JP2008195749A - Heteropolycyclic phenazine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound that emits strong fluorescence and exhibits excellent light resistance. <P>SOLUTION: The heteropolycyclic phenazine compound is represented by formula I [wherein R<SP>1</SP>and R<SP>2</SP>are each independently CN or the like; R<SP>3</SP>and R<SP>4</SP>form an -O- group or the like while R<SP>5</SP>and R<SP>6</SP>are each H, or R<SP>5</SP>and R<SP>6</SP>form an -O- group or the like while R<SP>3</SP>and R<SP>4</SP>are each H; R<SP>7</SP>and R<SP>8</SP>are each independently a 1-10C alkyl group or the like]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a compound having a heteropolycyclic phenazine skeleton and a fluorescent dye containing the compound.

  Highly π-conjugated organic compounds consume less energy due to rotational movement within the molecule, and therefore, some are excited by absorbed light energy and then emit the absorbed energy as fluorescence. Such an organic compound is used as a fluorescent dye.

  Examples of the use of such fluorescent dyes include dyes and pigments that are blended in paints and inks, or that color polymer resins and fibers.

  Here, the emission intensity of an organic compound used as a dye containing a fluorescent dye is generally stronger in a solution state than in a solid state. However, for practical use, it is more convenient to use it in a solid state. Moreover, when using for the above uses, it is important that the wavelength of fluorescence coloring light can be adjusted. From such a viewpoint, the present inventors have developed the following compounds and the like that can be used as a synthetic intermediate of a solid fluorescent fluorescent dye, have excellent stability, and can be used for a dye, pigment, or dye. Patent applications have been filed (Patent Documents 1 and 2).

JP 2004-263178 A International Publication No. 2004/072053 Pamphlet

  As described above, various compounds have already been developed as compounds having fluorescence coloring property. However, further variations of organic compounds having various light absorption characteristics and fluorescence characteristics are required.

  Therefore, the problem to be solved by the present invention is a compound that has an absorption characteristic for light of a specific wavelength, can emit high-intensity fluorescence, is excellent in light resistance, and can be synthesized relatively easily. Is to provide.

  In order to solve the above-mentioned problems, the present inventors have intensively studied the synthesis of a novel compound and its fluorescence characteristics. As a result, it was found that a highly π-conjugated phenazine compound has good light absorption characteristics and fluorescence characteristics and can be easily synthesized, and the present invention was completed.

  That is, the heteropolycyclic phenazine compound according to the present invention is represented by the following formula (I).

[Where:
R ¹ and R ² are each independently a C _1-10 alkyl group, a carboxyl group, a cyano group, an aryl group which may have a substituent α, or a heteroaryl group which may have a substituent α. Or an aryl group which may have a substituent α or a heteroaryl group which may have a substituent α together with R ¹ , R ² and the carbon atom adjacent to each other And
R ³ and R ^{4 form} an —O— group, —S— group or —N (R ⁹ ) — group, and R ⁵ and R ⁶ represent a hydrogen atom, or R ⁵ and R ⁶ represent —O—. Forming a group, —S— group or —N (R ⁹ ) — group and R ³ and R ⁴ represent a hydrogen atom, wherein R ⁹ represents a hydrogen atom or a C _1-10 alkyl group;
R ⁷ and R ⁸ independently represent a hydrogen atom, a C _1-10 alkyl group, or an aryl group which may have a substituent α;
The substituent α is selected from the group consisting of an amino group, an alkylamino group, a dialkylamino group, a hydroxyl group, a C _1-10 alkoxy group, a C _1-10 alkyl group, a halogen group, a carboxyl group, an alkoxycarbonyl group, and a cyano group. One or more groups are shown. ]

In the present invention, the “C _1-10 alkyl group” means a linear or branched monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isoamyl, hexyl, heptyl, octyl, nonanyl, decyl and the like. In the definition of R ⁷ and R ⁸ , a C _2-8 alkyl group is preferable, a C _3-7 alkyl group is more preferable, and an n-C _4-6 alkyl group is particularly preferable. In other cases, a C _1-6 alkyl group is preferred, and a C _1-4 alkyl group is more preferred.

  “Aryl group” means an aromatic hydrocarbon group having 6 to 12 carbon atoms. For example, phenyl, naphthyl, biphenyl and the like, and phenyl is preferable as the group.

  “Heteroaryl group” means a 5-membered or 6-membered ring or condensed ring aromatic heterocyclyl group having at least one heteroatom such as a nitrogen atom, oxygen atom or sulfur atom. "Heteroaryl" includes 5-membered heteroaryl groups such as pyrrolyl, imidazolyl, pyrazolyl, thienyl, furyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, thiadiazole; 6-membered heteroaryl groups such as pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl And fused heteroaryl groups such as indolyl, isoindolyl, quinolyl, isoquinolyl, quinolidinyl, benzofuranyl, benzofuranyl, isobenzofuranyl, chromenyl, benzothiophenyl and the like.

An “alkylamino group” refers to a group in which one C _1-10 alkyl group is bonded to an amino group. For example, methylamino, ethylamino, propylamino, isopropylamino, n-butylamino, isobutylamino, tert-butylamino, pentylamino, isoamylamino, hexylamino and the like. The group is preferably a C _1-6 alkylamino group, more preferably a C _1-4 alkylamino group, and particularly preferably a C _1-2 alkylamino group.

The “dialkylamino group” refers to a group in which two C _1-10 alkyl groups are bonded to an amino group. For example, dimethylamino, diethylamino, dipropylamino, diisopropylamino, di (n-butyl) amino, isobutylmethylamino, tert-butylmethylamino, dipentylamino, isoamylmethylamino, dihexylamino and the like. The group is preferably a di (C _1-6 alkyl) amino group, more preferably a di (C _1-4 alkyl) amino group, and particularly preferably a di (C _1-2 alkyl) amino group.

“C _1-10 alkoxy group” means a linear or branched aliphatic hydrocarbon oxy group having 1 to 10 carbon atoms. For example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, hexoxy, heptyloxy, octyloxy, nonanyloxy, decyloxy and the like. The group is preferably a C _1-6 alkoxy group, more preferably a C _1-4 alkoxy group, and particularly preferably a C _1-2 alkoxy group.

  Examples of the “halogen group” include fluoro, chloro, bromo and iodo. Of these, fluoro or chloro is preferable, and fluoro is more preferable.

The “alkoxycarbonyl group” refers to a group in which the C _1-10 alkoxy group is bonded to a carbonyl group. For example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl, pentoxycarbonyl, hexoxycarbonyl and the like. The group is preferably a (C _2-6 alkoxy) carbonyl group, more preferably a (C _3-5 alkoxy) carbonyl group, and particularly preferably an n-butoxycarbonyl group.

When the aryl group or heteroaryl group has a substituent α, the number of the substituent α is not particularly limited. Specifically, for example, when the aryl group formed by R ¹ and R ² together with adjacent carbon atoms is phenyl, the number of substituent α is 1 to 4, more preferably 1 to 3, 1 or 2 is preferable, and 1 is particularly preferable.

  The compound (I) of the present invention includes the following heteropolycyclic phenazine compounds (Ia) to (If).

[Wherein R ⁷ , R ⁸ and substituent α are as defined above; R ¹⁰ and R ¹¹ independently have a C _1-10 alkyl group, a carboxyl group, a cyano group, and a substituent α. An optionally substituted aryl group, or an optionally substituted heteroaryl group; X represents an —O— group, an —S— group or an —N (R ⁹ ) — group; A heteroaryl group; ]

  The fluorescent dye of the present invention contains the phenazine compound.

  The heteropolycyclic phenazine compound of the present invention has excellent absorption characteristics, fluorescence characteristics, and light resistance, and is relatively easy to synthesize. Therefore, the heteropolycyclic phenazine compound of the present invention is extremely useful industrially as a fluorescent dye that can be applied to fluorescent dyes and pigments.

  The heteropolycyclic phenazine compound (I) of the present invention can be produced according to the following synthesis scheme 1.

In the above synthesis scheme, R ^{1 to} R ¹¹ and the substituent α have the same meaning as described above.

  Synthesis scheme 1 is a process for producing a heteropolycyclic phenazine compound (I) by condensing a quinone compound (II) and a diamine compound (III) to form a pyrazine ring. When an ethylene derivative is used as the diamine compound (III), the compound (Ia) or (Ib) can be synthesized. When a benzene derivative is used, the compound (Ic) or (Id) is synthesized. be able to. Further, in the above synthesis scheme 1, compound (Ie) or (If) can be synthesized by using a compound in which the benzene ring of compound (III) which is a benzene derivative is heteroaryl.

  The quinone compound (II) as a starting material may be a commercially available product, synthesized from a commercially available compound by a method known to those skilled in the art, or synthesized according to Scheme 2 described below.

  In Synthesis Scheme 1, the quinone compound (II) and the diamine compound (III) are dissolved in acetic acid and heated. The concentration of the acetic acid solution is not particularly limited, but may be about 0.5 to 10% by mass in total of the compounds (II) and (III).

  The reaction temperature of this reaction may be adjusted as appropriate, for example, from 60 ° C. to about the reflux condition. The reaction time is not particularly limited as long as the consumption of the raw material compound (II) or (III) can be confirmed by thin layer chromatography (TLC) or the like, but is usually about 30 minutes to 12 hours. .

  After completion of the reaction, compound (I) may be purified by methods known to those skilled in the art. For example, the target compound is extracted from the reaction mixture with a highly soluble solvent such as methylene chloride, chloroform, ethyl acetate, the extract is washed with water or brine, dried, the solvent is distilled off, and the residue is chromatographed. Purify by etc.

  The substituent of the heteropolycyclic phenazine compound of the present invention obtained in the above synthesis scheme 1 may be further functionally converted. For example, the carboxyl group that is the substituent α may be esterified to form an alkoxycarbonyl group.

  The quinone compound (II), which is a raw material compound in the above synthesis scheme 1, can be produced by the following synthesis scheme 2.

In the above synthesis scheme, R ^{3 to} R ⁹ have the same meaning as described above. Z represents an -XH group, that is, an -OH group, -SH group, or -NR ⁹ H group.

  In Synthesis Scheme 2, first, a quinone compound (IV) and an aniline compound (V) are coupled to form a quinone compound (VI) in the presence of a catalyst, and a quinone compound forms a furan ring or a pyran ring by a cyclization reaction. Compound (II) is produced.

Since the quinone compound (IV) and the aniline compound (V), which are raw material compounds, have a relatively simple structure, a commercially available product may be used or synthesized from a commercially available compound by a method known to those skilled in the art. In Synthesis Scheme 2 above, the —NR ⁷ R ⁸ group in each compound may be deprotected as appropriate by carrying out the reaction after protecting with an appropriate protecting group.

  The catalyst used in this reaction is not particularly limited as long as it can couple the quinone compound (IV) and the aniline compound (V). For example, a metal salt such as nickel acetate, nickel chloride, or zinc acetate is used. Can do. The solvent is not particularly limited as long as it can dissolve the raw material compound appropriately and does not inhibit the reaction. For example, acetic acid, aqueous acetic acid solution, dimethylformamide (DMF), dimethylacetamide (DMA), etc. Amides can be used.

  The reaction temperature of this reaction may be adjusted as appropriate, for example, from room temperature to about 100 ° C. The reaction time is not particularly limited, and may be until the consumption of the raw material compound can be confirmed by thin layer chromatography (TLC) or the like, but is usually about 2 hours to 10 days.

  After completion of the reaction, it may be purified by a method known to those skilled in the art. For example, the reaction mixture is poured into water, and the resulting precipitate is filtered off and washed with water and then further purified by silica gel chromatography or the like.

  In the next reaction of Synthesis Scheme 2, the quinone compound (VI) obtained in the first reaction in a solvent in the presence of a catalyst is subjected to a ring closure reaction to give a quinone compound (II).

  The catalyst used in the reaction is not particularly limited as long as it is used in a ring-closing reaction of a heterocyclic organic compound. For example, a copper-based catalyst such as copper acetate can be used. The solvent is not particularly limited as long as it can dissolve the raw material compound appropriately and does not inhibit the reaction. For example, acetic acid, acetic acid aqueous solution, dimethyl sulfoxide, or amide such as dimethylformamide or dimethylacetamide is used. be able to.

  The reaction temperature of this reaction may be adjusted as appropriate, and may be, for example, about 50 to 100 ° C. The reaction time is not particularly limited, and may be until the consumption of the raw material compound can be confirmed by thin layer chromatography (TLC) or the like, but is usually about 6 to 24 hours.

  After completion of the reaction, it may be purified by a method known to those skilled in the art. For example, after pouring the reaction mixture into water, the precipitated target compound is further purified by chromatography or the like.

  In Synthesis Scheme 2, the quinone compound (II) can be obtained in one step by devising the starting material compound and reaction conditions. For example, by using a disulfide compound as a raw material compound corresponding to the aniline compound (V), a thiophene compound can be obtained without isolating the thiophenol compound.

  The heteropolycyclic phenazine compound (I) of the present invention can be synthesized relatively easily as described above, and is excellent in absorption characteristics, fluorescence characteristics, and light resistance. It can be applied to pigments. Moreover, since the heteropolycyclic phenazine compound of the present invention has a highly lipophilic structure, it is a general-purpose resin such as polyethylene, polystyrene and polymethyl methacrylate; engineering plastics such as polycarbonate and polyethylene terephthalate; biodegradation such as polylactic acid It is also possible to mix with plastic and make fluorescent plastic.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to implement, and they are all included in the technical scope of the present invention.

  Example 1-1 Synthesis of 4- (4-dibutylamino-2-hydroxyphenyl) -1,2-naphthoquinone

  1,2-Naphthoquinone-4-sulfonic acid sodium salt (1.00 g, 3.84 mmol) and nickel (II) chloride (0.50 g, 3.84 × 10 mmol) were dissolved in DMF (40 mL). The solution was heated to 50 ° C., N, N-dibutyl-3-aminophenol (1.28 g, 5.67 mmol) was added, and the mixture was stirred for 4 hours. After completion of the reaction, the reaction mixture was poured into water. The resulting precipitate was filtered off, washed with water, air-dried, and purified using silica gel column chromatography (developing solvent: dichloromethane / ethyl acetate = 20/1) to obtain the desired compound (0.77 g, yield) as blue powder crystals. Rate: 53%).

Melting point: 142-144 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 0.98 (6H, t), 1.24-1.43 (4H, m), 1.58-1.66 (4H, m), 3.31 (4H, t), 5.37 (1H, s), 6.23 (1H, d), 6.33 (1H, dd), 6.51 (1H, s), 7.07 (1H, d), 7.45 (1H, dd), 7.49 (1H, td), 7.59 (1H, td), 8.15 (1H, dd)
IR spectrum (KBr): 3365, 3241, 1693, 1640, 1606 cm ^-1
Elemental analysis _{(C 24 H 27 NO 3)} : measurement -C: 76.06, H: 7.01, N: 12.54, Calculated -C: 76.36, H: 7.21, N: 12.74

  Example 1-2 9-Dibutylamino-benzo [b] naphtho [1,2-d] furan-5,6-dione, and 9-dibutylamino-benzo [kl] xanthene-2,3-dione

  The naphthoquinone compound (1.44 g, 3.81 mmol) obtained in Example 1-1 and anhydrous copper (II) acetate (0.69 g, 3.81 mmol) are dissolved in DMSO (45 mL) and heated at 90 ° C. for 11 hours. Stir. After completion of the reaction, the reaction mixture was poured into water and the resulting precipitate was filtered off. Methylene chloride was added to the precipitate separated by filtration to extract the target compound. The obtained methylene chloride extract was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: dichloromethane / ethyl acetate = 10/1) to give a naphthofuran derivative (0.22 g, yield: 15) as green powder crystals. %), And a benzoxanthene derivative (0.95 g, yield: 66%) as purple powder crystals.

Naphthofuran derivative melting point: 149-153 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 1.00 (6H, t), 1.37-1.50 (4H, m), 1.62-1.74 (4H, m), 3.34 (4H, t), 6.44 (1H, d), 6.74 (1H, dd), 7.36 (1H, td), 7.57 (1H, td), 7.71 (1H, d), 7.78 (1H, dd), 7.96 (1H, dd)
IR spectrum (KBr): 2956, 2926, 2872, 1689, 1645, 1619, 1547, 1519, 1490, 1394, 1370 cm ^-1
Elemental analysis _{(C 24 H 25 NO 3)} : measurement -C: 76.91, H: 6.83, N: 3.76, Calculated -C: 76.77, H: 6.71, N: 3.73
Benzoxanthene derivative melting point: 132-134 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 0.97 (6H, t), 134-1.43 (4H, m), 1.57-1.65 (4H, m), 3.34 (4H, t), 6.20 (1H, d), 6.50 (1H, s), 6.58 (1H, dd), 7.39 (1H, dd), 7.49 (1H, dd), 7.56 (1H, d), 7.89 (1H, d)
IR spectrum (KBr): 2956, 2929, 2871, 1645, 1617, 1546, 1521, 1490, 1394, 1368 cm ^-1
Elemental analysis _{(C 24 H 25 NO 3)} : measurement -C: 76.88, H: 6.90, N: 3.59, Calculated -C: 76.77, H: 6.71, N: 3.73

  Example 1-3 Heteropolycyclic phenazine compound

  The benzoxanthene derivative (0.500 g, 1.33 mmol) and diaminomaleonitrile (0.215 g, 2.00 mmol) obtained in Example 1-2 were dissolved in acetic acid (50 mL) and stirred at 110 ° C. for 8 hours. After completion of the reaction, the target compound was extracted from the reaction mixture with methylene chloride. The methylene chloride extract was washed with water and concentrated under reduced pressure, and the residue was purified using silica gel column chromatography (solvent: dichloromethane). The target compound (0.29 g, yield: 34%) of brown powder crystals was obtained.

Melting point: 229-232 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 1.04 (6H, t), 1.41-1.50 (4H, m), 1.66-1.74 (4H, m), 3.42 (4H, t), 6.31 (1H, d), 6.56 (1H, dd), 7.10 (1H, s), 7.35 (1H, d), 7.46 (1H, d), 7.61 (1H, t), 8.38 (1H, d)
IR spectrum (KBr): 2959, 2831, 2872, 2227, 1632, 1595, 1548, 1527, 1506, 1427, 1397, 1359 cm ⁻¹

  Example 2 Heteropolycyclic phenazine compound

  The naphthoquinone derivative (1.00 g, 2.66 mmol) obtained in Example 1-2 and 3,4-diaminobenzoic acid (0.41 g, 2.66 mmol) were dissolved in acetic acid (50 mL) and 1. Stir for 5 hours. After completion of the reaction, the target compound was extracted from the reaction mixture with methylene chloride. The methylene chloride extract was washed with water, concentrated under reduced pressure, and then dried to obtain a mixture of target compounds (1.138 g, crude yield: 87%) as red powder crystals. The obtained heteropolycyclic phenazine compound was used in Example 3 below without further purification.

  Example 3 Heteropolycyclic phenazine compound

  A mixture (1.00 g, 2.03 mmol) of the heteropolycyclic phenazine compound obtained in Example 2, 1-iodobutane (0.70 g, 3.81 mmol), and sodium carbonate (0.51 g, 4.82 mmol) were added. Dissolved in DMF (50 mL) and stirred at 110 ° C. for 1 hour. After completion of the reaction, the target compound was extracted from the reaction mixture with methylene chloride. The methylene chloride extract was washed with water and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent; dichloromethane / n-hexane = 2/1) to give a heteropolycyclic phenazine compound (Example 3) as red powder crystals. (1)) (0.502 g, yield: 46%), a heteropolycyclic phenazine compound (Example 3 (2)) (0.479 g, yield: 44%) of deep red powder crystals was obtained.

Heteropolycyclic phenazine compound (Example 3 (1))
Melting point: 195-199 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 1.00-1.06 (9H, m), 1.39-1.48 (4H, m), 1.54-1.63 (2H, m), 1.65-1.72 (4H, m), 1.81-1.88 (2H, m), 3.41 (4H, t), 4.45 (2H, t), 6.85 (1H, dd), 7.04 (1H, d), 7.75 (1H, td), 7.88 (1H, td), 8.10 ( 1H, d), 8.34-8.42 (2H, m), 8.48 (1H, d), 9.15 (1H, d), 9.45 (1H, dd)
IR spectrum (KBr): 2954, 2929, 2871, 1717, 1626, 1518, 1415, 1403, 1365, 1253, 1229, 1213, 1121, 1099 cm ⁻¹
Elemental analysis _{(C 35 H 37 N 3 O} 3): measurement -C: 76.69, H: 6.82, N: 7.70, Calculated -C: 76.75, H: 6.81, N: 7.67
Heteropolycyclic phenazine compound (Example 3 (2))
Melting point: 158-164 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 1.00-1.07 (9H, m), 1.39-1.48 (4H, m), 1.54-1.67 (2H, m), 1.68-1.83 (4H, m), 1.85-1.90 (2H, m), 3.41 (4H, t), 4.46 (2H, t), 6.85 (1H, dd), 7.02 (1H, d), 7.77 (1H, td), 7.88 (1H, td), 8.11 ( 1H, d), 8.39-8.45 (2H, m), 8.49 (1H, d), 9.03 (1H, d), 9.46 (1H, dd)
IR spectrum (KBr): 2959, 2930, 2871, 1712, 1626, 1586, 1524, 1517, 1496, 1398, 1367, 1351, 1306, 1291, 1254, 1192, 1122, 1098 cm ⁻¹
Elemental analysis _{(C 35 H 37 N 3 O} 3): measurement -C: 77.05, H: 6.82, N: 7.75, Calculated -C: 76.75, H: 6.81, N: 7.67

  Example 4 Heteropolycyclic phenazine compound

  The benzoxanthene derivative (1.00 g, 2.66 mmol) obtained in Example 1-2 and 3,4-diaminobenzoic acid (0.41 g, 2.66 mmol) were dissolved in acetic acid (50 mL). Stir for hours. After completion of the reaction, the product was extracted from the reaction mixture with methylene chloride. The methylene chloride extract was washed with water, concentrated under reduced pressure, and dried to obtain a mixture of heteropolycyclic phenazine compounds (1.218 g, crude yield: 93%) as red powder crystals. The obtained heteropolycyclic phenazine compound was used in Example 5 below without further purification.

  Example 5 Heteropolycyclic phenazine compound

  A mixture of heteropolycyclic phenazine compounds obtained in Example 4 (2.00 g, 4.07 mmol), 1-iodobutane (1.40 g, 7.63 mmol), and sodium carbonate (1.02 g, 9.67 mmol). Dissolved in DMF (100 mL) and stirred at 110 ° C. for 2 hours. After completion of the reaction, the product was extracted from the reaction mixture with methylene chloride. The methylene chloride extract was washed with water and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: dichloromethane). Heteropolycyclic phenazine compound of red powder crystal (Example 5 (1)) (1.260 g, yield: 57%), heteropolycyclic phenazine compound of deep red powder crystal (Example 5 (2)) ( 0.365 g, yield: 10%) was obtained.

Heteropolycyclic phenazine compound (Example 5 (1))
Melting point: 197-199 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 0.99-1.06 (9H, m), 1.37-1.47 (4H, m), 1.53-1.69 (6H, m), 1.81-1.88 (2H, m), 3.34 (4H , T), 4.44 (2H, t), 6.34 (1H, d), 6.58 (1H, dd), 7.41 (1H, d), 7.67 (1H, s), 7.73 (1H, t), 7.84 (1H, d), 8.10 (1H, dd), 8.33 (1H, dd), 8.91 (1H, d), 8.93 (1H, dd)
IR spectrum (KBr): 2955, 2931, 2871, 1713, 1631, 1598, 1525, 1405, 1362, 1262, 1225, 1191 cm ⁻¹
Elemental analysis _{(C 35 H 37 N 3 O} 3): measurement -C: 76.74, H: 6.81, N: 7.62, Calculated: C: 76.75, H: 6.81 , N: 7.67
Heteropolycyclic phenazine compound (Example 5 (2))
Melting point: 142-156 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 0.98-1.05 (9H, m), 1.37-1.47 (4H, m), 1.52-1.69 (6H, m), 1.80-1.87 (2H, m), 3.35 (4H , T), 4.43 (2H, t), 6.35 (1H, d), 6.59 (1H, dd), 7.42 (1H, dd), 7.69 (1H, s), 7.72 (1H, t), 7.85 (1H, d), 8.23 (1H, dd), 8.28 (1H, dd), 8.83 (1H, d), 8.94 (1H, dd)
IR spectrum (KBr): 2956, 2930, 2872, 1712, 1624, 1601, 1527, 1434, 1403, 1375, 1361, 1226, 1194 cm ⁻¹
Elemental analysis _{(C 35 H 37 N 3 O} 3): measurement -C: 76.61, H: 6.87, N: 7.63, Calculated -C: 76.75, H: 6.81, N: 7.67

  Example 6-1 9-dibutylaminobenzo [b] naphtho [1,2-d] thiophene-5,6-dione

  In a three-necked flask, 1,2-naphthoquinone-4-sulfonic acid sodium salt (1.21 g, 4.65 mmol), 3,3′-di (dibutylamino) phenyl disulfide (1.10 g, 2.33 mmol) and nickel chloride 6 Hydrate (1.11 g, 4.65 mmol) was dissolved in acetic acid (33 mL) and stirred at 80 ° C. for 22 hours. After completion of the reaction, the reaction mixture was poured into water (400 mL), and the resulting precipitate was filtered off. Methylene chloride was added to the precipitate separated by filtration to extract the target compound. The resulting methylene chloride extract was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: dichloromethane / ethyl acetate = 10/1) to give the desired compound (0.569 g, yield: 31) as blue powder crystals. %).

Melting point: 221-224 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 1.00 (6H, t), 1.37-1.46 (4H, m), 1.61-1.69 (4H, m), 3.40 (4H, t), 6.90-6.92 (2H, m ), 7.44 (1H, td), 7.65 (1H, td), 8.15 (1H, dd), 8.23 (1H, d), 8.29 (1H, d)
IR spectrum (KBr): 2957, 2928, 2870, 1687, 1625, 1586, 1502, 1482, 1358 cm ^-1

  Example 6-2 Heteropolycyclic phenazine compound

  The benzonaphthothiophene derivative (500 mg, 128 mmol) obtained in Example 6-1 and 3,4-diaminobenzoic acid (0.195 g, 1.28 mmol) were dissolved in acetic acid (30 mL) and stirred at 110 ° C. for 2 hours. . After completion of the reaction, the reaction mixture was poured into water (400 mL). The resulting precipitate was filtered off, washed with water and dried. A mixture (638 mg, crude yield: 98%) of a heteropolycyclic phenazine compound as red powder crystals was obtained. The obtained heteropolycyclic phenazine compound was used in Example 7 below without further purification.

  Example 7 Heteropolycyclic phenazine compound

  Dissolve the mixture of symmetrical phenazine compounds obtained in Example 6-2 (638 mg, 1.26 mmol), 1-iodobutane (434 mg, 2.36 mmol), and sodium carbonate (316 g, 2.98 mmol) in DMF (20 mL). And stirred at 110 ° C. for 1 hour. After completion of the reaction, the reaction mixture was filtered. The target compound was extracted from the filtrate with methylene chloride. The methylene chloride extract was washed with water and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: dichloromethane) to give a heteropolycyclic phenazine compound (Example 7 (1)) (0 261 g, yield: 37%) and a heteropolycyclic phenazine compound (Example 7 (2)) (0.313 g, yield: 44%) of deep red powder crystals.

Heteropolycyclic phenazine compound (Example 7 (1))
Melting point: 168-171 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 1.01-1.07 (9H, m), 1.40-1.50 (4H, m), 1.54-1.73 (6H, m), 1.83-1.90 (2H, m), 3.42 (4H , T), 4.45 (2H, t), 6.94 (1H, dd), 7.15 (1H, d), 7.75 (1H, td), 7.88 (1H, td), 8.31-8.38 (2H, m), 8.54 ( 1H, d), 8.83 (1H, d), 9.00 (1H, d), 9.49 (1H, dd)
IR spectrum (KBr): 2956, 2931, 2870, 1715, 1600, 1536, 1526, 1416, 1253, 1208 cm ^-1
Elemental analysis _{(C 35 H 37 N 3 O} 2 S): measurements -C: 74.64, H: 6.63, N: 7.74, Calculated -C: 74.57, H: 6.62, N: 7.45
Heteropolycyclic phenazine compound (Example 7 (2))
Melting point: 221-224 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 1.01-1.07 (9H, m), 1.40-1.49 (4H, m), 1.54-1.72 (6H, m), 1.83-1.90 (2H, m), 3.42 (4H , T), 4.46 (2H, t), 6.84 (1H, dd), 7.14 (1H, d), 7.76 (1H, td), 7.86 (1H, td), 8.29 (1H, d), 8.39 (1H, dd), 8.55 (1H, d), 8.83 (1H, d), 9.01 (1H, d), 9.49 (1H, dd)
IR spectrum (KBr): 2955, 2931, 2871, 1713, 1602, 1573, 1538, 1524, 1413, 1365, 1345, 1292, 1250, 1195, 1091 cm ⁻¹
Elemental analysis _{(C 35 H 37 N 3 O} 2 S): measurements -C: 74.61, H: 6.75, N: 7.69, Calculated -C: 74.57, H: 6.62, N: 7.45

  Example 8 Heteropolycyclic phenazine compound

  The benzonaphthothiophene derivative (500 mg, 128 mmol) obtained in Example 6-1 and 2,3-diamino-5-bromopyridine (313 mg, 1.66 mmol) were dissolved in acetic acid (40 mL) and stirred at 110 ° C. for 11 hours. did. After completion of the reaction, the reaction mixture was poured into water (500 mL), and the resulting precipitate was filtered off. Methylene chloride was added to the precipitate separated by filtration to extract the target compound. The resulting methylene chloride extract was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: dichloromethane / ethyl acetate = 10/1) to give a deep red powder crystal heteropolycyclic phenazine compound (Example 8). (1)) (83 mg, yield: 12%) and a deep red powder crystal heteropolycyclic phenazine compound (Example 8 (2)) (174 mg, yield: 25%) were obtained.

Heteropolycyclic phenazine compound (Example 8 (1))
Melting point: 231 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 1.03 (6H, t), 1.40-1.50 (4H, m), 1.55-1.73 (4H, m), 3.42 (4H, t), 6.93 (1H, dd), 7.13 (1H, d), 7.70 (1H, td), 7.84 (1H, td), 8.50 (1H, d), 8.75 (1H, d), 8.78 (1H, d), 9.20 (1H, d), 9.30 (1H, dd)
IR spectrum (KBr): 2953, 2930, 2869, 1601, 1590, 1534, 1520, 1480, 1423, 1408, 1362, 1347, 1217, 1180, 1051, 1033 cm ⁻¹
Heteropolycyclic phenazine compound (Example 8 (2))
Melting point: 233 ° C
¹ H-NMR spectrum (CDCl ₃ ) δ = 1.01 (6H, t), 1.40-1.50 (4H, m), 1.55-1.73 (4H, m), 3.42 (4H, t), 6.93 (1H, dd), 7.09 (1H, d), 7.73 (1H, td), 7.86 (1H, td), 8.50 (1H, d), 8.75 (1H, d), 8.77 (1H, d), 9.17 (1H, d), 9.53 (1H, dd)
IR spectrum (KBr): 2954, 2927, 2869, 1602, 1588, 1523, 1481, 1405, 1365, 1218, 1182, 1051, 1032 cm ⁻¹

Test Example 1 Measurement of Light Absorption Property and Fluorescence Property The light absorption property and fluorescence property of the heteropolycyclic phenazine compound produced above were measured. Specifically, a fluorescent dye is dissolved in 1,4-dioxane to prepare a solution having a concentration of 2.5 × 10 ⁻⁵ M, and an ultraviolet / visible spectrophotometer (product name: Ubest-30, manufactured by JASCO Corporation). ) Was used to measure the ultraviolet / visible absorption spectrum. The result is defined as a light absorption characteristic. Further, the solution prepared above was diluted 10-fold with 1,4-dioxane to prepare a solution having a concentration of 2.5 × 10 ⁻⁶ M, and a fluorescence spectrophotometer (product name: FR- manufactured by JASCO Corporation). 777) was used to measure the fluorescence spectrum. The results are shown in Table 1.

  As shown in Table 1, the heteropolycyclic phenazine compound of the present invention emits strong orange to red fluorescence having a large Stokes shift value. Therefore, it was demonstrated that the heteropolycyclic phenazine compound of the present invention is extremely excellent as a fluorescent dye.

Claims (5)

A heteropolycyclic phenazine compound represented by the following formula (I):

[Where:
R ¹ and R ² are each independently a C _1-10 alkyl group, a carboxyl group, a cyano group, an aryl group which may have a substituent α, or a heteroaryl group which may have a substituent α. Or an aryl group which may have a substituent α or a heteroaryl group which may have a substituent α together with R ¹ , R ² and the carbon atom adjacent to each other And
R ³ and R ^{4 form} an —O— group, —S— group or —N (R ⁹ ) — group, and R ⁵ and R ⁶ represent a hydrogen atom, or R ⁵ and R ⁶ represent —O—. Forming a group, —S— group or —N (R ⁹ ) — group and R ³ and R ⁴ represent a hydrogen atom, wherein R ⁹ represents a hydrogen atom or a C _1-10 alkyl group;
R ⁷ and R ⁸ independently represent a hydrogen atom, a C _1-10 alkyl group, or an aryl group which may have a substituent α;
The substituent α is selected from the group consisting of an amino group, an alkylamino group, a dialkylamino group, a hydroxyl group, a C _1-10 alkoxy group, a C _1-10 alkyl group, a halogen group, a carboxyl group, an alkoxycarbonyl group, and a cyano group. One or more groups are shown. ] The heteropolycyclic phenazine compound according to claim 1, which is represented by the following formula (Ia) or (Ib).

[Wherein R ⁷ and R ⁸ have the same meanings as described above, and R ¹⁰ and R ¹¹ may independently have a C _1-10 alkyl group, a carboxyl group, a cyano group, or a substituent α. A good aryl group or a heteroaryl group optionally having substituent α; X represents an —O— group, —S— group or —N (R ⁹ ) — group; Synonymous with things. ] The heteropolycyclic phenazine compound according to claim 1 represented by the following formula (Ic) or (Id).

[Wherein R ⁷ , R ⁸ and substituent α are as defined above, and X represents an —O— group, an —S— group or an —N (R ⁹ ) — group. ] The heteropolycyclic phenazine compound according to claim 1 represented by the following formula (Ie) or (If).

[Wherein, R ⁷ , R ⁸ and substituent α are as defined above; X represents an —O— group, an —S— group or an —N (R ⁹ ) — group; and A represents a heteroaryl group. Indicates. ]   A fluorescent dye comprising the heteropolycyclic phenazine compound according to any one of claims 1 to 4.