Novel helisen derivatives and their precursors

Abstract

To provide a material which has a skeleton different from conventional materials and exhibits specific optical properties, and specifically, a material having a characteristic chirality and high circularly polarized light emission and a precursor thereof.SOLUTION: For example, the compound represented by the formula (II-1) in the figure is used.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to novel helicene derivatives and their precursors, and to circularly polarized luminescence materials using such derivatives. The novel helicene derivatives in the present invention have specific chirality properties and are expected to be applied, for example, to three-dimensional displays, optical communications, and the security field.

Background Art

[0002] Circularly polarized luminescence (CPL) is expected to be applied to next-generation optical information technologies such as polarized light sources for high-brightness displays and the security field. However, currently used CPL light sources are combinations of light-emitting materials that do not have CPL characteristics and emit linearly polarized light with circularly polarized transmission filters. Therefore, the manufacturing process is complex and costly, and the energy efficiency is also poor. Therefore, it is important to establish design guidelines for high-brightness and high-circularly polarized luminescence materials. From such a perspective, substances using metal ions have mainly been developed conventionally (for example, Patent Document 1), but the development of materials composed of inexpensive and environmentally friendly elements is required.

[0003] Helicene in which benzene rings are helically condensed is known as a chiral compound, and its application to circularly polarized luminescence materials is expected. For example, Patent Document 2 states that a helicene compound formed by condensing at least five aromatic rings is suitable as a charge transport material, a light-emitting material, a wavelength conversion material, etc. Further, Patent Document 3 states that azaphenylene-based compounds can be expected to be applied to organic EL elements, fluorescent materials, nonlinear optical materials, etc. Furthermore, Patent Document 4 exemplifies a helicene compound substituted with a cyano group, but its circularly polarized luminescence characteristics have not been investigated. In addition, [7]helicene in which seven benzene rings are condensed generally has a low fluorescence quantum yield, and further improvement is required for practical use, and studies such as Non-Patent Documents 1 to 2 are being advanced.

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-57367 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-195673 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-40145 [Patent Document 4] Japanese Patent Application Laid-Open No. 2018-177647 [Non-Patent Document]

[0005] [Non-Patent Document 1] Angewandte Chemie international Edition, vol. 56, 3906 - 3910, 2017 [Non-Patent Document 2] Organic Letters vol. 15, Issue 9, 2104 - 2107, 2013 [Summary of the Invention] [Problems to be Solved by the Invention]

[0006] An object of the present invention is to provide a material having a skeleton different from conventional materials and exhibiting specific optical properties. More specifically, it is to provide a material having characteristic chirality and high circularly polarized luminescence property and a precursor thereof. [Means for Solving the Problems]

[0007] As a result of intensive studies, the present inventors have found that the optically active helicene derivatives represented by General Formula (1) and General Formula (2) have specific chirality and high circularly polarized luminescence property, and have completed the present invention.

[0008] That is, the present invention relates to the optically active helicene derivatives represented by General Formula (1) and General Formula (2), or a racemic mixture thereof and their uses, and relates to the following inventions. [1] An optically active helicene derivative or a racemic mixture represented by the following general formula (1) and general formula (2). [Chemical formula] [Chemical formula] (In general formula (1) and general formula (2), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms, and adjacent R 1 and R 2 may be bonded to each other to form a ring, A and B each independently represent a substituted or unsubstituted aromatic ring having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic ring having 4 to 40 carbon atoms.) [2] The optically active helicene derivative or racemic mixture according to [1], wherein in the general formula (1) and general formula (2), A and B are each independently a structure selected from the group consisting of the following X-1, X-2, X-3, X-4 and X-5. [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [3] In the general formula (1) and general formula (2), R 1 and R 2The optically active helicene derivative or racemic mixture according to [1] or [2], each independently being a substituted or unsubstituted phenyl group. [4] A hexaaminobenzene derivative represented by the following general formula (3).

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0009] The optically active helicene derivative or racemic mixture thereof, and the hexaaminobenzene derivative of the present invention have a skeleton different from that of conventional materials and exhibit specific optical properties. Furthermore, they are materials having characteristic chirality and high circularly polarized luminescence properties, and precursors thereof. Therefore, they are extremely useful industrially.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Mode for Carrying Out the Invention

[0011] Hereinafter, the present invention will be described in detail. The optically active helicene derivatives represented by the general formula (1) and general formula (2) of the present invention are novel compounds, and the racemic mixture which is a mixture of the optically active helicene derivatives represented by the general formula (1) and general formula (2) is also a novel compound.

[0012] In the above general formula (1) and general formula (2), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms. Therefore, R 1 and R 2 may be the same as or different from these substituents, and adjacent R 1 and R 2 may be bonded to each other to form a ring.

[0013] R 1 , R 2 , R 3 and R 4Among them, specific examples of the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, 1,3-cyclohexadienyl group, 2-cyclopenten-1-yl group and the like.

[0014] Specific examples of the linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, stearyloxy group, trifluoromethoxy group and the like.

[0015] Examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms include a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthryl group, 9-anthryl group, 2-fluorenyl group, phenanthryl group, pyrenyl group, chrysenyl group, perylenyl group, picenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert-butylphenyl group, 3-tert-butylphenyl group, 2-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 2-neopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4-(2-ethylbutyl)phenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4-(2-ethylhexyl)phenyl group, 4-tert-octylphenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4-(4-methylcyclohexyl)phenyl group, 4-(4-tert-butylcyclohexyl)phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,4-diethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,6-diethylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 4,6-di-tert-butyl-2-methylphenyl group, 5-tert-butyl-2-methylphenyl group, 4-tert-butyl-2,6-dimethylphenyl group, 9-methyl-2-fluorenyl group, 9-ethyl-2-fluorenyl group, 9-n-hexyl-2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9-diethyl-2-fluorenyl group, 9,9-di-n-propyl-2-fluorenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 2-isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2-(2-ethylbutyl)oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-methoxy-1-naphthyl group, 4-methoxy-1-naphthyl group, 4-n-butoxy-1-naphthyl group, 5-ethoxy-1-naphthyl group, 6-methoxy-2-naphthyl group, 6-ethoxy-2-naphthyl group, 6-n-butoxy-2-naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 7-n-butoxy-2-naphthyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 3-ethyl-5-methoxyphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-6-ethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 4-(4-methylphenyl)phenyl group, 4-(3-methylphenyl)phenyl group, 4-(4-methoxyphenyl)phenyl group, 4-(4-n-butoxyphenyl)phenyl group, 2-(2-methoxyphenyl)phenyl group, 4-(4-chlorophenyl)phenyl group, 3-methyl-4-phenylphenyl group, 3-methoxy-4-phenylphenyl group, terphenyl group, 3,5-diphenylphenyl group, 10-phenylanthryl group, 10-(3,5-diphenylphenyl)-9-anthryl group, 9-phenyl-2-fluorenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 2-bromophenyl group, 4-chloro-1-naphthyl group, 4-chloro-2-naphthyl group, 6-bromo-2-naphthyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,5-dibromophenyl group, 2,4,6-trichlorophenyl group, 2,4-dichloro-1-naphthyl group, 1,6-dichloro-2-naphthyl group, 2-fluoro-4-methylphenyl group, 2-fluoro-5-methylphenyl group, 3-fluoro-2-methylphenyl group, 3-fluoro-4-methylphenyl group, 2-methyl-4-fluorophenyl group, 2-methyl-5-fluorophenyl group, 3-methyl-4-fluorophenyl group, 2-chloro-4-methylphenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2-methyl-3-chlorophenyl group, 2-methyl-4-chlorophenyl group, 3-chloro-4-methylphenyl group, 3-methyl-4-chlorophenyl group, 2-chloro-4,Examples include, but are not limited to, 6-dimethylphenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoro-4-ethoxyphenyl group, 2-fluoro-6-methoxyphenyl group, 3-fluoro-4-ethoxyphenyl group, 3-chloro-4-methoxyphenyl group, 2-methoxy-5-chlorophenyl group, 3-methoxy-6-chlorophenyl group, 5-chloro-2,4-dimethoxyphenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 3,5-bis(trifluoromethyl)phenyl group, etc.

[0016] The substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms is an aromatic ring group containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom. For example, heteroaryl groups such as 4-quinolyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 3-furyl group, 2-furyl group, 3-thienyl group, 2-thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group can be mentioned, but are not limited thereto.

[0017] Furthermore, for adjacent R 1 and R 2 , they may be bonded to each other to form a ring. Specific examples of the case where R 1 and R 2 are bonded to each other to form a ring include, for example, the examples shown in the following (Y-1), (Y-2), and (Y-3), but are not limited thereto.

Chemical formula

Chemical formula

Chemical formula

[0018] In the above general formula (1) and general formula (2), A and B which have a structure having an aromatic ring or an aromatic heterocycle each independently represent a substituted or unsubstituted aromatic ring having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocycle having 4 to 40 carbon atoms. A and B may be the same or different from each other, but considering the complexity of synthesis, it is preferable that they are the same.)

[0019] The aromatic ring is not particularly limited, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a triphenylene ring, a pyrene ring, a biphenyl, a terphenyl, etc. can be mentioned. The aromatic heterocycle is not particularly limited, and specifically, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a thiophene ring, a furan ring, a benzoxazole ring, a benzothiazole ring, etc. can be mentioned.)

[0020] Furthermore, it is more preferable that A and B which have a structure having an aromatic ring or an aromatic heterocycle in the general formula (1) and general formula (2) are a structure selected from the group consisting of the following X-1, X-2, X-3, X-4 and X-5.)

[0021]

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0022] General formulas (1) and (2) have the chirality of the helix depending on the overlapping manner of A and B having an aromatic ring or an aromatic heterocycle. When having a right-handed helical structure as shown in general formula (1), it has P helicity, and when having a left-handed helical structure as shown in general formula (2), it has M helicity, respectively. Furthermore, specific structural formulas of general formulas (1) and (2) are exemplified below, but the compounds are not limited thereto.

[0023] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

[0024] The hexaaminobenzene derivative represented by general formula (3) of the present invention is a novel compound and is an important precursor of the optically active helicene derivative and the racemic mixture represented by general formulas (1) and (2).

[0025] [Chemical formula] (R in general formula (3) 1 , R 2 , R 3 and R 4is, independently of each other, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 40 carbon atoms, and adjacent R 1 and R 2 may be bonded to each other to form a ring, A and B each independently represent a substituted or unsubstituted aromatic ring having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocycle having 4 to 40 carbon atoms.) In the above general formula (3), R 1 , R 2 , R 3 and R 4 are the same as those exemplified for R 1 , R 2 , R 3 and R 4 in general formula (1) and general formula (2).

[0026] Furthermore, specific structural formulas of the general formula (3) are exemplified below, but the compounds are not limited thereto.

[0027]

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0028] <Method for Producing Optically Active Helicene Derivatives and Racemic Mixture According to the Present Invention> The optically active helicene derivatives and racemic mixtures represented by General Formula (1) and General Formula (2) are not particularly limited, but can be produced from the steps shown below. That is, it consists of Step 1 (synthesis step of a precursor (tetrapyrrolodihalobenzene derivative)), Step 2 (synthesis step of a hexaaminobenzene derivative represented by General Formula (3)), Formula (1), Step 3 (synthesis step of a racemate which is a mixture of General Formula (1) and General Formula (2) from the hexaaminobenzene derivative represented by General Formula (3)), and Step 4 (optical resolution step of each optically active form from the mixture of General Formula (1) and General Formula (2)).

[0029] Step 1) Synthesis step of a precursor (tetrapyrrolodihalobenzene derivative) To a reaction vessel equipped with a reflux device, a pyrrole derivative which may have a substituent at the 3,4-position as a reaction reagent and a base such as sodium hydride are added, and after setting an inert gas atmosphere such as nitrogen, a solvent such as dimethylformamide is added, and the reaction is carried out by stirring or the like. The reaction temperature is not particularly limited as long as the target precursor can be obtained, and the pressure during the reaction can be selected from any of under pressure, normal pressure, and reduced pressure. As the reaction temperature, for example, it is preferably about -30°C to 50°C. The reaction time depends on the reactivity of the reaction reagent, but usually it may be reacted for 1 minute to 1 day, preferably 5 minutes to 10 hours, and more preferably 10 minutes to 2 hours. In a reaction vessel different from the above, 1,2-dihalogeno-3,4,5,6-tetrafluorobenzene is dissolved in a solvent such as dimethylformamide and added to the above reaction vessel under an inert gas atmosphere such as nitrogen or in an open system. The halogen atom of the above compound can be selected from bromine or iodine atoms. The reaction time depends on the reactivity of the reaction raw materials, but usually it may be reacted for 10 minutes to 3 days, preferably 30 minutes to 1 day, and more preferably 1 hour to 1 day. As the reaction temperature, for example, it is preferably about -80°C to 50°C, and more preferably -10°C to 30°C for both reactivity and selectivity. After the reaction is completed, a solvent in which the reaction product can be dissolved, such as water, may be added, and further extraction may be performed with a water-insoluble solvent such as ethyl acetate. Further, the organic layer may be washed according to a known formulation, for example, washed with water and saturated brine, and then dried with a desiccant such as sodium sulfate, and concentrated with a commonly used apparatus such as an evaporator to obtain a precursor. The obtained precursor can be confirmed for its structure, physical properties, degree of purification, etc. by analysis by methods known in the art such as elemental analysis, NMR, and mass spectrometry.

[0030] Step 2) Synthesis step of hexaaminobenzene derivative To a reaction vessel equipped with a reflux device, a reaction reagent such as indole and a base such as sodium hydride are added, and after setting an inert gas atmosphere such as nitrogen, a solvent such as dimethylformamide is added, and the mixture is stirred and reacted. The reaction temperature is not particularly limited as long as the target precursor can be obtained, and the pressure during the reaction can be selected from under pressure, normal pressure, and reduced pressure. As the reaction temperature, for example, it may be about -50°C to 50°C. The reaction time depends on the reactivity of the reaction reagent, but usually it may be reacted for 1 minute to 1 day, preferably 5 minutes to 10 hours, and more preferably 10 minutes to 2 hours. In a reaction vessel different from the above, the above-mentioned precursor is dissolved in a solvent such as dimethylacetamide, and added to the above reaction vessel under an inert gas atmosphere such as nitrogen or in an open system. The reaction time depends on the reactivity of the reaction raw materials, but usually it may be reacted for 10 minutes to 3 days, preferably 30 minutes to 1 day, and more preferably 1 hour to 1 day. As the reaction temperature, for example, it may be about 0°C to 100°C, and for the sake of both reactivity and selectivity, it is more preferable to set it at 10°C to 50°C. After the reaction is completed, a solvent in which the reaction product can be dissolved, such as water, may be added, and further extraction may be performed with a water-insoluble solvent such as ethyl acetate. Further, the organic layer may be washed according to a known formulation, for example, washed with water and saturated brine, and then dried with a desiccant such as sodium sulfate, and concentrated with a commonly used apparatus such as an evaporator to obtain a hexaaminobenzene derivative. The obtained hexaaminobenzene derivative can have its structure, physical properties, degree of purification, etc. confirmed by analysis using methods known in the art, such as elemental analysis, NMR, and mass spectrometry.

[0031] Step 3) Step of synthesizing a racemate which is a mixture of general formula (1) and general formula (2) The step of synthesizing the racemate which is a mixture of general formula (1) and general formula (2) of the present invention is produced by an oxidative coupling reaction of the above-mentioned hexaaminobenzene derivative. Specific methods of oxidative coupling include methods using an oxidizing agent catalyst, which are preferable as inexpensive and easily obtainable means. Examples of these oxidizing agent catalysts include compounds such as aluminum chloride, iron chloride, molybdenum chloride, tungsten chloride, and tin chloride. Into a reaction vessel equipped with a reflux device, an oxidizing agent catalyst such as iron chloride is added together with reaction reagents such as the above-mentioned hexaaminobenzene derivative and a solvent such as nitromethane or dichloromethane, and the mixture is stirred and reacted. The reaction temperature is not particularly limited as long as the target racemate can be obtained, and the pressure during the reaction can be selected from any of under pressure, normal pressure, and reduced pressure. For example, the reaction temperature may be about 0°C to 100°C. The reaction time depends on the reactivity of the reaction reagents, but usually, it may be reacted for 1 minute to 1 day, preferably 5 minutes to 10 hours, and more preferably 10 minutes to 5 hours. After completion of the reaction, the solid matter is filtered off by filtration or the like and concentrated using a commonly used device such as an evaporator. Further, purification is preferably carried out using commonly used purification means such as silica gel column chromatography and a solvent for the mobile phase such as methylene chloride / n-hexane. The obtained racemate can have its structure, physical properties, degree of purification, etc. confirmed by analysis using methods known in the art, such as elemental analysis, NMR, and mass spectrometry.

[0032] Step 4) Step of optically resolving each optically active form from the mixture of general formula (1) and general formula (2) It can be produced by optically resolving a racemate which is a mixture of the general formula (1) and the general formula (2). As the optical resolution method, for example, by using a column for high performance liquid chromatography for optical isomer separation, it can be separated into an (R) optical isomer and an (S) optical isomer. The column for high performance liquid chromatography for optical isomer separation is not particularly limited, but is generally commercially available. For example, CHIRALPAK IC, CHIRALPAK IA, CHIRALPAK AD-H or CHIRALPAK OD-H manufactured and sold by Daicel Chemical Industries, Ltd. etc. can be used. Examples of the solvent used in the optical resolution include aliphatic hydrocarbons such as hexane or heptane, alcohols such as methanol, ethanol, propanol, 2-propanol or butanol, halogenated hydrocarbons such as dichloromethane or chloroform, ethers such as diethyl ether, 1,2-dimethoxyethane, diisopropyl ether, tetrahydrofuran or dioxane, nitriles such as acetonitrile, amines such as diethylamine, acetic acid, trifluoroacetic acid, water, or a mixed solvent thereof. The temperature and time in the optical resolution can vary widely. Generally, the temperature is -20 to 60 °C, preferably 5 to 50 °C. The time is 0.05 hour to 50 hours, preferably 0.1 hour to 5 hours.

Examples

[0033] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples at all.

[0034] In addition, the analytical instruments and measurement methods used in this example are listed below. [Elemental analysis] Elemental analyzer: MICRO CORDER JM10T manufactured by J Science Lab [Mass spectrometry] Mass spectrometer: JMS-700V type manufactured by JEOL Ltd. (FAB-MS analysis) GC-2010 manufactured by Shimadzu Corporation (DI-MS analysis) JMS-S3000 manufactured by JEOL Ltd. (LDI analysis) [NMR measurement] Measuring device: JNM-AL400S manufactured by JEOL Ltd. [CD measurement] Measuring device: J-820 manufactured by JASCO Corporation [Absorption spectrum measurement] Measuring device: V-570 manufactured by JASCO Corporation [Emission spectrum measurement] Measuring device: RF-6000 manufactured by Shimadzu Corporation [Absolute quantum yield measurement] Measuring device: C-9920 manufactured by Hamamatsu Photonics K.K. [CPL measurement] Measuring device: CPL-200 manufactured by JASCO Corporation

[0035] [Synthesis Example 1] Synthesis of compound (I-1) [Chemical formula] To a 100 mL three-necked flask equipped with a reflux device, 810 mg (60% mineral oil dispersion, 20.3 mmol) of sodium hydride was added, and after purging with nitrogen, a dehydrated DMF solution (30 mL) of 4.80 g (13.5 mmol) of 3,4-di-(4-trifluoromethylphenyl)-1H-pyrrole was added dropwise at 0 °C with stirring, and the mixture was stirred for 30 minutes. This solution was added dropwise to a dehydrated DMF solution (15 mL) of 0.464 mL (3.37 mmol) of 1,2-dibromo-3,4,5,6-tetrafluorobenzene prepared in another reaction vessel at -10 °C over 20 minutes, and the mixture was stirred for 2 hours. After adding water to stop the reaction, the mixture was extracted with ethyl acetate, and the organic layer was washed with water and saturated brine. Then, it was dried using sodium sulfate and concentrated with an evaporator. The residue was purified by silica gel column chromatography (methylene chloride / n-hexane) to obtain 5.24 g of a white solid of compound (I-1) in a yield of 94%.

[0036] The analysis results were as follows. 11H-NMR (CDCl3, 25 °C, 400 MHz) δ 7.55 (d, J = 8.2 Hz, 8H, CF3Ph), 7.46 (d, J = 8.2 Hz, 8H, CF3Ph), 7.28 (d, J = 8.1 Hz, 2H, CF3Ph), 7.06 (d, J = 8.1 Hz, 8H, CF3Ph), 6.89 (s, 4H, Py-α), 6.47 (s, 4H, Py-α) 13 13C-NMR (CDCl3, 25 °C, 100 MHz) δ 137.64, 137.39, 137.05, 134.07, 129.73, 129.63, 129.30, 129.08, 128.98, 128.48, 128.15, 127.30, 125.69, 125.34, 125.06, 122.76, 122.63, 122.00, 120.81, 120.06, 119.90 19 19F-NMR (CDCl3, 376 MHz) δ -62.37, -62.80 MS (FAB-MS) m / z 1649 ([M + 3] + ) Anal. Calcd. for C78H40Br2F24N4·C6H14: C 58.15%, H 3.14%, N 3.23% Found: C 58.25%, H 3.20%, N 3.27%

[0037] Also, 1 The 1H-NMR measurement chart is shown in Figure 1.

[0038] [Example 1] Synthesis of Compound (II-1)

Chemical Structure

[0039] The analysis results were as follows. 1 H-NMR (tetrachloroethane-d2, 100 °C, 400 MHz) δ 7.59 (d, J = 8.4 Hz, 1.1H, Ind), 7.55 (d, J = 8.0 Hz, 8H, CF3Ph), 7.53 (d, J = 8.2 Hz, 0.9H, Ind), 7.46 (d, J = 7.8 Hz, 8H, CF3Ph), 7.22 (d, J = 8.0 Hz, 8H, CF3Ph), 7.20 - 7.05 (m, 5H, Ind), 6.94 (t, J = 7.7 Hz, 1H, Ind), 6.91 - 6.87 (m, 8H, CF3Ph), 6.78 (s, 2.3H, Py-α), 6.77 (s, 1.7H, Py-α), 6.69 (br s, 0.9H, Ind-α), 6.55 (br s, 1.1H, Ind-α), 6.36 (s, 2.3H, Py-α), 6.35 (s, 1.7H, Py-α), 2.26 (s, 2.6H, Ind-CH3), 2.22 (s, 3.4H, Ind-CH3) MS (FAB-MS) m / z 1749 ([M+1] + )

[0040] Also, 1 The H-NMR measurement charts are shown in Figure 2 respectively.

[0041] [Example 2] Synthesis of racemic compound (III-1)

Chemical formula

[0042] The analysis results were as follows. 1 H-NMR (tetrachloroethane-d2, 100 °C, 400 MHz) δ 7.61 (d, J = 8.5 Hz, 4H, CF3Ph), 7.52 (d, J = 7.8 Hz, 4H, CF3Ph), 7.39 (d, J = 8.4 Hz, 2H, Ind), 7.10 - 7.00 (m, 12H, CF3Ph), 6.96 (t, J = 7.5 Hz, 2H, Ind), 6.90 (d, J = 8.5 Hz, 4H, CF3Ph), 6.81 - 6.66 (m, 10H, CF3Ph + Ind), 6.50 (d, J = 8.4 Hz, 2H, Ind), 1.76 (s, 6H) MS (MALDI) calcd. for C96H46F24N6: 1738.3401, Found: 1738.3343

[0043] Also, 1 The H-NMR measurement chart is shown in Figure 3, and the LDI TOF-MS measurement chart is shown in Figure 4, respectively.

[0044] When compound (III-1) was analyzed by high performance liquid chromatography (HPLC) using Daicel chiralpak IA and a mixed solution of hexane / chloroform / ethanol (95 / 3 / 2 = v / v / v), it was confirmed to be a racemic compound composed of a mixture of compound (III-1P, elution time 27 minutes) and compound (III-1M, elution time 29 minutes). The analysis chart is shown in Figure 5. Furthermore, the ultraviolet-visible absorption spectrum and emission spectrum (excitation light: 430 nm) of the methylene chloride solution of compound (III-1) are shown in Figure 6. The fluorescence quantum yield Φ FL = 0.10, and the fluorescence lifetime = 4.7 ns. Also, the CD and CPL of compound (III-1P) and compound (III-1M) obtained by optical resolution of compound (III-1) by high performance liquid chromatography were measured in a methylene chloride solution at room temperature and are shown in Figures 7 and 8 (excitation light: 370 nm). By changing the chirality, circularly polarized luminescence with different signs was observed, and the anisotropy factor (glum) was 3.7×10 -2 and was a high value, indicating that it has excellent circularly polarized light characteristics.

Industrial Applicability

[0045] According to the helicene derivative of the present invention, it has unique chirality properties, and for example, applications to three-dimensional displays, optical communications, and the security field can be expected, and it can be industrially utilized.

Claims

1. An optically active helicene derivative or a racemic mixture represented by the following general formula (1) and general formula (2). 【Chemical 34】 【Chemical 35】 (In general formula (1) and general formula (2), R １ 、 R ２ 、 R ３ and R ４ each independently represents a hydrogen atom, or a substituted or unsubstituted phenyl group, A and B each independently represent a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring.)

2. The optically active helicene derivative or racemic mixture according to Claim 1, wherein in the above general formula (1) and general formula (2), A and B are each independently a structure selected from the group consisting of the following X-1 and X-2. 【Chemical 36】 【Chemical 37】

3. An optically active helicene derivative or a racemic mixture thereof represented by the following formula. 【Chemical 19】 【Chemical 20】 【Chemical 21】 【Chemical 24】

4. An optically active helicene derivative or a racemic mixture thereof represented by the following formula (4) or the following formula (5). 【Chemical Formula 42】 【Chemical 43】

5. A hexaaminobenzene derivative represented by the following general formula (3). 【Chemical 41】 (In general formula (3), R １ 、R ２ 、R ３ 、R ４ 、A and B, which are the same substituents as in claim 1.)

6. A hexaaminobenzene derivative represented by the following formula. 【Chemical 26】 【Chemical 27】 【Chemical Formula 28】 【Chemical Formula 31】

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