JP7699983B2 - Novel helicene derivatives and their precursors - Google Patents

Description

Article 30, paragraph 2 of the Patent Act is applicable. Published in the proceedings of the 30th Symposium on Fundamental Organic Chemistry held from September 25 to September 27, 2019 (published September 25, 2019)

The present invention relates to a novel helicene derivative and its precursor, and to a circularly polarized light-emitting material that utilizes the derivative. The novel helicene derivative of the present invention has a unique chirality property, and is expected to be applied to, for example, three-dimensional displays, optical communications, and security fields.

Circularly polarized luminescence (CPL) is expected to be applied to polarized light sources for high-brightness displays and next-generation optical information technology such as security. However, the currently used CPL light sources are a combination of a linearly polarized light-emitting material that does not have CPL characteristics and a circularly polarized transmission filter, which results in a complex and expensive manufacturing process and poor energy efficiency. Therefore, it is important to establish a design guideline for high-brightness, highly circularly polarized light-emitting materials.
From this perspective, conventionally, substances using metal ions have mainly been developed (for example, Patent Document 1), but there is a demand for the development of materials composed of elements that are inexpensive and have a low environmental impact.

Helicene, a compound in which benzene rings are condensed into a helical shape, is known as a chiral compound and is expected to be applied to circularly polarized luminescent materials.
For example, Patent Document 2 states that a helicene compound having at least five condensed aromatic rings is suitable as a charge transport material, a light emitting material, a wavelength conversion material, etc. Patent Document 3 states that azahelicene compounds are expected to be applied to organic EL devices, fluorescent materials, nonlinear optical materials, etc. Furthermore, Patent Document 4 lists examples of helicene compounds substituted with a cyano group, but does not investigate the circularly polarized light emission properties.
In addition, [7]helicene, which has seven fused benzene rings, generally has a low fluorescence quantum yield and requires further improvement for practical use. Studies are being conducted, for example in Non-Patent Documents 1 and 2.

JP 2009-57367 A JP 2000-195673 A JP 2013-40145 A JP 2018-177647 A

Angewandte Chemie international Edition, vol. 56, 3906-3910, 2017 Organic Letters vol. 15, Issue 9, 2104-2107, 2013

The object of the present invention is to provide a material that has a skeleton different from that of conventional materials and exhibits specific optical properties. More specifically, the object is to provide a material and its precursor that has a characteristic chirality and exhibits high circularly polarized luminescence.

As a result of intensive research, the inventors discovered that the optically active helicene derivatives represented by general formula (1) and general formula (2) have specific chirality and high circularly polarized luminescence, and thus completed the present invention.

（一般式（１）および一般式（２）中、
Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、各々独立して、水素原子、炭素数１～１８の直鎖もしくは分岐もしくは環状のアルキル基、炭素数１～１８の直鎖もしくは分岐もしくは環状のアルコキシ基、炭素数６～４０の置換もしくは無置換のアリール基、または炭素数４～４０の置換もしくは無置換のヘテロアリール基であり、隣接するＲ^１とＲ^２は、互いに結合して環を形成してもよく、
ＡおよびＢは、各々独立して、炭素数６～４０の置換もしくは無置換の芳香族環、または炭素数４～４０の置換もしくは無置換の芳香族ヘテロ環を表す。）
［２］上記一般式（１）および一般式（２）において、ＡおよびＢが、各々独立して、下記Ｘ－１、Ｘ－２、Ｘ－３、Ｘ－４及びＸ－５からなる群より選ばれる構造である、［１］に記載の光学活性ヘリセン誘導体又はラセミ体混合物。

［３］上記一般式（１）および一般式（２）において、Ｒ^１およびＲ^２が、各々独立して、置換もしくは無置換のフェニル基である、［１］又は［２］に記載の光学活性ヘリセン誘導体又はラセミ体混合物。
［４］下記一般式（３）で表されるヘキサアミノベンゼン誘導体。

（一般式（３）中、
Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、各々独立して、水素原子、炭素数１～１８の直鎖もしくは分岐もしくは環状のアルキル基、炭素数１～１８の直鎖もしくは分岐もしくは環状のアルコキシ基、炭素数６～４０の置換もしくは無置換のアリール基、または炭素数４～４０の置換もしくは無置換のヘテロアリール基であり、隣接するＲ^１とＲ^２は、互いに結合して環を形成してもよく、
ＡおよびＢは、各々独立して、炭素数６～４０の置換もしくは無置換の芳香環、または炭素数４～４０の置換もしくは無置換の芳香族ヘテロ環を表す。）
［５］下記式（４）または下記式（５）で表される、光学活性ヘリセン誘導体、又はこれらのラセミ体混合物。

That is, the present invention relates to an optically active helicene derivative represented by general formula (1) or general formula (2), or a racemic mixture thereof, and uses thereof, and relates to the following inventions.
[1] An optically active helicene derivative or a racemic mixture represented by the following general formula (1) or (2):

(In the general formula (1) and the general formula (2),
R ¹ , R ² , R ³ and R ⁴ each independently represent 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, 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.
[2] In the above general formula (1) and general formula (2), A and B are each independently a structure selected from the group consisting of X-1, X-2, X-3, X-4, and X-5 below. The optically active helicene derivative or racemic mixture according to [1].

[3] In the above general formula (1) and general formula (2), R ¹ and R ² are each independently a substituted or unsubstituted phenyl group. The optically active helicene derivative or racemic mixture according to [1] or [2].
[4] A hexaaminobenzene derivative represented by the following general formula (3):

(In general formula (3),
R ¹ , R ² , R ³ and R ⁴ each independently represent 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, 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.
[5] An optically active helicene derivative represented by the following formula (4) or the following formula (5), or a racemic mixture thereof.

The optically active helicene derivatives or racemic mixtures thereof and hexaaminobenzene derivatives of the present invention have skeletons different from those of conventional materials and are materials that exhibit specific optical properties. Furthermore, they are materials and precursors of materials that have characteristic chirality and high circularly polarized luminescence. For this reason, they are extremely useful industrially.

This is a ^1H -NMR measurement chart of the compound (I-1) produced in Synthesis Example 1, where the X-axis (horizontal axis) indicates the chemical shift (unit: ppm) and the Y-axis (vertical axis) indicates the intensity (unit: arbitrary). An enlarged view is shown in Fig. 1 (units are the same). 2 is a ¹ H-NMR measurement chart of the compound (II-1) produced in Example 1, in which the X-axis (horizontal axis) indicates the chemical shift (unit: ppm) and the Y-axis (vertical axis) indicates the intensity (unit: arbitrary). An enlarged view is shown in FIG. 3 is a ¹ H-NMR measurement chart of the compound (III-1) produced in Example 2, in which the X-axis (horizontal axis) indicates the chemical shift (unit: ppm) and the Y-axis (vertical axis) indicates the intensity (unit: arbitrary). An enlarged view is shown in FIG. 4 is an LDI TOF-MS measurement chart of the compound (III-1) produced in Example 2, in which the X-axis (horizontal axis) indicates the mass of the ion (or the mass-to-charge ratio, expressed as "m/z" in the figure), and the Y-axis (vertical axis) indicates the intensity (in arbitrary units). An enlarged view is shown in FIG. 4, in which the upper row is based on actual measurements and the lower row is based on calculated values (the units are the same). This is an HPLC measurement chart (optical resolution, (HPLC apparatus equipped with Daicel Chiral Pack IA)) of compound (III-1) produced in Example 2, in which the X-axis (horizontal axis) indicates elution time (unit: minutes) and the Y-axis (vertical axis) indicates relative intensity of peaks (unit: arbitrary). Numbers in the figure indicate retention times of peaks (unit: minutes). The UV-vis absorption spectrum and emission spectrum of compound (III-1) produced in Example 2, in which the X-axis (horizontal axis) indicates wavelength (unit: nm), the left Y-axis (vertical axis) indicates intensity (expressed as "ε" (molar absorption coefficient) in unit: M ^-1 cm ^-1 ), and the right Y-axis (vertical axis) indicates normalized emission intensity (unit: maximum peak is taken as 1). The absorption spectrum was measured in a methylene chloride solution at room temperature, and is shown by a solid line in the figure. The emission spectrum was measured in a methylene chloride solution (1.48 x ^10-5 M), at room temperature, with excitation light of 430 nm, and is shown by a dashed line in the figure. FIG. 1 is a measurement chart of circular dichroism (CD) of compound (III-1P) and compound (III-1M) obtained by optical resolution of compound (III-1) produced in Example 2 by high performance liquid chromatography, in which the X-axis (horizontal axis) represents wavelength (unit: nm) and the Y-axis (vertical axis) represents molar ellipticity (Δε, unit: M ⁻¹ cm ⁻¹ ). FIG. 1 is a measurement chart of circularly polarized luminescence (CPL) of compound (III-1P) and compound (III-1M) obtained by optical resolution of compound (III-1) produced in Example 2 by high performance liquid chromatography. In the figure, the X-axis (horizontal axis) represents wavelength (unit: nm), and the Y-axis (vertical axis) represents ΔI (unit: arbitrary).

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

In the above general formula (1) and general formula (2), it is preferable that 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 or different from these substituents, and adjacent R ¹ and R ² may be bonded to each other to form a ring.

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

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

Specific examples of substituted or unsubstituted aryl groups having 6 to 40 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 2-anthryl, 9-anthryl, 2-fluorenyl, phenanthryl, pyrenyl, chrysenyl, perylenyl, picenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-n-propylphenyl, 4-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 4-isobutylphenyl, 4-sec-butylphenyl, 2-sec-butylphenyl, 4-tert-butylphenyl, 3-tert-butylphenyl, 2-tert-butylphenyl, 4-n-pentylphenyl, 4-isopentylphenyl, 2-neopentylphenyl, 4-tert-pentyl phenyl 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 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-propyl oxyphenyl 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, a 6-methoxy-2-naphthyl group, a 6-ethoxy-2-naphthyl group, a 6-n-butoxy-2-naphthyl group, a 6-n-hexyloxy-2-naphthyl group, a 7-methoxy-2-naphthyl group, a 7-n-butoxy-2-naphthyl group, a 2-methyl-4-methoxyphenyl group, a 2-methyl-5-methoxyphenyl group, a 3-methyl-4-methoxyphenyl group, a 3-methyl-5-methoxyphenyl group, a 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, a 4-methoxyphenyl group, a 4-n-butoxyphenyl group, a 2-methoxyphenyl group, a 4-chlorophenyl group, a 3-methyl-4-phenylphenyl group, a 3-methoxy-4-phenylphenyl group, a terphenyl group, a 3,5-diphenylphenyl group, a 10-phenylanthryl group, a 10-(3,5-diphenylphenyl)-9-anthryl group, a 9-phenyl-2-fluorenyl group, a 4-fluorophenyl group, a 3-fluorophenyl group, a 2-fluorophenyl group, a 4-chlorophenyl group, a 3-chlorophenyl group, a 2-chlorophenyl group, a 4-bromophenyl group, a 2-bromophenyl group, a 4-chloro-1-naphthyl group, a 4-chlorophenyl group, a b-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-dibromo Phenyl 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-methyl Examples of the aryl group include, but are not limited to, a 2-chloro-5-methylphenyl group, a 2-chloro-6-methylphenyl group, a 2-methyl-3-chlorophenyl group, a 2-methyl-4-chlorophenyl group, a 3-chloro-4-methylphenyl group, a 3-methyl-4-chlorophenyl group, a 2-chloro-4,6-dimethylphenyl group, a 2-methoxy-4-fluorophenyl group, a 2-fluoro-4-methoxyphenyl group, a 2-fluoro-4-ethoxyphenyl group, a 2-fluoro-6-methoxyphenyl group, a 3-fluoro-4-ethoxyphenyl group, a 3-chloro-4-methoxyphenyl group, a 2-methoxy-5-chlorophenyl group, a 3-methoxy-6-chlorophenyl group, a 5-chloro-2,4-dimethoxyphenyl group, a 4-trifluoromethylphenyl group, a 3-trifluoromethylphenyl group, and a 3,5-bis(trifluoromethyl)phenyl group.

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, and examples of the heterocyclic group include, but are not limited to, a 4-quinolyl group, a 4-pyridyl group, a 3-pyridyl group, a 2-pyridyl group, a 3-furyl group, a 2-furyl group, a 3-thienyl group, a 2-thienyl group, a 2-oxazolyl group, a 2-thiazolyl group, a 2-benzoxazolyl group, a 2-benzothiazolyl group, and a 2-benzimidazolyl group.

（式中、Ｒ^５～Ｒ^７は、各々独立して、水素原子、ハロゲン原子で置換されても良い炭素数１～１８の直鎖もしくは分岐もしくは環状のアルキル基、ハロゲン原子で置換されても良い炭素数１～１８の直鎖もしくは分岐もしくは環状のアルコキシ基を示し、ｎ、ｍ、ｌは０もしくは１以上の整数である。） Furthermore, adjacent R ¹ and R ² may be bonded to each other to form a ring. Specific examples of when R ¹ and R ² are bonded to each other to form a ring include, but are not limited to, the following examples (Y-1), (Y-2) and (Y-3).

(In the formula, R ⁵ to R ⁷ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms which may be substituted with a halogen atom, or a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms which may be substituted with a halogen atom; and n, m and l each represent 0 or an integer of 1 or more.)

In the above general formula (1) and general formula (2), A and B, which are structures 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, but considering the complexity of synthesis, it is preferable that they are the same.

The aromatic ring is not particularly limited, but specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a triphenylene ring, a pyrene ring, a biphenyl, and a terphenyl. The aromatic heterocycle is not particularly limited, but specific examples thereof include a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a thiophene ring, a furan ring, a benzoxazole ring, and a benzothiazole ring.

Moreover, it is more preferable that A and B, which are structures having an aromatic ring or an aromatic heterocycle in general formula (1) and general formula (2), are structures selected from the group consisting of X-1, X-2, X-3, X-4, and X-5 below.

General formula (1) and general formula (2) have helical chirality depending on the overlapping of A and B, which are structures having an aromatic ring or an aromatic heterocycle. When the general formula (1) has a right-handed helical structure, it has P helicity, and when the general formula (2) has a left-handed helical structure, it has M helicity.
Further examples of specific structural formulae of general formula (1) and general formula (2) are given below, but the compounds are not limited to these.

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

（一般式（３）中のＲ^１、Ｒ^２、Ｒ^３およびＲ^４は、各々独立して、水素原子、炭素数１～１８の直鎖もしくは分岐もしくは環状のアルキル基、炭素数１～１８の直鎖もしくは分岐もしくは環状のアルコキシ基、炭素数６～４０の置換もしくは無置換のアリール基、または炭素数４～４０の置換もしくは無置換のヘテロアリール基であり、隣接するＲ^１とＲ^２は、互いに結合して環を形成してもよく、
ＡおよびＢは、各々独立して、炭素数６～４０の置換もしくは無置換の芳香環、または炭素数４～４０の置換もしくは無置換の芳香族ヘテロ環を表す。）
上記の一般式（３）において、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、一般式（１）および一般式（２）において、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４について例示したものと同様である。

(R ¹ , R ² , R ³ and R ⁴ in general formula (3) 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; 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 formulae (1) and (2).

Further examples of specific structural formulas of general formula (3) are given below, but the compounds are not limited to these.

<Method of producing optically active helicene derivative and racemic mixture according to the present invention>
The optically active helicene derivatives and racemic mixtures represented by the general formulas (1) and (2) can be produced by, but are not limited to, the steps shown below.
That is, it comprises step 1 (a synthesis step of a precursor (tetrapyrrolodihalobenzene derivative)), step 2 (a synthesis step of a hexaaminobenzene derivative represented by general formula (3)), formula (1), step 3 (a synthesis step of a racemic mixture of general formulas (1) and (2) from the hexaaminobenzene derivative represented by general formula (3)), and step 4 (a step of optically resolving each optically active substance from the mixture of general formulas (1) and (2)).

Step 1) Synthesis step of precursor (tetrapyrrolodihalobenzene derivative) A pyrrole derivative which may have a substituent at the 3,4-position as a reaction agent and a base such as sodium hydride are added to a reaction vessel equipped with a reflux device, and an inert gas atmosphere such as nitrogen is created, and then a solvent such as dimethylformamide is added and the mixture is reacted by stirring. The reaction temperature is not particularly limited as long as the desired precursor can be obtained, and the pressure during the reaction can be selected from any of pressurized, normal, and reduced pressure. The reaction temperature is preferably, for example, about -30°C to 50°C. The reaction time depends on the reactivity of the reaction agent, but the reaction is usually carried out for 1 minute to 1 day, preferably 5 minutes to 10 hours, and more preferably 10 minutes to 2 hours.
In a separate reaction vessel, 1,2-dihalogeno-3,4,5,6-tetrafluorobenzene is dissolved in a solvent such as dimethylformamide, and the resulting solution is added to the reaction vessel under an inert gas atmosphere such as nitrogen, or in an open system. The halogen atom in the compound can be selected from bromine and iodine atoms.
The reaction time depends on the reactivity of the reaction raw materials, but is usually 10 minutes to 3 days, preferably 30 minutes to 1 day, and more preferably 1 hour to 1 day. The reaction temperature is, for example, about -80°C to 50°C, and more preferably -10°C to 30°C in order to achieve both reactivity and selectivity.
After the reaction is completed, a solvent capable of dissolving the reaction product, such as water, is added, and the reaction product is extracted with a non-aqueous solvent such as ethyl acetate. The organic layer is washed in a known manner, for example, with water and saturated saline, and then dried with a drying agent 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 methods known in the art, such as elemental analysis, NMR, mass spectrometry, etc., to confirm its structure, physical properties, degree of purification, etc.

Step 2) Synthesis step of hexaaminobenzene derivative A reaction agent such as indole and a base such as sodium hydride are added to a reaction vessel equipped with a reflux device, and an inert gas atmosphere such as nitrogen is created. Then, a solvent such as dimethylformamide is added and the mixture is stirred to react. The reaction temperature is not particularly limited as long as the desired precursor can be obtained, and the reaction pressure can be selected from among pressurized, normal, and reduced pressure. The reaction temperature is preferably, for example, about -50°C to 50°C. The reaction time depends on the reactivity of the reaction agent, but it is usually 1 minute to 1 day, preferably 5 minutes to 10 hours, and more preferably 10 minutes to 2 hours.
In a separate reaction vessel, the precursor is dissolved in a solvent such as dimethylacetamide,
The reaction vessel is charged with the raw materials under an inert gas atmosphere such as nitrogen or in an open system. The reaction time depends on the reactivity of the raw materials, but it is usually 10 minutes to 3 days, preferably 30 minutes to 1 day, and more preferably 1 hour to 1 day. The reaction temperature is, for example, about 0°C to 100°C, and in order to achieve both reactivity and selectivity, it is more preferable to set the temperature at 10°C to 50°C.
After the reaction is completed, a solvent capable of dissolving the reaction product, such as water, is added, and the reaction product is extracted with a non-aqueous solvent such as ethyl acetate. The organic layer is washed in a known manner, for example, with water and saturated saline, and then dried with a drying agent such as sodium sulfate and concentrated with a commonly used device such as an evaporator to obtain a hexaaminobenzene derivative.
The structure, physical properties, degree of purification, etc. of the obtained hexaaminobenzene derivative can be confirmed by analysis using methods known in the art, such as elemental analysis, NMR, mass spectrometry, etc.

Step 3) Step of synthesizing a racemate which is a mixture of general formula (1) and general formula (2) The step of synthesizing a racemate which is a mixture of general formula (1) and general formula (2) of the present invention is carried out by the oxidative coupling reaction of the above-mentioned hexaaminobenzene derivative.
A specific example of the oxidative coupling method is a method using an oxidizing agent catalyst, which is preferable as a method that is inexpensive and easy to obtain. Examples of the oxidizing agent catalyst include compounds such as aluminum chloride, iron chloride, molybdenum chloride, tungsten chloride, and tin chloride.
A reaction vessel equipped with a reflux device is charged with a reaction reagent such as the hexaaminobenzene derivative, a solvent such as nitromethane, dichloromethane, and an oxidizing agent catalyst such as iron chloride, and the mixture is stirred to cause a reaction.
The reaction temperature is not particularly limited as long as the desired racemic compound can be obtained, and the pressure during the reaction can be selected from among pressurized, normal, and reduced pressure. The reaction temperature is preferably about 0° C. to 100° C. The reaction time depends on the reactivity of the reaction reagents, but is usually 1 minute to 1 day, preferably 5 minutes to 10 hours, and more preferably 10 minutes to 5 hours.
After the reaction is completed, the solid matter is separated by filtration or the like, and concentrated by a commonly used device such as an evaporator. It is preferable to further purify the product by a commonly used purification means such as silica gel column chromatography using a commonly used mobile phase solvent such as methylene chloride/n-hexane.
The structure, physical properties, degree of purity, etc. of the obtained racemic mixture can be confirmed by analysis using methods known in the art, such as elemental analysis, NMR, mass spectrometry, etc.

Step 4) Step of optically resolving each optically active substance from the mixture of general formula (1) and general formula (2) The racemate, which is a mixture of general formula (1) and general formula (2), can be produced by optically resolving. For example, the optical resolution method can be performed by using a high performance liquid chromatography column for separating optical isomers to separate the (R) optical isomer and the (S) optical isomer. The high performance liquid chromatography column for separating optical isomers is not particularly limited, but is generally commercially available, and for example, CHIRALPAK IC, CHIRALPAK IA, CHIRALPAK AD-H, or CHIRALPAK OD-H manufactured and sold by Daicel Chemical Industries, Ltd. 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; aminos such as diethylamine; acetic acid, trifluoroacetic acid, water, or a mixed solvent thereof.
The temperature and time in the optical resolution can vary within a wide range. In general, the temperature is −20 to 60° C., preferably 5 to 50° C. The time is 0.05 to 50 hours, preferably 0.1 to 5 hours.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

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

還流装置を装着した１００ｍＬ三つ口フラスコに、水素化ナトリウム ８１０ｍｇ（６０％ミネラルオイル分散（２０．３ｍｍｏｌ））を加え、窒素置換した後、３，４－ジ－（４－トリフルオロメチルフェニル）－１Ｈ－ピロール ４．８０ｇ（１３．５ｍｍｏｌ）の脱水ＤＭＦ溶液（３０ｍＬ）を撹拌しながら０℃で滴下し、３０分間撹拌した。
この溶液を、別の反応容器に調製した１，２－ジブロモ－３，４，５，６－テトラフルオロベンゼン ０．４６４ｍＬ（３．３７ｍｍｏｌ）の脱水ＤＭＦ溶液 (１５ｍＬ) に－１０ ℃で２０分かけて滴下し、２時間撹拌した。水を加えて反応を止めた後、酢酸エチルで抽出し、有機層を水及び飽和食塩水で洗浄した。その後、硫酸ナトリウムを用いて乾燥させ、エバポレーターで濃縮した。残渣をシリカゲルカラムクロマトグラフィー（塩化メチレン／ｎ－ヘキサン） により精製し、化合物（I－１）の白色固体 ５．２４ｇを収率９４％で得た。 [Synthesis Example 1] Synthesis of compound (I-1)

Into a 100 mL three-neck flask equipped with a reflux apparatus, 810 mg of sodium hydride (60% dispersion in mineral oil (20.3 mmol)) was added, and the inside of the flask was replaced with nitrogen. Then, a solution of 4.80 g (13.5 mmol) of 3,4-di-(4-trifluoromethylphenyl)-1H-pyrrole in dehydrated DMF (30 mL) was added dropwise with stirring at 0° C., 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 a separate reaction vessel over 20 minutes at -10°C, and the mixture was stirred for 2 hours. Water was added to stop the reaction, followed by extraction with ethyl acetate, and the organic layer was washed with water and saturated saline. It was then dried using sodium sulfate and concentrated using 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%.

The analysis results were as follows:
¹ H-NMR (CDCl ₃ , 25° C., 400 MHz) δ7.55 (d, J=8.2 Hz, 8H, CF ₃ Ph), 7.46 (d, J=8.2 Hz, 8H, CF ₃ Ph), 7.28 (d, J=8.1 Hz, 2H, CF ₃ Ph), 7.06 (d, J=8.1Hz, 8H, CF ₃ Ph), 6.89 (s, 4H, Py-α), 6.47 (s, 4H, Py-α)
^13C -NMR ( _CDCl3 , 25°C, 100MHz) δ137.64, 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
^19F -NMR (CDCl ₃ , 376MHz) 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%

In addition, ^{the 1} H-NMR measurement chart is shown in FIG.

還流装置を装着した５０ｍＬ三つ口フラスコに、水素化ナトリウム １９．６ｍｇ（６０％ミネラルオイル分散（０．４９１ｍｍｏｌ））を加え、窒素置換した後、３－メチルインドール ４８．０ｍｇ（０．３６８ｍｍｏｌ）の脱水ＤＭＦ溶液（２ｍＬ）を撹拌しながら、０℃で滴下し、３０分間撹拌した。
この溶液を、別の反応容器に調製した１，２－ジブロモ－３，４，５，６－テトラ［３，４－ジ－（トリフルオロメチルフェニル）］ピロリルベンゼン（化合物（I－１）） ２０２．４ｍｇ（０．１２３ｍｍｏｌ）の脱水ＤＭＦ溶液 (３ｍＬ) に０ ℃で５分かけて滴下し、室温で２時間撹拌した。
水を加えて反応を止めた後、酢酸エチルで抽出し、有機層を水及び飽和食塩水で洗浄した。その後、硫酸ナトリウムを用いて乾燥させ、エバポレーターで濃縮した。残渣をシリカゲルカラムクロマトグラフィー（塩化メチレン／ｎ－ヘキサン） により精製し、化合物（II－１）の単黄色固体 ６８．８ｍｇを収率３２％で得た。 [Example 1] Synthesis of compound (II-1)

Into a 50 mL three-neck flask equipped with a reflux apparatus, 19.6 mg of sodium hydride (60% dispersion in mineral oil (0.491 mmol)) was added, and the inside of the flask was replaced with nitrogen. Then, a solution of 48.0 mg (0.368 mmol) of 3-methylindole in dehydrated DMF (2 mL) was added dropwise at 0° C. with stirring, and the mixture was stirred for 30 minutes.
This solution was added dropwise at 0° C. over 5 minutes to a dehydrated DMF solution (3 mL) of 202.4 mg (0.123 mmol) of 1,2-dibromo-3,4,5,6-tetra[3,4-di-(trifluoromethylphenyl)]pyrrolylbenzene (compound (I-1)) prepared in a separate reaction vessel, and the mixture was stirred at room temperature 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 saline. It was then dried using sodium sulfate and concentrated using an evaporator. The residue was purified by silica gel column chromatography (methylene chloride/n-hexane) to obtain 68.8 mg of compound (II-1) as a pale yellow solid in a yield of 32%.

The analysis results were as follows:
^1H -NMR (tetrachloroethane-d2, 100°C, 400MHz) δ7.59 (d, J=8.4Hz, 1.1H, Ind), 7.55 (d, J=8.0Hz, 8H, _CF3 Ph), 7.53 (d, J = 8.2Hz, 0.9H, Ind), 7.46 (d, J = 7.8Hz, 8H, _CF Ph), 7.22 (d, J = 8.0Hz, 8H, CF ₃ Ph), 7.20-7.05 (m, 5H, Ind), 6.94 (t, J=7.7Hz, 1H, Ind), 6.91-6.87 (m, 8H, _CF3 Ph), 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-CH ₃ ), 2.22 (s, 3.4H, Ind-CH ₃ )
MS (FAB-MS) m/z 1749 ([M+1] ⁺ )

^{The 1} H-NMR measurement charts are shown in FIG.

化合物（III－１）を、化合物（III－１Ｐ）と化合物（III－１Ｍ）との混合物であり、ラセミ体（III－１）と定義する。
還流装置を装着した５００ｍＬ四つ口フラスコに、窒素雰囲気下、１，２，３，４－テトラ［３，４－ジ－（トリフルオロメチルフェニル）］ピロリル－５，６－（３－メチル）インドリルベンゼン ３６４ｍｇ（０．２０８ｍｍｏｌ）の脱水塩化メチレン溶液（２５０ｍＬ）、塩化第二鉄 ５０２ｍｇ（３．１０ｍｍｏｌ）のニトロメタン溶液（５ｍＬ）を入れ、撹拌しながら２時間還流した。
ヒドラジン一水和物を加えて反応を止めた後、有機層を水及び飽和食塩水で洗浄した。その後、硫酸ナトリウムを用いて乾燥させ、エバポレーターで濃縮した。残渣をアルミナカラムクロマトグラフィー（塩化メチレン／ｎ－ヘキサン） により精製し、更にトルエンとヘキサンの混合溶媒から再結晶して、化合物（III－１）３０．４ｍｇを収率８％で取得した。 [Example 2] Synthesis of racemic compound (III-1)

The compound (III-1) is a mixture of the compound (III-1P) and the compound (III-1M), and is defined as a racemate (III-1).
A 500 mL four-neck flask equipped with a reflux apparatus was charged with a dehydrated methylene chloride solution (250 mL) of 364 mg (0.208 mmol) of 1,2,3,4-tetra[3,4-di-(trifluoromethylphenyl)]pyrrolyl-5,6-(3-methyl)indolylbenzene and a nitromethane solution (5 mL) of 502 mg (3.10 mmol) of ferric chloride under a nitrogen atmosphere, and the mixture was refluxed with stirring for 2 hours.
After adding hydrazine monohydrate to stop the reaction, the organic layer was washed with water and saturated saline. It was then dried using sodium sulfate and concentrated using an evaporator. The residue was purified by alumina column chromatography (methylene chloride/n-hexane) and further recrystallized from a mixed solvent of toluene and hexane to obtain 30.4 mg of compound (III-1) in a yield of 8%.

The analysis results were as follows:
¹ H-NMR (tetrachloroethane-d2, 100°C, 400 MHz) δ7.61 (d, J = 8.5 Hz, 4H, CF ₃ Ph), 7.52 (d, J = 7.8 Hz, 4H, CF ₃ Ph), 7.39 (d, J=8.4Hz, 2H, Ind), 7.10-7.00 (m, 12H, _CF3Ph ), 6.96 (t, J=7.5Hz, 2H, Ind), 6.90 (d, J=8.5Hz, 4H, _CF3 Ph), 6.81-6.66 (m, 10H, _CF3Ph +Ind), 6.50 (d, J=8.4Hz, 2H, Ind), 1.76 (s, 6H)
MS (MALDI) calcd. for C96H46F24N6:1738.3401, Found:1738.3343

FIG. 3 shows a ¹ H-NMR measurement chart, and FIG. 4 shows an LDI TOF-MS measurement chart.

Compound (III-1) was analyzed by high performance liquid chromatography (HPLC) using Daicel Chiral Pack IA and a mixture of hexane/chloroform/ethanol (95/3/2=v/v/v), and was confirmed to be a racemic compound consisting 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 FIG.
Furthermore, the ultraviolet-visible absorption spectrum and emission spectrum (excitation light: 430 nm) of a methylene chloride solution of compound (III-1) are shown in Figure 6. The fluorescence quantum yield Φ _FL was 0.10, and the fluorescence lifetime was 4.7 ns.
In addition, 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 methylene chloride solution at room temperature, and the results are shown in Figure 7 and Figure 8 (excitation light: 370 nm). By changing the chirality, circularly polarized luminescence with different signs was observed, and the anisotropy factor (glum) was a high value of 3.7 × 10 ^-2 , indicating that the compound has excellent circular polarization properties.

The helicene derivatives of the present invention have unique chiral properties and are expected to be useful in industrial applications, for example, in three-dimensional displays, optical communications, and security.

Claims (6)

An optically active helicene derivative or a racemic mixture represented by the following general formula (1) or (2):


(In the general formula (1) and the general formula (2),
R ¹ , R ² , R ³ and R ⁴ each independently represent 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 . 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 X-1 and X-2 below.

An optically active helicene derivative represented by the following formula, or a racemic mixture thereof.



An optically active helicene derivative represented by the following formula (4) or (5), or a racemic mixture thereof:

A hexaaminobenzene derivative represented by the following general formula (3):

(In general formula (3),
R ¹ , R ² , R ³ , R ⁴ , A and B are the same substituents as in claim 1 . A hexaaminobenzene derivative represented by the following formula: