JP4018066B2 - New hexaperihexabenzocoronene derivatives - Google Patents

Description

  The present invention relates to hexaperihexabenzocoronene derivatives having a novel substitution mode for constructing nanoscale molecules and nano-sized structures formed by self-assembly thereof.

Hexaperhexabenzocoronene is a disk-like molecule having a diameter of about 1 nm. It is well known that a disk-shaped pi-electron compound with high planarity often exhibits a discotic liquid crystal phase. Derivatives (HBC) in which six long-chain alkyl groups are introduced into the molecule of hexaperhexabenzocoronene are representative molecules of a group of compounds having such properties and exhibit a discotic liquid crystal phase that is stable up to high temperatures. In addition, it is known to have luminous properties, high carrier mobility, and the like.
HBC easily forms a column structure in which molecules are stacked one-dimensionally due to π-π interaction, and shows high mobility because carriers can easily move through this column. In the liquid crystal phase of this molecule, this one-dimensional column is packed with hexagonal regularity, but if only this column can be cut out, this means that a nano-sized wire in which molecules are integrated in one dimension. Can be considered. The construction of such nanoscale molecular assemblies is important not only for basic science, but also for application to molecular devices, etc., and may exhibit unique functions that reflect the characteristics and structure of the constituent molecules. Expected.
HBC derivatives having various physical properties are: Although it is a promising molecule from this point of view, the number of its derivatives is limited. In particular, if several independent molecular units are introduced into the HBC. Although further functionalization is expected, such asymmetric substitutions are not well known so far.

In recent years, attempts have been actively made to use the above-described light and electronic characteristics of HBC for organic optoelectronic devices and the like. In addition to such totally symmetric substituents, if the central skeleton is compared with benzene, synthesis of derivatives with reduced symmetry such as para type (below HBC1) and ortho type (below HBC2) has been studied. However, there has been no report on a derivative having a meta-type substitution pattern. On the other hand, benzene derivatives having a substituent at the meta position are frequently used as one of the optimum units for constructing nanoscale molecules such as dendrimers, macrocyclic compounds, and helical polymers. Therefore, for hexaperhexabenzocoronene, by developing a new unit having a meta-type substitution pattern, it is possible to expect the construction of a unique higher-order structure and a structure exhibiting new functionality.

  The present invention has been made in view of the current situation as described above, and includes a novel hexaperihexabenzocoronene derivative having symmetry similar to that of a meta-substituted benzene, and a nano-sized structure formed by the self-assembly. The purpose is to provide.

The present invention provides the following general formula [1]
[Wherein R ¹ represents an alkyl group, R ² represents C ₆ H ₄ OR ³ or C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OR ³ (provided that R ³ represents a hydrogen atom or Represents an alkyl group, n represents a positive integer), and X represents a halogen atom. ]
It is related with the hexaperihexabenzocoronene derivative represented by these.

  The present invention also relates to a nano-sized self-assembled body formed in a solution comprising the compound represented by the general formula [1] and one or more solvents.

Furthermore, the present invention provides the following general formula [2]
[Wherein R ¹ represents an alkyl group, R ² represents C ₆ H ₄ OR ³ or C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OR ³ (provided that R ³ represents a hydrogen atom or Represents an alkyl group, n represents a positive integer.), R ⁴ represents -A-CO ₂ R ⁵ (where A represents a divalent hydrocarbon group, R ⁵ represents a hydrogen atom or an alkyl group). To express.). ]
It is related with the hexaperihexabenzocoronene derivative represented by these.

  Furthermore, the present invention relates to a nano-sized self-assembly formed in a solution comprising the compound represented by the general formula [2] and one or more solvents.

  That is, as described above, the present inventors, as described above, are benzene derivatives having a substituent at the meta position as one of the optimal units for constructing nanoscale molecules such as dendrimers, macrocyclic compounds, and helical polymers. Due to its frequent use, hexaperhexabenzocoronene also has a unique higher-order structure and a structure that exhibits new functionality by developing a new unit with a meta-type substitution pattern. As a result of intensive research on the synthesis of a new hexaperhexabenzobenzocorene derivative having similar symmetry to that of meta-substituted benzene, ribbon-like or tube-like nano-sized self-assembly in solvent solution And a compound represented by the above general formula [1], which is also derived from the compound and is also easily derived from the compound in the form of a ribbon or tube. In the above general formula may form a self-assembled body represented by [2] to create the compound, and have completed the present invention.

  The hexaperihexabenzocoronene derivative represented by the above general formula [1] of the present invention (hereinafter sometimes referred to as HBC derivative) forms a nano-sized self-assembled body in the form of a ribbon or tube itself. Although it is a molecule that can be widely used as the most basic precursor in synthesizing HBC derivatives of various meta-type substitution modes, the HBC derivative represented by the general formula [2] It is an example of a group of useful HBC derivatives derived from the precursor. The HBC derivative represented by the above general formula [1] of the present invention and the HBC derivative of various meta types including the HBC derivative represented by the general formula [2] derived from the compound include, for example, , By introducing hydrophilic and hydrophobic substituents into these to make them amphiphilic, self-assembly through the joint effect of amphiphilicity, hydrophobic effect and π-π stacking forms nanoscale aggregates can do. Therefore, the structure can be formed not only by covalent bonds but also by non-covalent interactions.

In the general formula [1] and the general formula [2], the alkyl group represented by R ¹ is, for example, a straight chain having 1 to 30, preferably 10 to 30, more preferably 10 to 20 carbon atoms. A branched or cyclic alkyl group, and preferred specific examples include, for example, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, and a nonadecyl group. These may be linear, branched or cyclic. In the case of an alkyl group having 10 or less carbon atoms, a bulky group such as a t-butyl group is preferable.
The alkyl group represented by ^{R 3} in _{C 6 H 4 OCH 2 CH 2} (OCH 2 CH 2) n OR 3 represented by ^{R 2,} for example, 1 to 20 carbons, preferably 1 to 10, more preferably 1-6 linear, branched or cyclic alkyl groups, and specific examples include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, Secondary butyl group, tertiary butyl group, pentyl group, hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned.
n is an arbitrary positive integer, but an integer of 2 or more is more preferable.
Preferable specific examples of R ² include, for example, C ₆ H ₄ OH, C ₆ H ₄ OCH ₃ , C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OH, C ₆ H ₄ OCH ₂ CH ₂ ( OCH ₂ CH ₂ ) _n OCH _{3 and the} like, and further preferable examples of CH ₂ (OCH ₂ CH ₂ ) _n OH and C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OCH ₃ include, for example, _{, C 6 H 4 OCH 2 CH} 2 (OCH 2 CH 2) 2 OH, C 6 H 4 OCH 2 CH 2 (OCH 2 CH 2) 3 OH, C 6 H 4 OCH 2 CH 2 (OCH 2 CH 2) 4 _{OH, C 6 H 4 OCH 2} CH 2 (OCH 2 CH 2) 2 OCH 3, C 6 H 4 OCH 2 CH 2 (OCH 2 CH 2) 3 OCH 3, C 6 H 4 OCH 2 CH _(OCH 2 _{CH 2)} 4 is OCH ₃ and the like, but the invention is not of course limited thereto.

  In the general formula [1], examples of the halogen atom represented by X include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. In synthesizing HBC derivatives in various meta-type substitution modes, When considered as a precursor, more reactive bromine and iodine atoms are preferred.

In the general formula [2], the alkyl group represented by ^{R 5} in _-A-CO 2 ^{R 5,} represented by ^{R 4,} same as the alkyl group represented by ^{R 3,} for example, carbon atoms Examples include 1-20, preferably 1-10, more preferably 1-6 linear, branched or cyclic alkyl groups. Specific examples include, for example, methyl group, ethyl group, propyl group, isopropyl group. Group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.
Examples of the divalent hydrocarbon group represented by A include a phenylene group, a biphenylene group, a naphthylene group, and an alkylene group. These hydrocarbon groups may have one or more of these substituents as long as they do not adversely affect the reaction and use.
Preferable specific examples of R ⁴ include, for example, —C ₆ H ₄ —COOH, —C ₆ H ₄ —CO ₂ CH _3, —C ₆ H ₄ —CO ₂ C ₂ H _5, etc. It is not limited to.

The method for synthesizing the compound represented by the general formula [1] is exemplified by the case where X is Br, R ¹ is C ₁₂ H ₂₅ , and R ² is C ₆ H ₄ OCH ₃ or C ₆ H ₄ OH. The reaction scheme is as follows.
For details of the reaction operation procedure and the like, refer to the description of Examples described later.

In the method for synthesizing the compound represented by the general formula [2], R ⁴ is —C ₆ H ₄ —CO ₂ C ₂ H ₅ or —C ₆ H ₄ —COOH, and R ¹ is C ₁₂ H _25. In the reaction scheme, R ² is C ₆ H ₄ OCH ₃ as an example.
For details of the reaction operation procedure and the like, refer to the description of Examples described later.

Further, in the above general formula [2], R ¹ is C ₁₂ H ₂₅ , R ² is C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) ₂ OCH ₃ , and R ⁴ is —C ₆ H ₄ —. A synthesis method of a compound of CO ₂ C ₂ H ₅ or —C ₆ H ₄ —COOH is shown in a reaction scheme as follows.

  The compound represented by the general formula [1] and the compound represented by the general formula [2] of the present invention forms a nano-sized self-assembled body in a solution by dissolving the compound in one or more solvents. . The self-assembly is usually in the form of a ribbon or a tube.

Next, the results of examination of the association behavior in solution of the compound 12a described in the above reaction scheme, which is the novel hexaperihexabenzocoronene derivative of the present invention, using ultraviolet-visible light and fluorescence spectrum will be described. .
Compound 12a showed no significant change in the ultraviolet absorption spectrum in an organic solvent such as THF, chloroform or benzene, but the fluorescence spectrum showed different results depending on the solvent. For example, a peak derived from a monomer appears in THF at 25 ° C., but a peak mainly attributed to an excimer was observed in benzene (see FIGS. 1 and 2). In addition, the fluorescence characteristics in benzene solvent showed a strong temperature dependence, giving monomer luminescence at high temperature, but again exhibiting excimer luminescence at low temperature.
On the other hand, Compound 12b in the form of removing the methyl group from a compound 12a is chloroform gelled nanofiber structure than observation field emission scanning electron microscope (FE-SEM) was observed (see Figure 3). Since the compound 12a does not gel in chloroform, it is considered that the intermolecular interaction of the compound 12b is strengthened by the hydrogen bond between phenols in addition to π-π stacking.

Therefore, in order to form a new aggregate by stronger structural control in the lateral direction of HBC, a compound 19a of the present invention in which a phenylacetylene derivative was introduced at the meta position and hydrophilic triethylene glycol was introduced at the center position was synthesized. The association property in the solution was examined. As a result, in the compound 19a , a capsule-like structure having a diameter of 300 nanometers was observed by FE-SEM in a THF-water (3: 1) mixed solution (see FIG. 4).
That is, an amphiphilic derivative molecule having hydrophilic and hydrophobic substituents introduced into the new hexaperhexabenzocoronene skeleton according to the present invention, which has symmetry similar to that of meta-substituted benzene, is a large pi In spite of the electronic compounds, it has been found that a spherical structure (vesicle) having a diameter of several hundred nanometers produces an interesting self-association behavior.
On the other hand, in the free compound 19b obtained by hydrolyzing this ester (compound 19a ), formation of fibers having a diameter of about 20 nanometers and a length of several micrometers was confirmed by FE-SEM under the same conditions. (See FIG. 5).
Further, by introducing a phenylacetylene derivative in the meta position, to synthesize a compound of the present invention 15b introduced with a 4-methoxyphenyl group to the center position, were examined associative in solution, the compound 15b is nanofiber structure in THF Forming a body was confirmed by FE-SEM (see FIG. 6).
Thus, it was also revealed that the self-association behavior can be controlled by fine modification of the molecular structure of HBC, and different nanostructures can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by these Examples.

Synthesis of 2,8-dibromo-11,14,17-dodecyl- (4-methoxyphenyl) hexaperhexabenzocoronene (Compound 12a) (1) Synthesis of 4-dodecylbenzyl alcohol (Compound 1 ) Under argon atmosphere, 4 -Bromodecylbenzene (3.25 g, 10.0 mmol) was dissolved in tetrahydrofuran (THF, 100 mL) and cooled to -78 ° C. N-Butyllithium (7 ml, 1.6 M hexane solution) was added to this solution and stirred for 1 hour, and then dimethylformamide (20 mL) was added and further stirred for 1 hour. The reaction mixture was warmed to room temperature, poured into water and extracted with ether. The organic layer was washed with water and then with saturated brine, and then dried over anhydrous sodium sulfate. The residue obtained after evaporation of the solvent was purified by silica gel column chromatography to give 4-bromododecylbenzaldehyde as a colorless oil. This aldehyde was dissolved in ethanol (30 mL), sodium borohydride (2.77 g, 73.2 mmol) was added, and the mixture was stirred at room temperature for 3 hr. After distilling off the solvent, dichloromethane was added, washed with 1M hydrochloric acid, water and then saturated brine, and dried over anhydrous sodium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography to obtain Compound 1 as a colorless solid (2.13 g, yield 77%).
¹ HNMR (500 MHz, CDCl ₃ ): δ = 7.25 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 8.0 Hz, 2H), 4.62 (d, J = 6) .5 Hz, 2H), 2.58 (t, J = 7.5 Hz, 2H), 1.58 (m, 2H), 1.19-1.27 (m, 18H), 0.86 (t, J = 7.0 Hz, 3H).

(2) Synthesis of 4-dodecylbenzyl bromide (Compound 2 ) Under an argon atmosphere, a THF (15 mL) solution of Compound 1 (1.11 g, 4.02 mmol) was cooled to 0 ° C., and carbon tetrabromide (1.60 g). , 4.82 mmol) and triphenylphosphine (1.26 g, 4.02 mmol) were added and stirred for 30 minutes. The reaction mixture was poured into water and extracted with dichloromethane. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain Compound 2 as a colorless solid (1.25 g, yield 85%).
¹ HNMR (500 MHz, CDCl ₃ ): δ = 7.29 (d, J = 8.0 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 4.47 (s, 2H), 2.59 (t, J = 7.5 Hz, 2H), 1.59 (m, 2H), 1.24-1.28 (m, 18H), 0.88 (t, J = 6.5 Hz, 3H) ).

(3) Synthesis of 1- (4-bromophenyl) -3- (4-dodecylphenyl) propanone (Compound 3 ) Tosylmethyl isocyanide (402 mg, 2.06 mmol) and tetrabutylammonium iodide (38. 10 mg, 0.10 mmol) was dissolved in dichloromethane / 40% aqueous sodium hydroxide solution (1: 1, 20 mL), 4-bromobenzyl bromide (514 mg, 2.06 mmol) was added thereto, and the mixture was stirred at room temperature for 90 minutes. Subsequently, Compound 2 (700 mg, 2.06 mmol) was added, and the mixture was further stirred at room temperature for 16 hours. The reaction mixture was poured into water, extracted with dichloromethane, the organic layer was washed with water and then with saturated brine, and the solvent was evaporated under reduced pressure. The resulting residue was dissolved in ether (9 mL) and dichloromethane (3 mL) and treated with 35% concentrated hydrochloric acid (1 mL). The reaction mixture was poured into water, extracted with dichloromethane, and washed with 1N aqueous sodium hydroxide solution, water and saturated brine. The residue obtained by evaporating the solvent was purified by silica gel column chromatography to obtain Compound 3 as a colorless solid (424 mg, yield 45%).
¹ HNMR (500 MHz, CDCl ₃ ): δ = 7.41 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 7.05 (d, J = 8 0.0 Hz, 2H), 6.97 (d, J = 8.0 Hz, 2H), 3.74 (s, 2H), 3.66 (s, 2H), 2.58 (t, J = 8.0 Hz) , 2H), 1.85 (m, 2H), 1.24-1.29 (m, 18H), 0.87 (t, J = 7.5 Hz, 3H).
MALDI-TOF-MS: [M + Na] ⁺ (calcd. 480.48): found.

(4) Synthesis of 2- (4′-bromo-biphenyl-4-yloxy) tetrahydro-2H-pyran (compound 4 ) 4,4′-dibromobiphenyl (9.96 g, 40.0 mmol) and p-toluenesulfonic acid Monohydrate (50 mg) was dissolved in dichloromethane and cooled on ice. 3,4-Dihydro-2H-pyran (6.0 mL, 65.8 mmol) was added dropwise to this solution, followed by stirring at 0 ° C. for 1 hour and then at room temperature for 1 hour, and then poured into a 10% aqueous sodium hydroxide solution. Extracted with. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography to obtain compound 4 as a colorless solid (12.3 g, yield 93%).
¹ HNMR (500 MHz, CDCl ₃ ): δ = 7.53 (d, J = 8.5 Hz, 2H), 7.48 (d, J = 8.5 Hz, 2H), 7.42 (d, J = 8 .5 Hz, 2H), 7.13 (d, J = 8.5 Hz, 2H), 5.46 (t, J = 3.0 Hz, 1H), 3.90-3.95 (m, 1H), 3 .60-3.64 (m, 1H), 1.99-2.06 (m, 1H), 1.87-1.90 (m, 2H), 1.60-1.74 (m, 3H) .

(5) Synthesis of 2-methyl-4- [4 ′-(tetrahydro-2H-pyran-2-yloxy) biphenyl-4-yl] -3-butyn-2-ol (Compound 5 ) 2-methyl-3- Butyn-2-ol (4.0 mL, 41.2 mmol), dichlorobistriphenylphosphine palladium (1.02 g, 1.45 mmol), copper iodide (554 mg, 2.91 mmol), compound 4 (9.69 g, 29. 1 mmol), triethylamine (50 mL) and benzene (50 mL) were heated and stirred at 60 ° C. for 32 hours under an argon atmosphere. After allowing to cool, the resulting precipitate was filtered off, washed with dichloromethane, the organic layers were combined, and the solvent was distilled off. The residue was recrystallized from dichloromethane to obtain Compound 5 as a colorless solid (7.97 g, yield 81%).
¹ HNMR (500 MHz, CDCl ₃ ): δ = 7.52 (d, J = 8.5 Hz, 2H), 7.50 (d, J = 8.5 Hz, 2H), 7.46 (d, J = 8 .5 Hz, 2H), 7.13 (d, J = 8.5 Hz, 2H), 5.47 (m, 1H), 3.90-3.95 (m, 1H), 3.60-3.64. (M, 1H), 2.01-2.04 (m, 1H), 1.60-1.72 (m, 6H).

(6) Synthesis of 2- (4′-ethynyl-biphenyl-4-yloxy) tetrahydro-2H-pyran (Compound 6 ) Compound 5 (7.90 g, 23.48 mmol) was dissolved in toluene (200 mL) under an argon atmosphere. After adding potassium hydroxide (1.97 g, 35.2 mmol), the mixture was heated to reflux for 3 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The obtained residue was purified by silica gel column chromatography to obtain compound 6 as a pale yellow solid (6.05 g, yield 93%).
¹ HNMR (500 MHz, CDCl ₃ ): δ = 7.48-7.52 (m, 6H), 7.12 (d, J = 8.5 Hz, 2H), 5.45 (t, J = 3.0 Hz) , 1H), 3.88-3.93 (m, 1H), 3.59-3.63 (m, 1H), 3.09 (s, 1H), 1.97-2.03 (m, 1H) ), 1.85-1.88 (m, 2H), 1.58-1.70 (m, 3H).

(7) Synthesis of 2-[(4 ′-(4-Bromo-phenylethynyl) biphenyl-4-yloxy) tetrahydro-2H-pyran (Compound 7 ) Compound 6 (6.00 g, 21.6 mmol) under argon atmosphere 4-iodobromobenzene (6.85 g, 24.2 mmol), copper iodide (410 mg, 2.16 mmol) and tetrakistriphenylphosphine palladium (0) (998 mg, 0.863 mmol) suspended in toluene (150 mL). Triethylamine (20 mL) was added thereto, and the mixture was stirred with heating at 50 ° C. for 12 hours. The resulting precipitate was collected by filtration and washed thoroughly with methanol. The obtained solid was repeatedly recrystallized from toluene to obtain Compound 7 as a colorless solid (8.47 g, yield 91%).
¹ HNMR (500 MHz, CDCl ₃ ): δ = 7.52-7.55 (m, 6H), 7.49 (d, J = 8.0 Hz, 2H), 7.14 (d, J = 9.0 Hz) , 2H), 5.48 (t, J = 3.0 Hz, 1H), 3.90-3.95 (m, 1H), 3.62-3.64 (m, 1H), 2.01-2 .03 (m, 1H), 1.87-1.90 (m, 2H), 1.61-1.74 (m, 3H).

(8) Synthesis of 1- (4-bromophenyl) -2- [4 ′-(tetrahydro-2H-pyran-2-yloxy) biphenyl-4-yl] ethane-1,2-dione (compound 8 ) Compound 7 (8.97 g, 20.7 mmol) was suspended in a mixed solution of carbon / acetonitrile / water (120 mL: 120 mL: 240 mL), sodium periodate (18.2 g, 85.1 mmol) was added, and at room temperature. The reaction was vigorously stirred. Next, ruthenium oxide monohydrate (60 mg, 0.45 mmol) was added thereto, stirred for 3 hours, poured into water and extracted with dichloromethane. The organic layer was washed with water and dried over anhydrous sodium sulfate. The reaction mixture was filtered through celite, concentrated, and the residue was purified by silica gel column chromatography to give compound 8 as a pale yellow solid (7.37 g, yield 77%).
¹ HNMR (500 MHz, CDCl ₃ ): δ = 7.99 (d, J = 8.5 Hz, 2H), 7.86 (d, J = 8.5 Hz, 2H), 7.69 (dd, J = 8 .5 Hz, J = 8.5 Hz, 4H), 7.56 (d, J = 8.5 Hz, 2H), 7.15 (d, J = 8.5 Hz, 2H), 5.47 (t, J = 3 Hz, 1H), 3.87-3.92 (m, 1H), 3.59-3.63 (m, 1H), 1.97-2.03 (m, 1H), 1.86-1. 89 (m, 2H), 1.59-1.73 (m, 3H).
MALDI-TOF-MS: [M + H] ⁺ (calcd.465.34): found.465.34.

(9) 2,4-bis (4-bromophenyl) -5- (4-dodecylphenyl) -3- [4 ′-(tetrahydro-2H-pyran-2-yloxy) biphenyl-4-yl] cyclopenta-2 Synthesis of 1,4-dienone (Compound 9a ) In an argon atmosphere, Compound 3 (1.97 g, 4.30 mmol) and Compound 8 (2.0 g, 4.30 mmol) were dissolved in 1,4-dioxane (4 mL). Heated to reflux. To this was added a methanol solution of tetrabutylammonium hydroxide (1.0 M, 2.15 mL, 2.15 mmol) and the mixture was further refluxed for 15 minutes, and then the reaction mixture was poured into water. Extraction was performed with dichloromethane, and the organic layer was washed with water and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain Compound 9a containing no isomer as a brown solid (1.0 g, yield 26%).
¹ HNMR (500 MHz, CDCl ₃ ): δ = 7.52 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.5 Hz, 2H), 7.37 (d, J = 8 .5 Hz, 2H), 7.31 (d, J = 8.5 Hz, 2H), 7.09-7.16 (m, 6H), 7.06 (d, J = 8.5 Hz, 2H), 6 .92 (d, J = 8.5 Hz, 2H), 6.82 (d, J = 8.5 Hz, 2H), 5.46 (t, J = 3 Hz, 1H), 3.90 (m, 1H) , 3.61 (m, 1H), 2.54 (m, 2H), 2.02 (m, 1H), 1.85-1.88 (m, 2H), 1.57-1.68 (m , 4H), 1.24-1.28 (m, 18H), 0.86 (t, J = 7.0 Hz, 3H).
MALDI-TOF-MS: [M + Na] ⁺ (calcd. 909.80): found. 909.82.

(10) Synthesis of 1,3-bis (4-bromophenyl) -4,5,6-tris (4-dodecylphenyl) -2- [4′-methoxybiphenyl-4-yl] benzene (Compound 11 ) Argon Under an atmosphere, compound 9a (220 mg, 0.25 mmol) and 4,4′-didodecylphenylacetylene (127 mg, 0.25 mmol) were dissolved in diphenyl ether (1.5 mL) and heated to reflux for 20 hours. After cooling to room temperature, the product was purified by silica gel column chromatography to obtain compound 10 as a colorless solid (200 mg, yield 63%). This alcohol 10 (200 mg, 0.16 mmol), potassium carbonate (53.6 mg, 0.39 mmol) and 18-crown-6-ether (21 mg, 0.078 mmol) were dissolved in THF (20 mL). After adding iodomethane (110 mg, 0.78 mmol), the mixture was heated to reflux for 3 hours. The reaction mixture was poured into water and extracted with dichloromethane. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain Compound 11 as a colorless solid (200 mg, yield 99%).
[Compound 10 ]
¹ HNMR (500 MHz, CDCl ₃ ): δ = 7.36 (d, J = 8.5 Hz, 2H), 7.10 (d, J = 8.5 Hz, 2H), 6.96 (d, J = 8 .5 Hz, 4H), 6.77-6.82 (dd, J = 8.5 Hz, J = 8.5 Hz, 4H), 6.68 (d, J = 8.5 Hz, 4H), 6.61- 6.65 (m, 12H), 4.73 (s, 1H), 2.30-2.36 (m, 6H), 1.09-1.42 (m, 60H), 0.86 (t, J = 6.5 Hz, 9H).
MALDI-TOF-MS: [M + H] ⁺ (calcd. 1289.53): found.
[Compound 11 ]
¹ HNMR (500 MHz, CDCl ₃ ): δ = 7.41 (d, J = 9.0 Hz, 2H), 7.12 (d, J = 8.5 Hz, 2H), 6.96 (d, J = 8 .5 Hz, 4H), 6.90 (d, J = 9.0 Hz, 2H), 6.80 (d, J = 8.5 Hz, 4H), 6.69 (d, J = 8.5 Hz, 4H) 6.60-6.66 (m, 12H), 3.80 (s, 3H), 2.31-2.37 (m, 6H), 1.09-1.43 (m, 60H), 0 .85-0.88 (m, 9H).
MALDI-TOF-MS: [M + H] ⁺ (calcd. 1303.56): found. 1303.64.

(11) Synthesis of 2,8-dibromo-11,14,17-tridodecyl- (4-methoxyphenyl) hexaperihexabenzocoronene (compound 12a ) Nitromethane of iron (III) chloride (1.10 g, 6.77 mmol) The (7 mL) solution was added dropwise to a solution of Compound 11 (490 mg, 0.38 mmol) in dichloromethane (70 mL) while passing argon gas. Subsequently, the mixture was stirred at room temperature for 20 minutes while passing argon through the reaction mixture, poured into excess methanol, and the resulting precipitate was collected by filtration. Purification by silica gel column chromatography gave the HBC derivative of the present invention (Compound 12a ) as a yellow solid (420 mg, yield 87%).
¹ HNMR (500 MHz, THF-d ₈ ): δ = 6.07-6.76 (m, 16H), 3.72 (s, 3H), 1.96-2.73 (m, 6H), 1. 18-1.35 (m, 60H), 0.83-0.86 (m, 9H).
MALDI-TOF-MS: [M + H] ⁺ (calcd. 1291.46): found.

Derivation from bromo-substituted HBC derivatives (compound 12a) to other meta-type substitutional HBC derivatives (synthesis of compound 15a)
Under an argon atmosphere, compound 12a (140 mg, 0.1 mmol), copper iodide (6 mg.0.08 mmol) and dichlorobistriphenylphosphine palladium (40 mg, 0.05 mmol) were dissolved in piperidine (20 mL), and triisopropyl was dissolved therein. Silylacetylene (2 mL) was added. The reaction mixture was stirred at 80 ° C. for 24 hours, poured into a saturated aqueous ammonium chloride solution, and extracted with dichloromethane. The organic layer was washed with a saturated aqueous ammonium chloride solution, water, and then saturated brine, and then dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography to obtain a triisopropylsilylethynyl derivative (compound 13 ) in a yield of 86%. Next, this compound 13 (40 mg, 0.09 mol) was dissolved in THF (10 mL), tetrabutylammonium fluoride (74 mg, 0.19 mmol) was added, and the mixture was stirred at room temperature for 1 hour, and then dichloromethane and water were added. And separated. The organic layer was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain an ethynyl derivative (compound 14 ) in a yield of 91%. Various substituents can be further introduced from this ethynyl derivative.
That is, for example, compound 14 in THF / piperidine mixed solvent, where the copper iodide and tetrakis triphenylphosphine palladium using Sonogashira reaction as a catalyst was ethyl coupled 4-iodobenzoic acid, compound 15a Was obtained in 96% yield.

Derivation of bromo-substituted HBC derivatives (compound 12a) into other meta-type substitutional HBC derivatives (synthesis of compound 19a)
(1) Synthesis of Compound 12b Under an argon atmosphere, Compound 12a (70 mg, 0.054 mmol) was dissolved in dry dichloromethane (15 mL), and boron tribromide (27 mg, 0.084 mmol) was added. The reaction mixture was stirred at room temperature overnight, then poured into ice-water solution and extracted with dichloromethane. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain a yellow crude product of Compound 12b almost quantitatively (68 mg, yield 99%).
MALDI-TOF-MS: [M + H] ⁺ (calcd. 1277.44): found. 1277.18.

(2) Synthesis of Compound 16 Compound 12b (68 mg, 0.053 mmol) obtained in (1) above, potassium carbonate (40 mg, 0.29 mmol) and 18-crown-6-ether (20 mg, 0.076 mmol) were combined. It melt | dissolved in THF (20 mL), Triethylene glycol methyl tosyl ether (1 mL) was added to this, and it was made to heat and reflux for 60 hours. The reaction mixture was poured into water and extracted with dichloromethane. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography to obtain Compound 16 as a yellow solid (62 mg, yield 82%).
¹ HNMR (500 MHz, CDCl ₃ ): δ = 6.09-6.72 (m, 16H), 4.09 (br, 2H), 3.38 (m, 2H), 3.67-3.76 ( m, 6H), 3.57 (m, 2H), 3.39 (s, 3H), 2.12 (br, 2H), 1.98 (br, 4H), 1.11-1.26 (m , 60H), 0.80-0.87 (m, 9H).
MALDI-TOF-MS: [M + H] ⁺ (calcd. 1423.62): found.1423.10.

(3) Synthesis of Compound 17 Compound 16 (62 mg, 0.043 mmol) obtained in (2) above, copper iodide (6 mg, 0.08 mmol) and dichlorobistriphenylphosphine palladium (40 mg, 0. 0) under an argon atmosphere. (05 mmol) was dissolved in piperidine (10 mL), and triisopropylsilylacetylene (1 mL) was added thereto. The reaction mixture was stirred at 80 ° C. for 24 hours, poured into a saturated aqueous ammonium chloride solution, and extracted with dichloromethane. The organic layer was washed with a saturated aqueous ammonium chloride solution, water, and then with saturated brine, and then dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent was purified by silica gel column chromatography to obtain 62 mg of a triisopropylsilylethynyl derivative (Compound 17 ) (yield 88%).
MALDI-TOF-MS: [M + H] ⁺ (calcd. 1626.25): found. 1626.72.

(4) Synthesis of Compound 18 Compound 17 (50 mg, 0.03 mol) obtained in (3) above was dissolved in THF (20 mL), and tetrabutylammonium fluoride (74 mg, 0.19 mmol) was added thereto. Stir at room temperature for 1 hour. After the reaction, dichloromethane and water were added to the reaction solution for liquid separation, and the organic layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 32 mg of an ethynyl derivative (compound 18 ) (yield 79%).
¹ HNMR (500 MHz, CDCl ₃ ): δ = 6.95-7.33 (m, 16H), 4.28 (br, 2H), 4.01 (m, 2H), 3.74-3.81 ( m, 6H), 3.63 (m, 2H), 3.43 (s, 3H), 3.09 (s, 2H), 2.33-2.37 (m, 6H), 1.17-1 .38 (m, 60H), 0.81-0.87 (m, 9H). MALDI-TOF-MS: [M + H] ⁺ (calcd. 1313.87): found.

(5) Synthesis of Compound 19a Various substituents can be further introduced from the ethynyl derivative (Compound 18 ) obtained in (4) above. That is, for example, the compound 18 in THF / piperidine mixture solvent, by copper iodide and tetrakis triphenylphosphine palladium using Sonogashira reaction as a catalyst is 4-iodo repose ethyl coupling, compound 19a Was obtained in 96% yield.
¹ HNMR (500 MHz, THF-d ₈ ): δ = 7.99 (d, J = 7.5 Hz, 4H), 6.83-7.53 (m, 20H), 4.38 (m, 4H), 4.07 (m, 2H), 3.86 (m, 2H), 3.60-3.70 (m, 8H), 3.33 (s, 3H), 2.21 (m, 2H), 1 18-1.49 (m, 70H), 0.83-0.84 (m, 9H). MALDI-TOF-MS: [M + H] ⁺ (calcd. 1610.19): found. 1610.42.

Vesicle-like nanostructure-forming compound 19a (0.16 mg, 0.1 × 10 ⁻³ mmol) was dissolved in THF (0.75 mL), ion-exchanged water (0.25 mL) was added, and ultrasonic waves were applied for 1 hour. Irradiated. When this mixture was allowed to stand at room temperature for 1 hour or longer, a vesicle-like structure was produced. The field emission scanning electron microscope (FE-SEM) image is shown in FIG.

  The hexaperihexabenzocoronene derivative represented by the general formula [1] of the present invention and various hexaperiper derivatives derived from the compound, such as a hexaperihexabenzocoronene derivative represented by the general formula [2]. Hexabenzocoronene derivatives are expected to have various uses such as gelling agents for organic solvents, optoelectronic device materials, nonlinear optical materials, inorganic / organic composite material mold materials, solar cell materials, fuel cell materials, and the like.

It is an ultraviolet absorption spectrum of the compound 12a which is one of the hexaperihexabenzocoronene derivatives represented by the general formula [1] of the present invention. It is a fluorescence spectrum of the compound 12a which is one of the hexaperihexabenzocoronene derivatives represented by the general formula [1] of the present invention. It is a FE-SEM image (photograph replaced with drawing) of the self-assembly body of the compound 12b which is one of the hexaperihexabenzocoronene derivatives represented by General formula [1] of this invention. It is a FE-SEM image (photograph replaced with drawing) of the self-assembly body of the compound 19a which is one of the hexaperihexabenzocoronene derivatives represented by General formula [2] of this invention. (Example 4) It is a FE-SEM image (photograph replaced with drawing) of the self-assembly body of the compound 19b which is one of the hexaperihexabenzocoronene derivatives represented by General formula [2] of this invention. It is a FE-SEM image (photograph replaced with drawing) of the self-assembly body of the compound 15b which is one of the hexaperihexabenzocoronene derivatives represented by General formula [2] of this invention.

Claims (25)

The following general formula [1]
[Wherein R ¹ represents an alkyl group, R ² represents C ₆ H ₄ OR ³ or C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OR ³ (provided that R ³ represents a hydrogen atom or Represents an alkyl group, n represents a positive integer), and X represents a halogen atom. ]
A hexaperihexabenzocoronene derivative represented by:   The hexaperihexabenzocoronene derivative according to claim 1, wherein, in the general formula [1], X is a bromine atom or an iodine atom.   The hexaperihexabenzocoronene derivative according to claim 1, wherein, in the general formula [1], X is a bromine atom. The hexaperihexabenzocoronene derivative according to any one of claims 1 to 3, wherein in the general formula [1], R ¹ is an alkyl group having 10 to 30 carbon atoms. The hexaperihexabenzocoronene derivative according to any one of claims 1 to 3, wherein in the general formula [1], R ¹ is an alkyl group having 10 to 20 carbon atoms. The hexaperihexabenzocoronene derivative according to any one of claims 1 to 3, wherein in the general formula [1], R ¹ is a bulky alkyl group. In the general formula [1], R ² is C ₆ H ₄ OH, C ₆ H ₄ OCH ₃ , C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OH, or C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂₎ a _n OCH _3, hexa peri hexabenzocoronene derivative according to any one of claims 1 to 6.   A nano-sized self-assembly formed in a solution comprising the hexaperihexabenzocoronene derivative according to claim 1 and one or more solvents.   The self-assembly body according to claim 8, which is in the form of a ribbon or a tube. The following general formula [2]
[Wherein R ¹ represents an alkyl group, R ² represents C ₆ H ₄ OR ³ or C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OR ³ (provided that R ³ represents a hydrogen atom or Represents an alkyl group, and n represents a positive integer.), R ⁴ represents -A-CO ₂ R ⁵ (wherein A represents a divalent hydrocarbon group, and R ⁵ represents a hydrogen atom). . ]
A hexaperihexabenzocoronene derivative represented by: In the general formula [2], R ⁴ is —C≡C—C ₆ H ₄ —COOH, —C≡C—C ₆ H ₄ —CO ₂ CH ₃ or —C≡C—C ₆ H ₄ —CO ₂ C. a ₂ H _5, hexa peri hexabenzocoronene derivative according to claim 10. In the general formula [2], ^{R 1} is an alkyl group having 10 to 30 carbon atoms, hexa peri hexabenzocoronene derivative according to claim 10 or 11. In the general formula [2], ^{R 1} is an alkyl group having 10 to 20 carbon atoms, hexa peri hexabenzocoronene derivative according to claim 10 or 11. The hexaperihexabenzocoronene derivative according to claim 10 or 11, wherein in general formula [2], R ¹ is a bulky alkyl group. In the general formula [2], R ² is C ₆ H ₄ OH, C ₆ H ₄ OCH ₃ , C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OH, or C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂₎ a _n OCH _3, hexa peri hexabenzocoronene derivative according to any one of claims 10 to 14.   A nano-sized self-assembled body formed in a solution comprising the hexaperihexabenzocoronene derivative according to claim 10 and one or more solvents.   The self-assembly body according to claim 16, which is in the form of a ribbon or a tube. The following general formula [2]
[Wherein R ¹ represents an alkyl group, R ² represents C ₆ H ₄ OR ³ or C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OR ³ (provided that R ³ represents a hydrogen atom or Represents an alkyl group, and n represents a positive integer.), R ⁴ represents -A-CO ₂ R ⁵ (where A represents a divalent hydrocarbon group, and R ⁵ represents an alkyl group). . ]
A hexaperihexabenzocoronene derivative represented by: In the general formula [2], R ⁴ is —C≡C—C ₆ H ₄ —COOH, —C≡C—C ₆ H ₄ —CO ₂ CH ₃ or —C≡C—C ₆ H ₄ —CO ₂ C. a ₂ H _5, hexa peri hexabenzocoronene derivative according to claim 18. In the general formula [2], ^{R 1} is an alkyl group having 10 to 30 carbon atoms, hexa peri hexabenzocoronene derivative according to claim 18 or 19. In the general formula [2], ^{R 1} is an alkyl group having 10 to 20 carbon atoms, hexa peri hexabenzocoronene derivative according to claim 18 or 19. The hexaperihexabenzocoronene derivative according to claim 18 or 19, wherein, in the general formula [2], R ¹ is a bulky alkyl group. In the general formula [2], R ² is C ₆ H ₄ OH, C ₆ H ₄ OCH ₃ , C ₆ H ₄ OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OH, or C ₆ H ₄ OCH ₂ CH ₂ (OCH a ₂ CH _{2) n} OCH _3, hexa peri hexabenzocoronene derivative according to any one of claims 18 to 22.   A nano-sized self-assembled body formed in a solution comprising the hexaperihexabenzocoronene derivative according to claim 18 and one or more solvents.   25. Self-assembled body according to claim 24, which is spherical or capsule-like.