Phenazine derivative and method for producing same

Abstract

Provided are: a phenazine derivative; and a method for producing a phenazine derivative, in which a reaction proceeds under mild conditions without the use of a catalyst such as a metal or an enzyme.　The phenazine derivative is represented by general formula (1). (In the formula, R1 moieties are each independently a hydrogen atom, a primary amino group (-NH2), a secondary amino group (-NHR'), an acylamido group (-NHCOR') or a hydroxyl group (-OH), R2 moieties are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amido group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamido group (-S(=O)NR'R''), a sulfonyl group (-S(=O)2R'), a sulfonamido group (-S(=O)2NR'R''), a sulfonate group (-S(=O)2OR'), a phosphinyl group (-P(=O)2R') or a nitrile group (-CN), R3 moieties are each independently a hydrogen atom, a primary amino group (-NH2), a secondary amino group (-NHR'), an acylamido group (-NHCOR'), a hydroxyl group (-OH) or a monovalent organic group, R44 moieties are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amido group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamido group (-S(=O)NR'R''), a sulfonyl group (-S(=O)2R'), a sulfonamido group (-S(=O)2NR'R''), a sulfonate group (-S(=O)2OR'), a phosphinyl group (-P(=O)R'2), a nitrile group (-CN) or a monovalent organic group, R' moieties are each independently an alkyl group or aryl group in which at least one hydrogen may be substituted, R'' is a hydrogen atom or an alkyl group or aryl group in which at least one hydrogen atom may be substituted, and alkyl groups and aryl groups in R' and R'' may be the same as, or different from, each other.)

Description

Phenazine derivatives and methods for producing the same

[0001] The present invention relates to novel polysubstituted phenazine derivatives and methods for synthesizing the same.

[0002] Phenazines are nitrogen-containing heterocyclic compounds produced by various microorganisms in nature. They have antioxidant, antibiotic, anticancer, and antibacterial properties and the ability to bind to extracellular DNA. Furthermore, phenazines have redox activity and are suitable for electrochemical applications, making them useful in electrochemical devices such as sensors and batteries. Furthermore, phenazines are expected to be used as building blocks in organic semiconductors, chemical switches, organic electroluminescence (EL), sensors, and biosensors.

[0003] Various compounds containing the phenazine skeleton have already been reported, including the synthesis of phenazine by the rhodium-catalyzed cyclization reaction of azobenzene with nitrosoarenes (Non-Patent Document 1), the copper-catalyzed homocoupling reaction of 2-iodoaniline or 2-bromoaniline in water, and the condensation reaction of o-phenylenediamine with catechol (Non-Patent Document 2).

[0004] Non-Patent Document 3 reports a synthesis reaction of phenazine via the self-coupling of aniline, in which a bimetallic nanocluster catalyst (Pd-Ag catalyst) is used to non-radically activate the aryl carbon-hydrogen bond at the ortho position of aniline, resulting in the simultaneous formation of two C-N bonds. Other examples include the synthesis of phenazine via the oxidative cyclization of aniline and o-phenylenediamine using a reusable cobalt catalyst, a nitrogen-doped carbon-supported cobalt nanoparticle catalyst (Non-Patent Document 4), the synthesis of phenazine via the oxidation of o-phenylenediamine and other amines using laccase, a type of multicopper oxidase (Non-Patent Document 5), the conversion of o-phenylenediamine to phenazine via photooxidation (Non-Patent Document 6), and the synthesis of phenazine via the reaction of nitrobenzene and aniline in the presence of a strong base (Non-Patent Document 7).

[0005] Fluorescent materials with a phenazine skeleton have also been developed. Reported examples of phenazine-based fluorescent materials include luminescent materials with a donor-acceptor-donor (D-A-D) structure, which have phenoxazine or phenothiazine as the donor and dibenzophenazine as the acceptor. These phenazine-based fluorescent materials are known to not only emit multicolored light, but also exhibit TADF (Non-Patent Documents 8 and 9). In addition to fluorescent dyes based on tetraguanidinophenazine (Non-Patent Document 10), there have also been reports that phenazine derivatives bearing a dicyano-vinyl group, which serves as a recognition site, and an electron-withdrawing group at both ends can be used in chemical dosimeters (Non-Patent Document 11).

[0006] Non-Patent Document 12 reports that a tetraaminophenazine dye is synthesized by using a 5-nitrobenzene-1,2,4-triamine precursor as a substrate and forming two intermolecular C—N bonds under oxidation conditions, and that the tetraaminophenazine absorbs green light and emits its complementary color, reddish-orange.

[0007] Oxidizing agents with a phenazine skeleton have also been developed. Non-Patent Document 13 reports that 1,2,3,4,5,6,7,8-octafluorophenazine (F-Phen) has a higher positive oxidation potential than phenazine and an absorption spectrum in the visible light wavelength range, and is converted to F-Phen-2-OH by the photoexcited triplet state of F-Phen, and oxidizes water to generate hydroxyl radicals.

[0008] However, the conventional phenazine synthesis methods generally use metal catalysts and require harsh reaction conditions, resulting in low product yields, slow reaction rates, and limited types of substrates that can be used as starting materials. Furthermore, the limited types of substrates limit the freedom of chemical modification, restricting the selective introduction of a specific number of substituents at the desired positions.

[0009] Yan Xiao, Xiaopeng Wu, Hepan Wang, Song Sun, Jin-Tao Yu and Jiang Cheng, Organic Letters, 2019, 21, 2565-2568.Lintao Yu, Xiangge Zhou, Di Wu and Haifeng Xiang, Journal of Organometallic Chemistry,2012, 705, 75-78.Kapileswar Seth, Sudipta Raha Roy and Asit K. Chakraborti, Chemical Communications, 2015, 52, 922-925.Qingqing Liu, Chenggang Ci, He Zhao, Rong Xie, HuanFeng Jiang and Min Zhang, Green Chemistry, 2023, 25, 678-683.Ana Catarina Sousa, M. Conceicao Oliveira, Ligia O. Martins and M. Paula Robalo, Green Chemistry, 2014, 16, 4127-4136.G. Crank and M. I. H. Makin, Journal of Heterocyclic Chemistry, 1989, 26, 1163-1165.A. Wohl and W. Aue, Berichte der Deutschen Chemischen Gesellschaft, 1901, 34, 2442-2450.Mingchen Xie, Jiaheng Cai, Xueqi Wang, Tong Shan, Sinyeong Jung, Hongliang Zhong, Xiaojun Guo, Dongying Zhou and Tao Li, Advanced Optical Materials, 2022, 10, 2102443-2102452.Masato Okazaki, Youhei Takeda, Przemyslaw Data, Piotr Pander, Heather Higginbotham,Andrew P. Monkman and Satoshi Minakata, Chemical Science, 2017, 8, 2677-2686. Elvira Bindewald, Roxana Lorenz, Olaf Hubner, Dominik Brox, Dirk-Peter Herten, Elisabeth Kaifer and Hans-Jorg Himmel, Dalton Transactions, 2015, 44, 3467-3485. Lin Yang, Xin Li, Jiabao Yang, Yi Qu and Jianli Hua, ACS Applied Materials & Interfaces, 2013, 5, 1317-1326. Tatiana Munteanu, Valerie Mazan, Mourad Elhabiri, Camil Benbouziyane, Gabriel Canard, Denis Jacquemin, Oliver Siri and Simon Pascal, Organic Letters, 2023, 25, 3886-3891. Takayuki Kitamura, Hiroyuki Fudemoto, Yuji Wada, Kei Murakoshi, Mitsuhiro Kasuba, Nobuaki Nakashima, Tetsuro Majima and Shozo Yanagida, Journal of the Chemical Society, Faraday Transactions, 1997, 93 (2), 221-229.

[0010] An object of the present invention is to provide a novel phenazine derivative and a method for producing the novel phenazine derivative, which reaction proceeds under mild conditions without using a metal catalyst or enzyme.

[0011] The present invention comprises the following items.

[0012] [1] The phenazine derivative of the present invention is a compound represented by the following general formula (1):

[0013]

[0014] In general formula (1), R １ are each independently a hydrogen atom, a primary amino group (—NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ２ each independently represents an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R ’’ ), sulfinyl group (-S(=O)R'), sulfinamide group (-S(=O)NR'R''), sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), and R ３ are each independently a hydrogen atom, a primary amino group (—NH ２ ), a secondary amino group (—NHR′), an acylamide group (—NHCOR′), a hydroxy group (—OH), or a monovalent organic group, ４ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２), a nitrile group (—CN), or a monovalent organic group; each R′ is independently an alkyl group or an aryl group in which at least one hydrogen atom may be substituted; R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted; and in R′ and R″, the alkyl groups and aryl groups may be the same or different.

[0015] [2] The phenazine derivative according to aspect [1], represented by the following general formula (3): (In general formula (3), R ５ are each independently a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ６ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), R′ is each independently an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, in R′ and R″, the alkyl groups and aryl groups may be the same or different, R ７ and R ８ are each independently a hydrogen atom or a monovalent organic group.

[0016] [3] The phenazine derivative according to aspect [1], represented by the following general formula (5): (In general formula (5), R １０is a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ９ and R １２ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), R′ is an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, In R′ and R″, the alkyl group and the aryl group may be the same or different, and R １１ and R １３ are each independently a hydrogen atom or a monovalent organic group.

[0017] [4] The method for producing a phenazine derivative represented by the general formula (3) of the present invention includes a step of adding an oxidizing agent to an aniline derivative represented by the general formula (2).

[0018]

[0019] In general formulas (2) and (3), R ５ is a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ６ represents an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R ’’), sulfinyl group (-S(=O)R'), sulfinamide group (-S(=O)NR'R''), sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O) ２ R' is a nitrile group (-CN), or a nitrile group (-CN), each R' independently represents an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R'' is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, in R' and R'', the alkyl group and the aryl group may be the same or different, and R ７ and R ８ are each independently a hydrogen atom or a monovalent organic group.

[0020] [5] The method for producing a phenazine derivative represented by the general formula (5) of the present invention includes a step of adding an oxidizing agent to an aniline derivative represented by the general formula (4). (In general formula (4) and general formula (5), R １０ is a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ９ and R １２ are each independently a hydrogen atom, an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２), or a nitrile group (—CN), R′ is an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, In R′ and R″, the alkyl group and the aryl group may be the same or different, and R １１ and R １３ are each independently a hydrogen atom or a monovalent organic group.

[0021] [6] The method for producing the phenazine derivative represented by the general formula (7) of the present invention includes a step of adding an oxidizing agent to the aniline derivative represented by the general formula (2) and the general formula (6). (In general formula (2), general formula (6), and general formula (7), R ５ and R １５ are each independently a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ６ and R １６ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), R′ is each independently an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, in R′ and R″, the alkyl groups and aryl groups may be the same or different, R ７ , R８ , R １７ , and R １８ are each independently a hydrogen atom or a monovalent organic group.

[0022] [7] The method for producing the phenazine derivative represented by the general formula (9) of the present invention includes a step of adding an oxidizing agent to the aniline derivative represented by the general formula (4) and the general formula (8). (In general formula (4), general formula (8), and general formula (9), R １２ and R ２２ are each independently a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ９ , R １０ , R １９ , and R ２０ are each independently a hydrogen atom, an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), R′ is an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, In R′ and R″, the alkyl group and the aryl group may be the same or different, and R １１ , R １３ , R ２１ , and R ２３ are each independently a hydrogen atom or a monovalent organic group.

[0023] The novel phenazine derivatives of the present invention are compounds whose emission wavelengths can be freely designed by controlling the structure of the phenazine derivatives in accordance with the desired absorption and emission wavelengths.

[0024] Furthermore, the novel phenazine derivative of the present invention has high solubility in water and excellent light resistance.

[0025] According to the method for producing a phenazine derivative of the present invention, a phenazine derivative can be synthesized in good yield by simply mixing a relatively easily available aniline derivative with an oxidizing agent without using a catalyst such as a metal or an enzyme or requiring severe reaction conditions.

[0026] Furthermore, by changing the type and position of the substituents on the substrate aniline derivative, it is possible to introduce a substituent at any position on the resulting phenazine derivative, which allows the structure of the phenazine derivative to be freely adjusted to match the desired absorption and emission wavelengths, such as polysubstituted phenazine derivatives.

[0027] Furthermore, in the phenazine derivative of the present invention, not only one molecule of the aniline derivative is used as the substrate, but also two molecules of the aniline derivative are used as the substrate, thereby enabling the preparation of a heterostructure phenazine derivative. By varying the types and positions of the substituents of the two aniline derivative molecules, it is possible to obtain phenazine derivatives with a wider variety of structures with a higher degree of freedom.

[0028] According to the present invention, problems associated with conventional methods, such as limitations on mass-scale production due to the need for selective catalysts and strict reaction conditions, can be overcome, and a variety of phenazine derivatives can be efficiently synthesized.

[0029] For TMsDAP1 (Example 1) and TMsDAP2 (Example 2), the structural formula, fluorescence color, fluorescence spectrum in DMF solution, and absorption maximum wavelength (λ ｍａｘ ａｂｓ ), fluorescence absorption maximum (λ ｍａｘ ｅｍ ), maximum molar extinction coefficient (ε ｍａｘTMsDAP3 (Example 5) is a table showing the absorption spectrum and fluorescence spectrum measurement results in a DMF solution, and the absorption maximum wavelength (λ ｍａｘ ａｂｓ ), fluorescence absorption maximum (λ ｍａｘ ｅｍ ), maximum molar extinction coefficient (ε ｍａｘ 1 shows the light resistance evaluation results of TMsDAP1 (Example 1), TMsDAP2 (Example 2), BMsDAP (Example 3), TMsDAP3 (Example 5), and a comparative fluorescent dye.

[0030] The phenazine derivative of the present invention and its production method will be described in detail below.

[0031] <Phenazine Derivative> The phenazine derivative of the present invention is a compound represented by the following general formula (1). The phenazine derivative of the present invention is a compound whose emission wavelength can be freely designed by controlling the structure of the phenazine derivative to match the desired absorption and emission wavelength. Furthermore, the novel phenazine derivative of the present invention has high solubility in water and excellent light resistance.

[0032] In general formula (1), R １ are each independently a hydrogen atom, a primary amino group (—NH ２ ), a secondary amino group (-NHR'), an acyl amide group (-NHCOR'), or a hydroxy group (-OH).

[0033] In general formula (1), R ２ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２), or an electron-withdrawing group such as a nitrile group (—CN). In the following structural formulas, * indicates the position of the bond.

[0034]

[0035] In general formula (1), R ３ are each independently a hydrogen atom, a primary amino group (—NH ２ ), a secondary amino group (-NHR'), an acylamide group (-NHCOR'), a hydroxy group (-OH), or a monovalent organic group.

[0036] In general formula (1), R ４ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), an electron-withdrawing group such as a nitrile group (—CN), or a monovalent organic group.

[0037] Each R' is independently an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, and each R'' is a hydrogen atom, or an alkyl group or aryl group in which at least one hydrogen atom may be substituted.

[0038] In R' and R'', the alkyl groups and aryl groups may be the same or different.

[0039] The alkyl group is an alkyl group which may be linear or branched and has 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms. Although not particularly limited, examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, and a 2-ethylhexyl group. Of these, a methyl group, an ethyl group, and an isopropyl group are preferred.

[0040] The alkyl group may have at least one hydrogen atom substituted with, for example, a halogen atom, an oxygen atom, a nitrogen atom, etc., within the range that does not impair the effects of the present invention. Specific examples include a trifluoromethyl group in which a hydrogen atom of the alkyl group is substituted with a fluorine atom.

[0041] The aryl group is an aryl group having 6 to 24 carbon atoms. Examples include, but are not limited to, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 4-propylphenyl group, a 4-n-butylphenyl group, a 4-isobutylphenyl group, a 4-t-butylphenyl group, a 4-cyclopentylphenyl group, a 4-cyclohexylphenyl group, a 2,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 3,4-dimethylphenyl group, a 1-biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-phenanthryl group. Of these, the phenyl group, the 2-naphthyl group, and the 9-phenanthryl group are preferred.

[0042] In the aryl group, at least one of the hydrogen atoms constituting the aryl group may be substituted with, for example, a halogen atom, an oxygen atom, a nitrogen atom, or the like, within the range that does not impair the effects of the present invention.

[0043] R ３ and R ４The monovalent organic group that can be taken is various organic groups having various substituents without any particular limitation. Examples of the monovalent organic group include the above-mentioned alkyl group and aryl group, hydrogen atom, alkoxy group, aryloxy group, heteroaryl group, heteroaryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, acyl group, alkylthio group, arylthio group, heteroarylthio group, hydroxy group, silyl group, halogen atom, nitro group, cyano group, amino group, carbamoyl group, ureido group, imido group, alkylsulfonyl group, arylsulfonyl group, and heteroarylsulfonyl group. At least one hydrogen atom of the alkyl group may be substituted with a halogen atom, oxygen atom, nitrogen atom, etc., and may be, for example, a trifluoromethyl group.

[0044] Of the phenazine derivatives of the present invention, those represented by the following general formula (3) are preferred among the compounds represented by the general formula (1).

[0045] In general formula (3), R ５ are each independently a primary amino group (-NH ２ ), a secondary amino group (-NHR'), an acyl amide group (-NHCOR'), or a hydroxy group (-OH).

[0046] In general formula (3), R ６ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN).

[0047] Each R' is independently an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, and each R'' is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted.

[0048] In R' and R'', the alkyl groups and aryl groups may be the same or different.

[0049] In general formula (3), R ７ and R ８ are each independently a hydrogen atom or a monovalent organic group.

[0050] Of the phenazine derivatives of the present invention, those represented by the following general formula (5) are preferred among the compounds represented by the general formula (1).

[0051] In general formula (5), R １０ is a primary amino group (-NH ２ ), a secondary amino group (-NHR'), an acyl amide group (-NHCOR'), or a hydroxy group (-OH).

[0052] In general formula (5), R ９ and R １２ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN).

[0053] R' is an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, and R'' is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted.

[0054] In R' and R'', the alkyl groups and aryl groups may be the same or different.

[0055] In general formula (5), R １１ and R １３ are each independently a hydrogen atom or a monovalent organic group.

[0056] Of the compounds represented by general formula (1), the phenazine derivatives of the present invention are particularly preferably TMsDAP1, TMsDAP2, BMsDAP, TMsDAP3, and TMsDAP4, which are represented by the following structural formulas.

[0057]

[0058]

[0059] The phenazine derivative represented by the general formula (1) exhibits optical absorption, fluorescence, and carrier transport properties derived from π-conjugation. For example, TMsDAP1 emits a fluorescent yellow color, and its absorption maximum wavelength (λ ｍａｘ ａｂｓ ) is 521 nm, and the maximum emission wavelength of the emission spectrum (λ ｍａｘ ｅｍ On the other hand, TMsDAP2 emits a fluorescent orange color, and its absorption maximum wavelength (λ ｍａｘ ａｂｓ ) is 535 nm, and the maximum emission wavelength of the emission spectrum (λ ｍａｘ ｅｍ ) is 626 nm. In particular, TMsDAP1 has a higher molar extinction coefficient (ε) and quantum yield (φ), and a higher fluorescence intensity, compared to TMsDAP2 (Figure 1).

[0060] As described above, the phenazine derivative represented by general formula (1) absorbs light of a specific wavelength and emits highly intense fluorescence, and therefore is expected to be applied to organic EL devices using this as a light-emitting material, bioimaging using fluorescent dyes, and the like.

[0061] <Method for Producing Phenazine Derivative> The method for producing the phenazine derivative represented by general formula (3) of the present invention includes a step of adding an oxidizing agent to the aniline derivative represented by general formula (2).

[0062]

[0063] In the general formula (2) and the general formula (3), R ５ is a primary amino group (-NH ２ ), a secondary amino group (-NHR'), an acyl amide group (-NHCOR'), or a hydroxy group (-OH).

[0064] In the general formula (2) and the general formula (3), R ６ is an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN).

[0065] Each R' is independently an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, and each R'' is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted.

[0066] In R' and R'', the alkyl groups and aryl groups may be the same or different.

[0067] In the general formula (2) and the general formula (3), R ７ and R ８ are each independently a hydrogen atom or a monovalent organic group.

[0068] The aniline derivative represented by the general formula (2) is a compound having an amino group and R ６ The substituent between is a hydrogen atom, and the amino group has a specific substituent (i.e., a primary amino group, a secondary amino group, an acylamide group, or a hydroxy group) at the p-position. The amino group may have a hydrogen atom at both o-positions.

[0069] Furthermore, the aniline derivative represented by the general formula (2) has an amino group and R ２ The substituent between is a hydrogen atom, and in addition to having the specific substituent at the p-position of the amino group, there is also a substituent (=R ６ ) preferably has an electron-withdrawing group. Specific examples of the electron-withdrawing group are as described above. However, among the electron-withdrawing groups, nitro (—NO ２ ) group is not preferred because a phenazine derivative having a nitro group (see Reference Example 1 below) is polarized and does not emit light.

[0070] Such a structure reduces the electron density of the aromatic ring and promotes the addition of an amino group, so that when NBS is added to the aniline derivative represented by general formula (2), a phenazine derivative can be produced without brominating the aromatic ring.

[0071] The method for producing the phenazine derivative represented by the general formula (5) of the present invention includes a step of adding an oxidizing agent to the aniline derivative represented by the general formula (4).

[0072] In the general formula (4) and the general formula (5), R １０ is a primary amino group (-NH ２ ), a secondary amino group (-NHR'), an acyl amide group (-NHCOR'), or a hydroxy group (-OH).

[0073] In the general formula (4) and the general formula (5), R ９ and R １２ are each independently a hydrogen atom, an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN).

[0074] R' is an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, and R'' is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted.

[0075] In R' and R'', the alkyl groups and aryl groups may be the same or different.

[0076] In the general formula (4) and the general formula (5), R １１ and R １３ are each independently a hydrogen atom or a monovalent organic group.

[0077] The method for producing the phenazine derivative represented by the general formula (7) of the present invention includes a step of adding an oxidizing agent to the aniline derivative represented by the general formula (2) and the general formula (6).

[0078] In general formula (2), general formula (6), and general formula (7), R ５ and R １５ are each independently a primary amino group (-NH ２ ), a secondary amino group (-NHR'), an acyl amide group (-NHCOR') or a hydroxy group (-OH).

[0079] In general formula (2), general formula (6), and general formula (7), R ６ and R １６ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN).

[0080] Each R' is independently an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, and each R'' is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted.

[0081] In R' and R'', the alkyl groups and aryl groups may be the same or different.

[0082] In general formula (2), general formula (6), and general formula (7), R ７ , R ８ , R １７ , and R １８ are each independently a hydrogen atom or a monovalent organic group.

[0083] The method for producing the phenazine derivative represented by the general formula (9) of the present invention includes a step of adding an oxidizing agent to the aniline derivative represented by the general formula (4) and the general formula (8).

[0084] In general formula (4), general formula (8), and general formula (9), R １２ and R ２２ are each independently a primary amino group (-NH ２ ), a secondary amino group (-NHR'), an acyl amide group (-NHCOR'), or a hydroxy group (-OH).

[0085] In general formula (4), general formula (8), and general formula (9), R ９ , R １０ , R １９ , and R ２０ are each independently a hydrogen atom, an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２), or a nitrile group (—CN).

[0086] R' is an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, and R'' is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted.

[0087] In R′ and R″, the alkyl group and the aryl group may be the same or different from each other;

[0088] In general formula (4), general formula (8), and general formula (9), R １１ , R １３ , R ２１ , and R ２３ each independently represents a hydrogen atom or a monovalent organic group.

[0089] The method for producing a phenazine derivative of the present invention includes a step of adding an oxidizing agent to a reaction system. The oxidizing agent used in the present invention is not particularly limited as long as it has the ability to remove electrons from other substances. Among these, one-electron oxidizing agents are preferred, and one-electron oxidizing agents with weak Lewis acidity are more preferred because they do not interact with or deactivate functional groups in the aniline derivative substrate.

[0090] Examples of such oxidizing agents include N-bromosuccinimide (NBS), N-chlorosuccinimide (NCS), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), chloranil, 1,3-dibromo-5,5-dimethylhydantoin (DBH), and 1-bromo-3-chloro-5,5-dimethylhydantoin (BCDMH), which are represented by the following chemical formulas.

[0091]

[0092] Here, the reaction mechanism when an oxidizing agent is added to the aniline derivative represented by general formula (2) will be explained using the synthesis method of TMsDAP1 using NBS as an oxidizing agent as an example.

[0093] TMsDAP1 is synthesized using 1,4-diamino-2,5-bis(methylsulfonyl)benzene (2,5-BMeS-p-A) as a substrate via the following synthetic pathway.

[0094]

[0095] When 1 equivalent of NBS is added to the substrate 1,4-diamino-2,5-bis(methylsulfonyl)benzene (2,5-BMeS-p-A), half a molar amount of 2,5-BMeS-p-A is oxidized to produce 2,5-bis(methylsulfonyl)-1,4-quinonediimine.

[0096] In a reaction system containing 2,5-BMeS-p-A and 2,5-bis(methylsulfonyl)-1,4-quinonediimine, 2,5-BMeS-p-A acts as a nucleophile, forming a new bond between the nitrogen of the amino group of 2,5-BMeS-p-A and 2,5-bis(methylsulfonyl)-1,4-quinonediimine, resulting in hydrogen transfer.

[0097] Here, when one equivalent of NBS is added again, oxidation occurs via deprotonation of the amino group, and a cyclization reaction occurs via intramolecular condensation. As a result, the desired TMsDAP1 is produced in good yield by self-condensation of 2,5-BMeS-p-A.

[0098] The reaction proceeds at temperatures between room temperature (25°C) and 50°C, and TMsDAP1 is produced in a yield of 76% when the reaction is carried out at 50°C for 2 hours, and in a yield of 61% when the reaction is carried out at 25°C for 2 hours.

[0099] The phenazine derivative represented by the general formula (1) of the present invention can be synthesized by combining various known methods without being limited to the above method.

[0100] In the above-described method for producing a phenazine derivative of the present invention, even if the derivative has an electron-donating group such as an amino group, the phenazine skeleton is formed via the generation of a quinone diimine without being brominated by the addition of NBS, which is known as a brominating agent. For example, when NBS is added to BMeSA or o-MeSA, which have the structural formulas shown below, as a substrate, NBS acts electrophilically on the aromatic ring, selectively brominating the aromatic ring without generating a quinone imine. In the case of aromatic rings having electron-rich amino groups, such as BMeSA or o-MeSA, bromination with NBS proceeds in a solvent alone.

[0101]

[0102] The phenazine derivative represented by general formula (1) of the present invention can be produced by a very simple and easy method of simply mixing an aniline derivative as a substrate with an oxidizing agent. This method allows the substrate aniline derivative to be selected in accordance with the absorption and emission wavelengths of the target phenazine derivative, and a substituent to be introduced at any position of the phenazine derivative.

[0103] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0104] <Measurement Instruments and Methods> The instruments and methods used to identify the synthesized products in the Examples and Comparative Examples are as follows: (1) １ H nuclear magnetic resonance method ( １ H NMR) Measurement was performed using a 500 MHz ECX-500-NMR manufactured by JEOL Ltd. (2) Absorption spectrum 5.0 × 10 －５ A DMF solution was prepared and measured using a UV-2600i ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation. (3) Fluorescence spectrum 5.0 x 10 －５ A DMF solution was prepared and measured using a spectrofluorometer RF-6000 manufactured by Shimadzu Corporation.

[0105] Example 1: Synthesis and evaluation of TMsDAP1

[0106]

[0107] (Preparation of Phenazine Derivative) A 100 mL three-neck flask equipped with a reflux condenser was purged with nitrogen, and then 100 mg (0.38 mmol) of 1,4-diamino-2,5-bis(methylsulfonyl)benzene (2,5-BMeS-p-A) and 22 mL of dry N,N-dimethylformamide (DMF) were added, followed by stirring at 50° C. for 30 minutes.

[0108] To this solution, 148 mg (0.83 mol) of N-bromosuccinimide (NBS), equivalent to 2.2 equivalents relative to 2,5-BMeS-p-A, was added, and the mixture was stirred at 50°C for 2 hours. Subsequently, TMsDAP1 (61.5 mg, 62%) was obtained as a red solid by membrane filtration. Furthermore, 200 mL of purified water was added to the filtrate, and the mixture was stirred at 0°C for 30 minutes, concentrated, and then subjected to membrane filtration to obtain a brown solid (28.6 mg) as a filtrate. The obtained brown solid was purified by NH silica gel column chromatography (dichloromethane:ethyl acetate = 1:1) to obtain TMsDAP1 (14.3 mg, 14%) as a red solid. The overall yield of TMsDAP1 was 76%. TMsDAP1 emitted yellow light.

[0109] When the synthesis reaction was carried out at 25°C for 2 hours instead of at 50°C for 2 hours, the yield was 61%, indicating that the reaction also proceeds at room temperature.

[0110] ( １ 1 H NMR measurement) of TMsDAP1 １ The results of H NMR measurement are shown below. １ H NMR (500MHz, DMSO-d ６ ): δ = 8.35 (s, 1H, -Ph), 8.12 (s, 2H, -NH ２ ), 3.74 (s, 3H, -CH ３ ), 3.68 (s, 3H, -CH ３ ).

[0111] (Measurement of Fluorescence Spectrum) For TMsDAP1 of Example 1, the wavelength giving the maximum fluorescence intensity was 521 nm. ｍａｘ ａｂｓThe wavelength (λ ) corresponding to the maximum fluorescence intensity at 521 nm excitation light was used as the optimal excitation wavelength, and the fluorescence intensity was measured. ｍａｘ ｅｍ The molar extinction coefficient (ε ｍａｘ ) is 15580M －１ cm －１ The quantum yield (φ) was 0.68. The quantum yield (φ) is the absolute quantum efficiency determined using an integrating sphere. The DMF solution of TMsDAP1 emitted fluorescent light (yellow). The results are shown in Figure 1.

[0112] Example 2: Synthesis and evaluation of TMsDAP2

[0113]

[0114] (Preparation of Phenazine Derivative) A 100 mL three-necked flask equipped with a reflux condenser and a 30 mL dropping funnel was purged with nitrogen, and then 100 mg (0.38 mmol) of 1,4-diamino-2,6-bis(methylsulfonyl)benzene (2,6-BMeS-p-A) and 4 mL of dry DMF were added, followed by stirring at 50° C. for 20 minutes.

[0115] Then, 148 mg of NBS (2.2 equivalents relative to 2,6-BMeS-p-A) and 4 mL of DMF were added to a 30 mL dropping funnel and added dropwise to the 2,6-BMeS-p-A solution over 5 minutes, followed by stirring at 50°C for 2 hours. After cooling for 30 minutes, a purple solid (89.4 mg) was obtained as a filter cake by membrane filtration. 200 mL of dichloromethane was then added to the purple solid, followed by stirring at room temperature (25°C) for 30 minutes and membrane filtration to obtain TMsDAP2 (63.6 mg, 58%) as a purple solid.

[0116] When the synthesis reaction was carried out at 25°C for 2 hours instead of at 50°C for 2 hours, the yield was 36%, indicating that the reaction also proceeds at room temperature.

[0117] ( １ 1 H NMR measurement) of TMsDAP2 １ The results of H NMR measurement are shown below. １ H NMR (500MHz, DMSO-d ６): δ=8.73(s, 1H, -Ph), 3.72(s, 3H, -CH ３ ), 3.52 (s, 3H, -CH ３ ).

[0118] (Measurement of Fluorescence Spectrum) For TMsDAP2, the absorption maximum wavelength (λ ｍａｘ ａｂｓ ) is 535 nm, and the wavelength (λ ) showing the maximum fluorescence intensity with excitation light of 535 nm is ｍａｘ ｅｍ The absorption maximum wavelength (λ ｍａｘ ａｂｓ ) at the molar extinction coefficient (ε ｍａｘ ) is 10680M －１ cm －１ The quantum yield (φ) was 0.28. The DMF solution of TMsDAP2 emitted fluorescent light (orange). The results are shown in Figure 1.

[0119] [Example 3] Synthesis of BMsDAP

[0120]

[0121] (Preparation of Phenazine Derivative) A 50 mL three-necked flask equipped with a reflux condenser and a 30 mL dropping funnel was purged with nitrogen, and then 100 mg (0.53 mmol) of 1,4-diamino-2-methylsulfonylbenzene (2-MeS-p-A) and 4 mL of dry DMF were added, followed by stirring at 50° C. for 20 minutes.

[0122] Next, 191 mg of NBS (2 equivalents relative to 2-MeS-p-A) and 5 mL of DMF were added to a 30 mL dropping funnel and added dropwise to the 2-MeS-p-A solution over 3 minutes. The mixture was then stirred at 50°C for 25 minutes. After cooling for 30 minutes, the mixture was separated into 100 mL of ethyl acetate, 25 mL of hexane, and 400 mL of purified water. The organic layer was concentrated, 30 mL of ethyl acetate was added, and the mixture was filtered to obtain BMsDAP (18.7 mg, 19%) as a brown solid. The filtrate was purified by neutral silica gel column chromatography (ethyl acetate) to obtain BMsDAP (3.8 mg, 3.9%). The total yield of BMsDAP was 23%. BMsDAP exhibited a fluorescent (green) color.

[0123] ( １ 1 H NMR measurement) of BMsDAP １ The results of H NMR measurement are shown below. １ H NMR (500MHz, DMSO-d ６ ): δ = 7.97, 7.95 (d, 1H, -Ph), 7.44, 7.42 (d, 1H, -Ph), 7.67 (2H, -NH ２ ), 3.61 (s, 3H, -CH ３ ).

[0124] [Example 4]

[0125] (Preparation of Phenazine Derivative) In the same manner as in Examples 1 to 3, 1,4-diamino-2,5-ditrifluoromethylsulfonyl-3-(trifluoromethyl)benzene and dry DMF are added to a nitrogen-purged 50 mL three-neck flask equipped with a reflux condenser, and NBS is then added and stirred. After completion of the reaction, the phenazine derivative having the above structural formula is obtained by purifying the mixture.

[0126] [Example 5] Synthesis and evaluation of TMsDAP3

[0127]

[0128] (Preparation of Phenazine Derivative) To a 100 mL three-necked flask equipped with a reflux condenser and a 30 mL dropping funnel, 100 mg (0.38 mmol) of 1,4-diamino-2,5-bis(methylsulfonyl)benzene (2,5-BMeS-p-A), 100 mg (0.38 mmol) of 1,4-diamino-2,6-bis(methylsulfonyl)benzene (2,6-BMeS-p-A), and 32 mL of DMF were added, and the mixture was stirred at 50° C. for 1 hour.

[0129] Then, 296 mg of NBS (4.4 equivalents relative to 2,5-BMeS-p-A and 2,6-BMeS-p-A) and 12 mL of DMF were added to a 30 mL dropping funnel and added dropwise to the 2,5-BMeS-p-A and 2,6-BMeS-p-A solution over 3 minutes, followed by stirring at 50°C for 2 hours. After cooling for 30 minutes, a residue and filtrate were obtained by membrane filtration. The filtrate was concentrated and washed with ethyl acetate, resulting in separation into a residue (5.7 mg) and a filtrate (629 mg). The resulting filtrate was purified by neutral silica gel chromatography (ethyl acetate) to yield TMsDAP3 (58.6 mg, 28%).

[0130] ( １ 1 H NMR measurement) of TMsDAP3 １ The results of H NMR measurement are shown below. １ H NMR (500MHz, DMSO-d ６ ): δ = 8.70 (s, 1H, -Ph), 8.41 (s, 1H, -Ph), 3.75 (s, 3H, -CH ３ ), 3.75(s, 3H, -CH ３ ), 3.64 (s, 3H, -CH ３ ), 3.50(s, 3H, -CH ３ ).

[0131] (Measurement of Fluorescence Spectrum) For TMsDAP3, the absorption maximum wavelength (λ ｍａｘ ａｂｓ ) is 531 nm, and the wavelength (λ ) showing the maximum fluorescence intensity with excitation light of 530 nm is ｍａｘ ｅｍ The absorption maximum wavelength (λ ｍａｘ ａｂｓ ) at the molar extinction coefficient (ε ｍａｘ ) is 11,180M －１ cm －１ The quantum yield (φ) was 0.50. The DMF solution of TMsDAP3 emitted fluorescent light (orange). The results are shown in Figure 2.

[0132] (Evaluation of Solubility) The solubility of TMsDAP3 was calculated by the equilibrium method. 10 mg of TMsDAP3 was added to 2 L of purified water and stirred at room temperature for 12 hours. Then, filtration was performed, and the amount of TMsDAP3 dissolved in water was calculated from the amount of filtrate obtained. As a result, TMsDAP3 showed a solubility of 4.26 mg / L.

[0133] Therefore, TMsDAP3 has high solubility in water and is applicable to bioimaging.

[0134] <Evaluation of Light Fastness> Light fastness was evaluated for TMsDAP1 prepared in Example 1, TMsDAP2 prepared in Example 2, BMsDAP prepared in Example 3, and TMsDAP3 prepared in Example 5. For comparison, light fastness was evaluated for Rhodamine B (manufactured by TCI) and BODIPY (manufactured by TCI, [[(3,5-dimethyl-1H-pyrrol-2-yl)(3,5-dimethyl-2H-pyrrol-2-ylidene)methyl]methane](difluoroborane)), which are highly versatile fluorescent dyes.

[0135] (Measurement of Fluorescence Spectrum) For each compound, 5.0 × 10 －５ A DMF solution of M was prepared and measured using a spectrofluorometer RF-6000 manufactured by Shimadzu Corporation. The measurement conditions were as follows. The results are shown in Figure 3.

[0136] Light source: 150W xenon lamp Distance from light source: 15cm Fluorescence measurement: 1, 3, 5, 10, 15, 30, and 45 minutes after the start of measurement

[0137] As shown in Figure 3, TMsDAP1 prepared in Example 1, TMsDAP2 prepared in Example 2, BMsDAP prepared in Example 3, and TMsDAP3 prepared in Example 5 exhibited higher photostability than Rhodamine B and BODIPY.

[0138] [Example 6] Synthesis and evaluation of TMsDAP4

[0139]

[0140] (Preparation of Phenazine Derivative) 50 mg (0.38 mmol) of 1,2-diamino-3,6-bis(methylsulfonyl)benzene (3,6-BMeS-o-A) and 4 mL of DMF were added to a 50 mL three-necked flask equipped with a reflux condenser and a 30 mL dropping funnel, and the mixture was stirred at 50° C. for 15 minutes.

[0141] Then, 74 mg of NBS (2.2 equivalents relative to 3,6-BMeS-o-A) and 6 mL of DMF were added to a 30 mL dropping funnel and added dropwise to the 3,6-BMeS-o-A solution over 3 minutes, followed by stirring at 50°C for 2 hours. After allowing to cool for 30 minutes, the reaction solution was concentrated to give a solid (116.5 mg). Purification by neutral silica gel chromatography (ethyl acetate) gave TMsDAP4 (22.1 mg, 44%).

[0142] ( １ 1 H NMR measurement) of TMsDAP4 １ The results of H NMR measurement are shown below. １ H NMR (500MHz, DMSO-d ６ ): δ=8.74(2H,NH ２ ), 8.52 (s, 1H, -Ph), 3.78, 3.75 (s, 3H, -CH ３ ).

[0143] Reference Example 1: Synthesis and evaluation of DNDAP

[0144]

[0145] (Preparation of Phenazine Derivative) A 100 mL three-necked flask equipped with a reflux condenser and a 30 mL dropping funnel was purged with nitrogen, and then 1,4-diamino-2-nitrobenzene (2-NO ２ 100 mg (0.65 mmol) of 1-p-A) and 21 mL of DMF were added, and the mixture was stirred at 50° C. for 5 minutes.

[0146] Then, add 2-NO ２ 256 mg of NBS (2.2 equivalents to -p-A) and 7 mL of DMF were added, and 2-NO ２The resulting mixture was added dropwise to the -p-A solution over 3 minutes and stirred at 50°C for 2 hours. After allowing to cool for 30 minutes, a brown solid (1.1 mg) was obtained as a residue by membrane filtration. 700 mL of purified water was added to the filtrate, and the mixture was stirred at room temperature for 15 hours. A black solid (98.2 mg) was obtained as a residue by membrane filtration. The black solid was purified by neutral silica gel chromatography (ethyl acetate) to obtain DNDAP (52.9 mg, 54%).

[0147] ( １ H NMR measurement) of DNDAP １ The results of H NMR measurement are shown below. １ H NMR (500MHz, DMSO-d ６ ): δ=7.93, 7.91 (d, 1H, -Ph), 7.77 (2H, -NH ２ ), 7.53, 7.51 (d, 1H, -Ph).

[0148] The phenazine derivatives of the present invention absorb light of a specific wavelength and emit highly intense fluorescence. Therefore, by using them as light-emitting materials, they are expected to be applicable to organic electroluminescence devices and bioimaging using fluorescent dyes.

Claims

1. A phenazine derivative represented by the following general formula (1): (In general formula (1), R １ are each independently a hydrogen atom, a primary amino group (—NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ２ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), and R ３ are each independently a hydrogen atom, a primary amino group (—NH ２ ), a secondary amino group (—NHR′), an acylamide group (—NHCOR′), a hydroxy group (—OH), or a monovalent organic group, ４ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), a nitrile group (—CN), or a monovalent organic group; R' is each independently an alkyl group or an aryl group in which at least one hydrogen atom may be substituted; R'' is a hydrogen atom, or an alkyl group or aryl group in which at least one hydrogen atom may be substituted; and in R' and R'', the alkyl groups and aryl groups may be the same or different.

2. The phenazine derivative according to claim 1, which is represented by the following general formula (3): (In general formula (3), R ５ are each independently a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ６ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), R′ is each independently an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, in R′ and R″, the alkyl groups and aryl groups may be the same or different, R ７ and R ８ are each independently a hydrogen atom or a monovalent organic group.

3. The phenazine derivative according to claim 1, which is represented by the following general formula (5): (In general formula (5), R １０ is a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ９ and R １２ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), R′ is an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, In R′ and R″, the alkyl group and the aryl group may be the same or different, and R １１ and R １３ are each independently a hydrogen atom or a monovalent organic group.

4. A method for producing a phenazine derivative represented by the following general formula (3), which comprises a step of adding an oxidizing agent to an aniline derivative represented by the following general formula (2). (In general formula (2) and general formula (3), R ５ is a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ６ is an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), R′ is each independently an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, in R′ and R″, the alkyl groups and aryl groups may be the same or different, R ７ and R ８ are each independently a hydrogen atom or a monovalent organic group.

5. A method for producing a phenazine derivative represented by the following general formula (5), which comprises a step of adding an oxidizing agent to an aniline derivative represented by the following general formula (4). (In general formula (4) and general formula (5), R １０ is a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ９ and R １２ are each independently a hydrogen atom, an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), R′ is an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, In R′ and R″, the alkyl group and the aryl group may be the same or different, and R １１ and R １３ are each independently a hydrogen atom or a monovalent organic group.

6. A method for producing a phenazine derivative represented by the following general formula (7), comprising a step of adding an oxidizing agent to aniline derivatives represented by the following general formulas (2) and (6): (In general formula (2), general formula (6), and general formula (7), R ５ and R １５ are each independently a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ６ and R １６ are each independently an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), R′ is each independently an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, in R′ and R″, the alkyl groups and aryl groups may be the same or different, R ７ , R ８ , R １７ , and R １８ are each independently a hydrogen atom or a monovalent organic group.

7. A method for producing a phenazine derivative represented by the following general formula (9), which comprises a step of adding an oxidizing agent to aniline derivatives represented by the following general formulas (4) and (8). (In general formula (4), general formula (8), and general formula (9), R １２ and R ２２ are each independently a primary amino group (-NH ２ ), a secondary amino group (—NHR′), an acyl amide group (—NHCOR′), or a hydroxy group (—OH), and R ９ , R １０ , R １９ , and R ２０ are each independently a hydrogen atom, an alkoxycarbonyl group (-C(=O)OR'), an aryloxycarbonyl group (-C(=O)OR'), a carbonyl group (-C(=O)R'), an amide group (-C(=O)NR'R''), a sulfinyl group (-S(=O)R'), a sulfinamide group (-S(=O)NR'R''), a sulfonyl group (-S(=O) ２ R'), sulfonamide group (-S(=O) ２ NR'R''), sulfonate group (-S(=O) ２ OR'), phosphinyl group (-P(=O)R' ２ ), or a nitrile group (—CN), R′ is an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, R″ is a hydrogen atom, or an alkyl group or an aryl group in which at least one hydrogen atom may be substituted, In R′ and R″, the alkyl group and the aryl group may be the same or different, and R １１ , R １３ , R ２１ , and R ２３ are each independently a hydrogen atom or a monovalent organic group.

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