Anal. _{calcd for C 46 H 36 F 2} N 4: C, 80.92; H, 5.31; F, 5.56; N, 8.21.
Anal. _{calcd for C 46 H 40 F 2} N 4 · 0.25CHCl 3: C, 77.95; H, 5.13; Cl, 3.73; F, 5.33; N, 7.86.
Found: C, 77.57; H, 5.23; N, 7.87.

  Synthesis Example 2-7 (6BCPy-BN-OX)

96.1 mg (0.103 mmol) of 6BCPy-BN was placed in a reaction vessel, dissolved in 80.0 ml of dichloromethane, and then 20.0 ml of acetonitrile was added. Iodine (I ₂ ) 165.3 mg (0.651 mmol) was added, and the mixture was stirred for 1.5 hours.
After the reaction, the reaction mixture was quenched with an aqueous sodium nitrite solution, extracted with dichloromethane, washed with water and saturated brine, dried over dry sodium sulfate, and concentrated under reduced pressure. The crude yield of the reaction product obtained was 65.1 mg.

  Synthesis Example 2-8 (2,4,6-Py-3,5- (n-Pen) Py-pyridine-OX)

In a 5 ml reaction vessel, 0.10 g (0.15 mmol) of 2,4,6-Py-3,5- (n-Pen) Py-pyridine and 3 g of dichloromethane were weighed and stirred to obtain a homogeneous solution. To this reaction solution, a dichloromethane solution of iodine <0.30 g (1.18 mmol) of iodine (I ₂ ) dissolved in 3 g of dichloromethane> was added with stirring, and then irradiated with light with a UV lamp for 10 hours.
After irradiation, the reaction was quenched with an aqueous sodium hydrogen sulfite solution, and chloroform and water were further added to the reaction solution, and the organic layer was washed with water three times. The organic layer was dried using anhydrous sodium sulfate, concentrated with an evaporator, and purified by silica gel column chromatography (chloroform / hexane). As a result, 0.02 g (0.03 mmol) of the compound represented by the formula (2-1) was obtained. , Yield 20 mol%, orange solid), and 0.005 g (0.007 mmol, 4.9 mol%, reddish brown solid) of the compound represented by formula (2-2) was obtained.

Analytical data of the obtained compound (2-1) and compound (2-2) are as follows.
Compound (2-1):
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 0.87-0.93 (m, 12H), 1.25-1.42 (m, 24H), 2.30 (t, J = 7.6 Hz) , 4H), 2.62 (t, J = 8.0 Hz, 4H), 6.40-6.42 (m, 2H), 6.58-6.59 (m, 2H), 6.63-6 .64 (m, 2H), 6.76-6.77 (m, 2H) 7.91-7.92 (m, 2H).
UV-bis (CHCl ₃ ): λmax, 408 nm
Compound (2-2):
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 0.90-0.95 (m, 12H), 1.25-1.47 (m, 18H), 2.31-2.34 (m, 2H) ), 2.46-2.49 (m, 2H) 2.62-2.66 (m, 2H) 2.79-2.82 (m, 2H), 2.86-2.90 (m, 2H) ), 4.17-4.21 (m, 2H), 5.09-5.13 (m, 2H), 5.18 (s, 1H), 5.59 (s, 1H), 6.46- 6.47 (m, 1H), 6.62-6.64 (m, 1H), 6.77 (t, J = 2.0 Hz, 2H), 6.92 (t, J = 2.0 Hz, 2H) ), 7.27 (s, 1H), 7.84-7.85 (m, 1H).
UV-bis (CHCl ₃ ): λmax, 450, 472 nm

  Synthesis Example 2-9 (2,3,5,6-BCPy-pyridine-OX)

In a 20 ml reaction vessel, 0.11 g (0.17 mmol) of 2,3,5,6-BCPy-pyridine and 9.4 g of dichloromethane were weighed and stirred to obtain a uniform solution. To this reaction solution, a dichloromethane solution of iodine <0.13 g (0.51 mmol) of iodine (I ₂ ) was dissolved in 3.9 g of dichloromethane> was added with stirring, and then irradiated with light with a UV lamp for 10 hours.
After the irradiation, the reaction was quenched with an aqueous sodium hydrogen sulfite solution, the reaction solution was filtered to remove insolubles, chloroform was added to the filtrate, and the reaction solution was washed with water three times. The organic layer was washed with anhydrous sodium sulfate, concentrated and purified by silica gel column chromatography (chloroform) to obtain a compound represented by the formula (2-3) (hereinafter “2, 3, 5, 6”). -BCPy-pyridine-OX ") was obtained in 0.07 g (0.11 mmol, yield 64 mol%).

Analytical data of the obtained 2,3,5,6-BCPy-pyridine-OX are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.56-1.71 (m, 16H), 3.95-3.99 (m, 4H), 4.41-4.48 (m, 4H) ), 6.57-6.64 (m, 8H), 7.10 (s, 2H), 7.65 (s, 2H), 7.74 (s, 1H).

3. Expansion of conjugated system Synthesis example 3-1 (thermal decomposition reaction of 2,3,5,6-BCPy-TPN-OX)

By heat-treating 2,3,5,6-BCPy-TPN-OX 13.9 mg (0.02 mmol) obtained above at 300 ° C. for 30 minutes, 11.4 mg of the compound represented by the formula (1-8) ( 0.0196 mmol, yield 98 mol%).
The analytical data of the obtained compound (1-8) are as follows.
MS (MALDI-TOF) m / z = 585.5077
(Calculated value: exact mass = 584.1749, molecular weight = 584.6270)

  Synthesis Example 3-2 (2,3,5,6-BCPy-1,4-DF-BN-OX thermal decomposition reaction)

By heat-treating 18.5 mg (0.027 mmol) of 2,3,5,6-BCPy-1,4-DF-BN-OX obtained above at 300 ° C. for 30 minutes, it is represented by the formula (1-9). 14.8 mg (0.026 mmol, yield 96 mol%) of the above compound was obtained.
The analytical data of the obtained compound (1-9) are as follows.
UV-bis (CH ₂ Cl ₂ ): λmax, 441, 437, 303 nm
MS (MALDI-TOF) m / z = 570.421
(Calculated value: exact mass = 570.1656, molecular weight = 570.5890)
Anal. _{calcd for C 46 H 40 F 2} N 4 · 1 / 2H 2 O: C, 79.99; H, 3.53; F, 6.66; N, 9.82
Found: C, 79.69; H, 3.60; N, 9.63

  The highly conjugated compound of the present invention is useful as an organic field effect transistor or a conductive material.

Claims (7)

A highly conjugated compound represented by formula (1), formula (2a) or formula (2b).

Wherein ^(1), R 1 ~R ⁴ are the same or different, represent a hydrogen atom or a halogenated optionally an aliphatic hydrocarbon group. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of aliphatic hydrocarbon groups which may be halogenated, and these aliphatic hydrocarbon groups which may be halogenated are bonded to each other. Thus, a ring structure may be formed.
X represents a hydrogen atom or forms a carbon-carbon bond between adjacent XX.
A ^{1 to} A ⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (3). ]

[In formulas (2a) and (2b), R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an optionally halogenated hydrocarbon group. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of hydrocarbon groups which may be halogenated, and these hydrocarbon groups which may be halogenated are bonded to each other to form a ring structure. May be formed.
X represents a hydrogen atom or forms a carbon-carbon bond between adjacent XX.
A ^{1 to} A ³ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (3). ]

[In Formula (3), R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or a hydrocarbon group which may be halogenated, and may be bonded to each other to form a ring structure.
X represents a hydrogen atom or forms a carbon-carbon bond between adjacent XX.
* Represents a bonding position.
Note that when substituents plurality of A ¹ to A ⁴ is represented by the formula (3), a plurality of R ⁵ may be the same or different, may be different in each of a plurality of R ⁶ are the same. ] The highly conjugated compound according to claim 1, wherein the compound represented by the formula (1) has a skeleton other than R ^{1 to} R ⁶ corresponding to the formulas (4a) to (4c).

[In the formulas (4a) to (4c), ** represents a bonding position of R ^{1 to} R ⁶ .
D ¹ and D ² are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6a). ]

[In the formula (6a), ** represents the bonding position of R ⁵ and R ⁶ .
* Represents a bonding position. ] The highly conjugated compound according to claim 1, wherein the compound represented by the formula (2a) or the formula (2b) has a skeleton other than R ^{1 to} R ⁶ corresponding to the formulas (5a) to (5c).

[In the formulas (5a) to (5c), ** represents the bonding position of R ^{1 to} R ⁶ .
D ¹ represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6a). ] The ring structure formed by R ¹ and R ² , R ³ and R ⁴ , or R ⁵ and R ⁶ is represented by formula (7a) or formula (7b). Highly conjugated compounds as described.

[In formulas (7a) and (7b), * indicates a bonding position. ] A highly conjugated compound precursor represented by formula (8), formula (9a), or formula (9b):

[In Formula (8), R < ¹ > -R < ⁴ > is the same or different, and represents the aliphatic hydrocarbon group which may be a hydrogen atom or halogenated. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of aliphatic hydrocarbon groups which may be halogenated, and these aliphatic hydrocarbon groups which may be halogenated are bonded to each other. Thus, a ring structure may be formed.
F ^{1 to} F ⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6). ]

[In the formulas (9a) and (9b), R ^{1 to} R ⁴ are the same or different and each represents a hydrogen atom or an optionally halogenated hydrocarbon group. Note that at least one pair of R ¹ and R ² or R ³ and R ⁴ represents a group of hydrocarbon groups which may be halogenated, and these hydrocarbon groups which may be halogenated are bonded to each other to form a ring structure. May be formed.
F ^{1 to} F ³ are the same or different and each represents a hydrogen atom, a fluorine atom, a cyano group, or a substituent represented by the formula (6). ]

[In formula (6), R ⁵ and R ⁶ represent a hydrogen atom or a hydrocarbon group which may be halogenated, and may be bonded to each other to form a ring structure.
* Represents a bonding position.
Note that when substituents plurality of F ¹ to F ⁴ are represented by the formula (6), a plurality of R ⁵ may be the same or different, may be different in each of a plurality of R ⁶ are the same. ] Two or more of the compounds represented by formula (10) or (11) and the compounds represented by formulas (12a) to (12c) (provided that the compound is represented by formula (12a) and formula (12b)) Compound is necessarily included), and after synthesizing a highly conjugated compound precursor represented by the formula (8), formula (9a) or formula (9b), the highly conjugated compound precursor is oxidized to give the formula (1 ), A highly conjugated compound represented by the formula (2a) or the formula (2b), and a method for producing a highly conjugated compound.

[In the formulas (10) and (11), E ^{1 to} E ⁶ are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, or a cyano group. ]

[In the formulas (12a) to (12c), R ^{1 to} R ⁶ are the same or different and each represents a hydrogen atom or a hydrocarbon group which may be halogenated and bonded to each other to form a ring structure. Also good. ]   The method for producing a highly conjugated compound according to claim 6, wherein the highly conjugated compound precursor is purified and then oxidized.