JP7044580B2 - New aromatic compounds - Google Patents

Description

The present invention relates to a novel aromatic compound in which an arbitrary aromatic ring is substituted with a pyrrolidine group having an amino group and a chirality group, and a circularly polarized light emitting material using a derivative thereof. The novel aromatic compound in the present invention has a specific chirality property, and is expected to be applied to, for example, three-dimensional displays, optical communications, and security fields.

Circularly polarized light emission (CPL) is expected to be applied to next-generation optical information technologies such as deflection light sources for high-brightness displays and security fields. However, the CPL light source currently used is a combination of a light emitting material that does not have CPL characteristics and emits linearly polarized light and a circularly polarized light transmission filter, so that the manufacturing process is complicated and costly, and energy efficiency is poor. .. Therefore, it is important to establish design guidelines for high-brightness, high-circularly polarized light-emitting materials. From this point of view, substances using metal ions have been mainly developed, but there is a demand for the development of materials composed of elements that are inexpensive and have a low environmental load.

For example, focusing on the propeller chirality (axis isomer) of hexaphenylbenzene, an example in which the chirality is controlled by introducing a chiral alkoxy group in the outer peripheral portion has been reported (for example, Non-Patent Document 1). However, the circularly polarized light emission characteristics have not been investigated.

Further, there has been reported an example in which the outer peripheral portion of borondipyrromethene known as a luminescent material is substituted with the same phenyl group to induce chirality and circularly polarized light emission is observed (for example, Non-Patent Document 2). ). However, the observed luminescence is due to the dimerization of the dye in a chiral orientation in the methylcyclohexane solvent at very low temperatures (−120 ° C.). That is, it is not a circularly polarized light emission characteristic based on propeller chirality control in a single molecule.

On the other hand, carbazoles have high luminous efficiency and a large π plane, and are therefore considered to be preferable to the above-mentioned phenyl group in controlling propeller chirality (axis isomer), but there are reports of hexacarbazolylbenzene. Only, chirality control is not performed (for example, Non-Patent Document 3).

The Journal of Physical Chemistry Letters, vol. 7, 783-788, 2016 The Journal of Physical Chemistry Letters, vol. 8, 42-48, 2017 Chemical Physics Letters, vol. 289, 13-18, 1998

An object of the present invention is to provide a material having a skeleton different from that of a conventional material and exhibiting specific optical properties. More specifically, it is an object of the present invention to provide a material having characteristic chirality and having high circularly polarized light emission.

As a result of diligent studies, the present inventors have found that the aromatic compound represented by the general formula (1) has characteristic chirality and high circularly polarized light emission, and completes the present invention. I arrived. That is, the present invention relates to an aromatic compound represented by the following general formula (1) and its use.

(In the formula, X is a structure having one or more aromatic rings.
R ¹ and R ² are independently hydrogen atoms, a linear or branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear or branched or cyclic alkoxy group having 1 to 18 carbon atoms, and 6 carbon atoms. It is a substituted or unsubstituted aryl group of ~ 40, or a substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms, and R ¹ and R ² may be bonded to each other to form a ring, and n is X. It is the maximum integer that can be bonded to the carbon atom of, and m is an integer of 1 or more.
R ³ is a linear or branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear or branched or cyclic alkoxy group having 1 to 18 carbon atoms, may contain a hetero atom, and is bonded to a pyrrolidine ring. Is optically active, o is an integer of 1 to 3, and R ⁴ is a hydrogen atom, a carbonyl group, or a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms. )

Further, the present invention relates to the above aromatic compound having a structure in which X having an aromatic ring in the general formula (1) is selected from the group consisting of the following X-1 to X-6.

Further, the present invention relates to the above aromatic compound in which NR ¹ R ² in the general formula (1) is represented by the following general formula (2).

(In the formula, R ⁵ and R ⁶ are independently hydrogen atoms, linear or branched or cyclic alkyl groups having 1 to 18 carbon atoms, and linear or branched or cyclic alkoxy groups 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 5 to 40 carbon atoms, and p and q are integers of 1 or more.)
Further, the present invention relates to the above aromatic compound represented by the following formula (3) or (4).

Hereinafter, the present invention will be described in detail.
The aromatic compound represented by the general formula (1) of the present invention is a novel compound.
In the above general formula (1), X is a structure having an arbitrary aromatic ring, that is, one or a plurality of aromatic rings. The aromatic ring is not particularly limited, but specifically, for example, a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a phenanthrene ring, a chrysen ring, a triphenylene ring, a tetraphenene ring, and a pyrene. Examples thereof include a ring, a picene ring, a pentaphene ring, a perylene ring, a helisene ring, a coronene ring, biphenyl, terphenyl, and tetraphenyl.

Further, it is preferable that X, which is a structure having an aromatic ring in the general formula (1), is a structure selected from the group consisting of the following X-1 to X-6.

In the general formula (1), R ¹ and R ² are independently hydrogen atoms, linear or branched or cyclic alkyl groups having 1 to 18 carbon atoms, and linear or branched or cyclic groups having 1 to 18 carbon atoms. Alkoxy group, substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms is preferable. Therefore, R ¹ and R ² may be the same as or different from these substituents, respectively.

Further, in the general formula (1), n is the maximum integer that can be bonded to the carbon atom of X, that is, the maximum number that X, which is a structure having an aromatic ring, can be bonded to a substituent, and m is 1 or more. It is an integer. Therefore, as shown in the general formula (1), the difference nm from m, which is the number of substituents having n, R ³ and R ⁴ bonded to X, is the substituent having R ¹ and R ² . Is the number to combine with X.

In R ¹ and R ² , the linear or branched or cyclic alkyl group having 1 to 18 carbon atoms is specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, or a 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- Butyl group and the like can be mentioned.

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

Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-anthryl group, a 9-anthryl group, a 2-fluorenyl group, and a phenanthryl. Group, pyrenyl group, chrysenyl group, perylenel group, pisenyl 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- Naftyl 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-methoxy Phenyl 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-isopentyloxy Phenyl 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 -Methone-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 Enyl 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, turphenyl 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-4,6-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 The basics can be mentioned, but the present invention is not limited to these.

The substituted or unsubstituted heteroaryl group having 5 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, and is, for example, a 4-quinolyl group and 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 Examples thereof include, but are not limited to, a heterocyclic group such as a group, a 2-benzothiazolyl group and a 2-benzoimidazolyl group.

Further, R ¹ and R ² may be combined with 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 (1-1) to (1-4), but are limited thereto. is not it.

(In the formula, R ⁵ to R ⁹ are independently hydrogen atoms, linear or branched or cyclic alkyl groups having 1 to 18 carbon atoms, and linear or branched or cyclic alkoxy groups 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 5 to 40 carbon atoms, and p, q, r, s, t are integers of 0 or 1 or more. be.)

In the general formula (1), R ³ is a linear or branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear or branched or cyclic alkoxy group having 1 to 18 carbon atoms, and contains a heteroatom. Often, specific examples of R ³ include, but are not limited to, the same groups described in the specific examples of R ¹ and R ² described above.

Further, in the general formula (1), the bond between R ³ and the pyrrolidine ring has optical activity, that is, R ³ binds to the pyrrolidine ring in a state of having chirality. Further, in the general formula (1), o is an integer of 1 to 3, and ^R4 is a hydrogen atom or a carbonyl group or an arbitrary substituent, for example, a linear or branched or cyclic alkyl group having 1 to 18 carbon atoms. , Preferably a linear or branched or cyclic alkyl group having 1 to 6 carbon atoms.

More specifically, for example, the structural formulas shown in the following (2-1) to (2-6) can be mentioned, but the structural formulas are not necessarily limited thereto.

The specific structural formula of the general formula (1) will be further illustrated below, but the present invention is not limited to these compounds.

<Method for producing aromatic compound according to the present invention>
The aromatic compound represented by the general formula (1) is not particularly limited, but can be produced by the steps shown below. That is, the aromatic compound can be produced by step 1 (the step of synthesizing the precursor (optical isomer (R) or (S))) and step 2 (the step of producing the aromatic compound).

Step 1) Synthesis of precursor (optical isomer (R) or (S)) In a reaction vessel, a raw material for precursor synthesis such as (R) -2- (methoxymethyl) pyrrolidine is dissolved in a solvent such as THF. , Add in an inert gas atmosphere such as nitrogen. The reaction temperature is not particularly limited as long as the target aromatic compound and its precursor can be obtained, and the pressure at the time of reaction can be selected from under pressure, under normal pressure, and under reduced pressure. When the reaction product is easily decomposed by heat, it is preferable to cool it to a low temperature, for example, −100 ° C. to 0 ° C. A solution prepared by dissolving n-butyllithium or the like as a base in n-hexane or the like is added thereto and reacted. The amount to be added may be any amount as long as the reaction raw material can be sufficiently subjected to the reaction. The reaction time depends on the reactivity of the reaction raw material, but usually the reaction may be carried out for 1 minute to 1 day, preferably 5 minutes to 10 hours, more preferably 10 minutes to 2 hours, and the reaction may be carried out with or without stirring. You can also do it.

A raw material for precursor synthesis such as hexafluorobenzene is mixed with a solvent such as THF in a reaction vessel different from the above, and added to the above reaction vessel in an atmosphere of an inert gas such as nitrogen or in an open system. The reaction time depends on the reactivity of the reaction raw material, but usually the reaction may be carried out for 10 minutes to 2 days, preferably 1 hour to 10 hours, more preferably 2 hours to 5 hours, and the reaction may be carried out with or without stirring. You can also do it.

After completion of the reaction, a solvent capable of dissolving the reaction product, for example, water may be added, and the mixture may be further extracted with a non-aqueous solvent such as ethyl acetate. Further, the organic layer can be washed with a known formulation, for example, with water and saturated brine, dried with a desiccant such as sodium sulfate, and concentrated with a commonly used device such as an evaporator to obtain a precursor. ..

The obtained precursor can be analyzed by a method known in the art such as elemental composition, properties such as oil, NMR, mass spectrometry, etc., and the degree of purification, structure, physical properties, etc. can be confirmed.

Step 2) Production of aromatic compound A reaction reagent such as carbazole and a base such as calcium hydride are added to a reaction vessel equipped with a reflux device to create an inert gas atmosphere such as nitrogen, and then a solvent such as dimethylacetamide is added. React by stirring or the like. The reaction temperature is not particularly limited as long as the target aromatic compound and its precursor can be obtained, and the pressure at the time of reaction can be selected from under pressure, under normal pressure, and under reduced pressure. The reaction temperature may be, for example, about 0 ° C to 50 ° C. The reaction time depends on the reactivity of the reaction reagent, but usually the reaction may be carried out for 1 minute to 1 day, preferably 5 minutes to 10 hours, more preferably 10 minutes to 2 hours, and the reaction may be carried out with or without stirring. You can also do it.

The precursor is dissolved in a solvent such as dimethylacetamide in a reaction vessel different from the above, and added to the reaction vessel in an atmosphere of an inert gas such as nitrogen or in an open system. The reaction time depends on the reactivity of the reaction raw material, but usually the reaction may be carried out for 1 hour to 3 days, preferably 5 hours to 1 day, more preferably 10 hours to 1 day, and the reaction may be carried out with or without stirring. You can also let it. The reaction temperature may be, for example, about 100 ° C to 200 ° C.

After completion of the reaction, the reaction vessel is cooled, the reaction solvent is distilled off, and a commonly used purification means such as silica gel column chromatography is used, and a commonly used mobile phase solvent such as methylene chloride / n-hexane is used. It is good to purify.
The obtained aromatic compound, which is the target product, can be analyzed by a method known in the art such as elemental composition, properties such as oil, NMR, mass spectrometry, etc., and the degree of purification, structure, physical properties, etc. can be confirmed.

Since the novel aromatic compound represented by the general formula (1) according to the present invention has a skeleton different from that of the conventional material and characteristic chirality, it is possible to exhibit high circularly polarized light emission.

CD spectra (top: (R) -2 and (S) -2)) and absorption spectra (bottom: (R) -2) (methylene chloride solution, room temperature) shown in Examples, and the horizontal axis (X-axis). ) Is the wavelength (nm), and the vertical axis (Y-axis) is circular dichroism (ellipticity) on the upper side and absorbance (Norm.Abs.) On the lower side. CPL spectra (top: (R) -2 and (S) -2)) and emission spectra (bottom: (R) -2) (methylene chloride solution (1.16 × 10 ^-4 M), shown in Examples, Room temperature. Excitation light: 290 nm), the horizontal axis (X axis) is the wavelength (nm), and the vertical axis (Y axis) is CPL (Intensity) on the upper side and emission intensity (Intensity) on the lower side.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

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 (FAB-MS analysis)
Shimadzu GC-2010 (DI-MS analysis)
[NMR measurement] Measuring device: JNM-AL400S manufactured by JEOL Ltd.
[CD measurement] Measuring device: J-820 manufactured by JASCO Corporation
[CPL measurement] Measuring device: JASCO CPL-200
[Absorption spectrum measurement] Measuring device: JASCO V-570
[Measurement of emission spectrum] Measuring device: Hitachi F-7000

Synthesis Example 1 (R) -1 synthesis

0.53 mL (4.32 mmol) of (R) -2- (methoxymethyl) pyrrolidine and 20 mL of THF were added to a 100 mL three-mouth reaction vessel under a nitrogen atmosphere, and the reaction solution was cooled to -70 oC. After cooling, 3.10 mL of n-butyllithium / n-hexane solution (n-BuLi content 4.96 mmol) was added dropwise, and the mixture was stirred as it was for 20 minutes.

A mixed solution of 2.20 mL (19.0 mmol) of hexafluorobenzene and 10 mL of THF was prepared in another reaction vessel, and the mixed solution was added dropwise to the reaction solution cooled to -70 oC, and the mixture was stirred for 4 hours. After the stirring was completed, water was added and the mixture was extracted with ethyl acetate, and the organic layer was washed with water and saturated brine. Then, it was dried over sodium sulfate and concentrated on an evaporator to obtain 872 mg (3.10 mmol, yield 72 mol% from (R) -2- (methoxymethyl) pyrrolidine) of (R) -1. ..

The analysis results are as follows.
Mol. Form .: C ₁₂ H ₁₂ F ₅ NO (Exact Mass: 281.08, Mol. Wt .: 281.23)
Appearance: Oil
¹ H NMR (CDCl ₃ ) δ 4.04-3.96 (m, 1H), 3.66-3.38 (m, 1H), 3.33-3.14 (m, 3H), 3.24 (s, 3H), 2.18-2.09 (m, 1H) , 2.02-1.83 (m, 2H), 1.82-1.72 (m, 1H)
MS (DI-MS): 236.10 (M-45 ⁺ )

Example 1 Synthesis of (R) -2

To a 100 mL three-mouth reaction vessel equipped with a reflux device, add 1.610 g (9.63 mmol) of carbazole and 1.232 g (29.3 mmol) of calcium hydride, replace with nitrogen, add 60 mL of dimethylacetamide, and add 60 mL of dimethylacetamide for 20 minutes at room temperature. Stirred.

In another reaction vessel, prepare a dimethylacetamide solution (20 mL) of (R) -1 270 mg (0.960 mmol) prepared by the same method as in Synthesis Example 1, add this solution to the reaction vessel, and add 19 at 160 oC. Stir for hours. After cooling to room temperature, the solvent was distilled off, and the residue was purified by silica gel column chromatography (methylene chloride / n-hexane). (R) -2 491 mg (0.483 mmol, yield 50 mol from (R) -1). %) Was obtained.

The analysis results are as follows.
Mol. Form .: C ₇₂ H ₅₂ N ₆ O (Exact Mass: 1016.42, Mol. Wt .: 1017.25)
Appearance: White solid
^{1 1} H NMR (CDCl ₃ ) δ 7.84 (d, J = 7.6 Hz, 2H), 7.60-7.53 (m, 4H), 7.32-7.14 (m, 14H), 6.87-6.48 (m, 20H), 3.38 (dd) , J = 8.4, 7.0 Hz, 1H), 3.01-2.96 (m, 1H), 2.80 (t, J = 8.4 Hz, 1H), 2.17-2.08 (m, 1H), 1.56-1.48 (m, 1H), 1.13-1.04 (m, 1H), 0.97-0.77 (m, 2H), 0.57-0.44 (m, 1H)
MS (FAB-MS): 1018 (MH ⁺ ), 972 (MH-45 ⁺ )
Anal. Calcd. For C ₇₂ H ₅₂ N ₆ O: C, 85.01; H, 5.15; N, 8.26
Found; C, 85.04; H, 5.39; N, 8.30

Synthesis Example 2 (S) -1 synthesis

0.21 mL (1.69 mmol) of (S) -2- (methoxymethyl) pyrrolidine and 5 mL of THF were added to a 50 mL two-mouth reaction vessel under a nitrogen atmosphere, and the reaction solution was cooled to -70 oC. After cooling, 1.16 mL of n-butyllithium / n-hexane solution (n-BuLi content 1.86 mmol) was added dropwise, and the mixture was stirred as it was for 20 minutes.

A mixed solution of 0.78 mL (6.76 mmol) of hexafluorobenzene and 7 mL of THF was prepared in another reaction vessel, and the mixed solution was added dropwise to the reaction solution cooled to -70 oC, and the mixture was stirred for 4 hours. After the stirring was completed, water was added and the mixture was extracted with ethyl acetate, and the organic layer was washed with water and saturated brine. Then, it was dried over sodium sulfate and concentrated on an evaporator to obtain (S) -1 264 mg (0.939 mmol, yield 56 mol% from (S) -2- (methoxymethyl) pyrrolidine).

The analysis results are as follows.
Mol. Form .: C ₁₂ H ₁₂ F ₅ NO (Exact Mass: 281.08, Mol. Wt .: 281.23)
Appearance: Oil
¹ H NMR (CDCl ₃ ) δ 4.04-3.96 (m, 1H), 3.66-3.58 (m, 1H), 3.34-3.12 (m, 3H), 3.25 (s, 3H), 2.18-2.08 (m, 1H) , 2.01-1.84 (m, 2H), 1.82-1.71 (m, 1H)
MS (DI-MS): 236.10 (M-45 ⁺ )

Example 2 Synthesis of (S) -2

Add 1.193 g (7.13 mmol) of carbazole and 0.934 g (22.2 mmol) of calcium hydride to a 100 mL three-mouth reaction vessel equipped with a reflux device, replace with nitrogen, add 40 mL of dimethylacetamide, and add 20 at 90 oC. Stir for minutes.

In another reaction vessel, prepare a dimethylacetamide solution (20 mL) of (S) -1 201 mg (0.715 mmol) prepared by the same method as in Synthesis Example 2, add this solution to the reaction vessel, and add 14 at 160 oC. Stir for hours. After cooling to room temperature, the solvent was distilled off, and the residue was purified by silica gel column chromatography (methylene chloride / n-hexane). (S) -2 455 mg (0.447 mmol, yield 63 mol from (S) -1). %) Was obtained.

The analysis results are as follows.
Mol. Form .: C ₇₂ H ₅₂ N ₆ O (Exact Mass: 1016.42, Mol. Wt .: 1017.25)
Appearance: White solid
^{1 1} H NMR (CDCl ₃ ) δ 7.84 (d, J = 7.6 Hz, 2H), 7.60-7.54 (m, 4H), 7.32-7.13 (m, 14H), 6.87-6.48 (m, 20H), 3.39 (dd) , J = 8.4, 7.0 Hz, 1H), 3.02-2.96 (m, 1H), 2.80 (t, J = 8.4 Hz, 1H), 2.17-2.07 (m, 1H), 1.55-1.46 (m, 1H), 1.13-1.04 (m, 1H), 0.98-0.75 (m, 2H), 0.56-0.44 (m, 1H)
MS (FAB-MS): 1018 (MH ⁺ ), 972 (MH-45 ⁺ )
Anal. Calcd. For C ₇₂ H ₅₂ N ₆ O: C, 85.01; H, 5.15; N, 8.26
Found; C, 85.03; H, 5.42; N, 8.28

From FIGS. 1 and 2, by changing the chirality of the proline derivative of the optically active proline derivative ((R) -2 and (S) -2)), circularly polarized light emission having a different sign is emitted in a methylene chloride solution at room temperature. Observed, its anisotropic factor (glum) was ^2x10-3 .

According to the aromatic compound of the present invention, for example, it has a specific chirality property, and is expected to be applied to, for example, three-dimensional displays, optical communications, and security fields, and can be used industrially.

Claims (2)

An aromatic compound represented by the following general formula (1).

[In equation (1) , X has the following structure of X-1 .

NR ¹ R ² in the formula (1) is expressed by the following general formula (2).

In formula (2), R ⁵ and R ⁶ are independently hydrogen atoms, linear or branched or cyclic alkyl groups having 1 to 18 carbon atoms, and linear or branched or cyclic groups having 1 to 18 carbon atoms. Alkoxy group, substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms, and p and q are integers of 1 or more.)
R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, a linear or branched alkoxyalkyl group having 1 to 18 carbon atoms, an acetyl group, and the like. Alternatively, it is a methoxycarbonyl group , the bond with the pyrrolidine ring has optical activity, and o is an integer of 1 to 3.
^R4 is a hydrogen atom or a carbonyl group . ] The compound according to claim 1 , wherein the compound is represented by the following formula (3) or (4).

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