JP2017088879A - Method for producing aminobenzopyranoxanthene (abpx) dye compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an aminobenzopyranoxanthene (ABPX) dye compound in a high yield.SOLUTION: The method for producing an ABPX compound represented by formula (3) comprises reacting a compound represented by formula (1) with a compound represented by formula (2) in the presence of a condensing agent. [Each Ris independently H, a 1-6C alkyl group, or the like; Rand Rare each independently H, an alkyl group, or the like, provided that at least one of Rand Ris an alkyl group or the like; Rand Rare each independently a halogen atom, a 1-6C alkyl group, or a carboxyl group; m is an integer of 0-3; and n is an integer of 0-4.]SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an aminobenzopyranoxanthene-based (ABPX) dye compound.

  Aminobenzopyranoxanthene-based (ABPX) dye compounds condensed with two rhodamine molecules are organic dye compounds that exhibit single-molecule polychromaticity, and are widely applied as sensing materials by utilizing their optical properties. (Patent Document 1 and Non-Patent Documents 1 and 2).

  In aminobenzopyranoxanthene-based (ABPX) dye compounds, it is known that derivatives fused to the nitrogen moiety of the xanthene ring structure have higher luminous efficiency and change in absorption wavelength and fluorescence wavelength. In the conventional synthesis method using a melt-heat reaction between a derivative and resorcinol, the production of by-products such as rhodol (Rhodol) has a problem in that the reaction yield is reduced, which is not practical (non-practical). Patent Document 3).

U.S. Pat. No. 8,134,017

Y. Shirasaki et al., "New Aminobenzopyranoxanthene-Based Colorimetric Sensor for Copper (II) Ions with Dual-Color Signal Detection System", Chem. Asian. J, 2013, 8, p.2609-2613 M. Tanioka et al., "Reversible Near-Infrared / Blue Mechanofluorochromism of Aminobenzopyranoxanthene", J. Am. Chem. Soc., 2015, 137, p.6436-6439 S. Kamino et al., "Design and Syntheses of Highly Emissive Aminobenzopyrano-xanthene Dyes in the Visible and Far-Red Regions", Org. Lett., 2014, 16, p.258-261

Therefore, an object of the present invention is to provide a production method capable of obtaining an aminobenzopyranoxanthene-based (ABPX) dye compound with high yield.
The present invention also provides an aminobenzopyranoxanthene-based (ABPX) dye compound in which two nitrogen atoms of a xanthene ring structure have an asymmetric substituent, and a substituent in which two phenyl ring structures are asymmetric, which could not be synthesized conventionally. It is an object of the present invention to provide a method for producing an aminobenzopyranoxanthene-based (ABPX) dye compound having the following.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the following manufacturing method can solve the above-described problems, and have come to the present invention.

  That is, the present invention provides the following inventions.

<1>
A compound represented by the following general formula (3), characterized in that a compound represented by the following general formula (1) and a compound represented by the following general formula (2) are reacted in the presence of a condensing agent. Production method.

[In General Formulas (1) to (3), each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, or two R ¹ bonded to each other. May form a ring, or may form a heterocycle together with the nitrogen atom to which R ¹ is bonded. R ² and R ⁴ each independently represent a hydrogen atom or a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. However, at least one of R ² and R ⁴ is a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. R ³ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but a plurality of R ³ may be bonded to form a ring. R ⁸ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but R ¹ and R ⁸ may be bonded to form a ring. m shows the number of 0-3. n shows the number of 0-4. ]

<2>
The compound represented by general formula (1) and the compound represented by general formula (2) are reacted in the presence of a condensing agent to obtain a compound represented by general formula (4),
Next, the compound represented by the general formula (4) and the compound represented by the general formula (5) are reacted in the presence of a condensing agent to obtain a compound represented by the general formula (6).
Furthermore, the compound represented by the general formula (6) is cyclized. A method for producing the compound represented by the general formula (7).

[In General Formulas (1) to (2) and (4) to (7), R ¹ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Or two R ^{1 s} or two R ^{5 s} may be bonded to form a ring, or a heterocycle may be formed together with the nitrogen atom to which R ¹ or R ⁵ is bonded. . R ² , R ⁴ and R ⁶ each independently represent a hydrogen atom or a group selected from an alkyl group, an acyl group, a silyl group and a tetrahydropyranyl group. However, at least one of R ² and R ⁴ is a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. R ³ and R ⁷ are each independently a halogen atom or an alkyl group or a carboxyl group having 1 to 6 carbon atoms, may form a ring plurality of R ³ s or more R ⁷ are bonded to each other . R ⁸ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but R ¹ and R ⁸ may be bonded to form a ring. R ⁹ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group, but R ⁵ and R ⁹ may be bonded to form a ring. m shows the number of 0-3. n shows the number of 0-4. o shows the number of 0-3. p shows the number of 0-4. ]

<3>
The compound represented by General formula (7).

[In the general formula (7), R ¹ and R ⁵ each independently represent a hydrogen atom, or an alkyl group or an aryl group having 6 to 14 carbon atoms having 1 to 6 carbon atoms, the two R ¹ together or two R ⁵ may be bonded to each other to form a ring, or a heterocycle may be formed together with the nitrogen atom to which R ¹ or R ⁵ is bonded. R ³ and R ⁷ are each independently a halogen atom or an alkyl group or a carboxyl group having 1 to 6 carbon atoms, may form a ring plurality of R ³ s or more R ⁷ are bonded to each other . R ⁸ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but R ¹ and R ⁸ may be bonded to form a ring. R ⁹ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group, but R ⁵ and R ⁹ may be bonded to form a ring. However, at least one of R ¹ and R ⁵ , R ³ and R ⁷ and R ⁸ and R ⁹ is different from each other. m shows the number of 0-3. n shows the number of 0-4. o shows the number of 0-3. p shows the number of 0-4. ]

<4>
The compound represented by General formula (4).

[In General Formula (4), each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, or two R ¹ 's bonded to form a ring. Or may form a heterocycle together with the nitrogen atom to which R ¹ is bonded. R ² and R ⁴ each independently represent a hydrogen atom or a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. However, at least one of R ² and R ⁴ is a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. R ³ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group, but a plurality of R ³ may be bonded to form a ring. R ⁸ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but R ¹ and R ⁸ may be bonded to form a ring. m shows the number of 0-3. n shows the number of 0-4. ]

  According to the present invention, an aminobenzopyranoxanthene-based (ABPX) dye compound can be obtained with high yield. Furthermore, according to the production method of the present invention, an aminobenzopyranoxanthene-based (ABPX) dye compound in which two nitrogen atoms of the xanthene ring structure have an asymmetric substituent, and two phenyl ring structures, which could not be synthesized conventionally, It is possible to synthesize aminobenzopyranoxanthene (ABPX) dye compounds having an asymmetric substituent.

  Hereinafter, the present invention will be described in detail.

First, the manufacturing method of the compound represented by following General formula (3) is demonstrated.
This method is characterized by reacting a compound represented by the following general formula (1) and a compound represented by the following general formula (2) in the presence of a condensing agent.

[In General Formulas (1) to (3), each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, or two R ¹ bonded to each other. May form a ring, or may form a heterocycle together with the nitrogen atom to which R ¹ is bonded. R ² and R ⁴ each independently represent a hydrogen atom or a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. However, at least one of R ² and R ⁴ is a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. R ³ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but a plurality of R ³ may be bonded to form a ring. R ⁸ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but R ¹ and R ⁸ may be bonded to form a ring. m shows the number of 0-3. n shows the number of 0-4. ]

The alkyl group having 1 to 6 carbon atoms of R ^{1 in} the general formulas (1) and (3) may be linear or branched and includes a cycloalkyl group and a bicycloalkyl group. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group and the like.

The aryl group having 6 to 14 carbon atoms of R ^{1 in} the general formulas (1) and (3) may be monocyclic or polycyclic, and two or more benzene rings or condensed rings are single. A group bonded through a bond, a group bonded through a divalent organic group (for example, an alkenylene group such as vinylene group), and a heteroaryl group are also included. Specifically, phenyl group, alkylphenyl group, alkoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 2-biphenyl group, 3-biphenyl group 4-biphenyl group, thienyl group, pyridyl group, indolyl group and the like. The hydrogen atom of the aryl group may be substituted with a halogen atom or the like. Among these, a phenyl group is preferable.

When two R ¹ are bonded to form a ring, the two R ¹ may be bonded through a hetero atom such as an oxygen atom or a sulfur atom. As a case where two R ^1s are bonded to form a ring, for example, the following structures may be mentioned when expressed together with the nitrogen atom to which R ¹ is bonded.

As if together with the nitrogen atom to which R ¹ is attached form a heterocyclic ring, it expressed together with the nitrogen atom to which R ¹ is bonded, for example, the following structure.

In the general formulas (1) and (3), two R ^{1 s} may be the same or different. The case where two of R ¹ are different, for example, one R ¹ is an alkyl group, the other one R ¹ can be mentioned structure forming a hetero ring together with the nitrogen atom to which R ¹ is attached.

In the general formulas (1) to (3), examples of the alkyl group represented by R ² and R ⁴ include those having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, which may be linear or branched. Groups and bicycloalkyl groups are also included. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group and the like. Of these, the alkyl group of R ⁴ is preferably a methyl group, an ethyl group or an isopropyl group.
The alkyl group of R ² and R ⁴ may have a substituent. Examples of the substituent include alkoxy groups such as methoxy group and ethoxy group; aryl groups such as phenyl group; alkoxyaryl groups such as methoxyphenyl group and ethoxyphenyl group.
Of those described above, a methyl group, a methoxymethyl group, a benzyl group, a methoxybenzyl group, and the like are preferable, and a methyl group is particularly preferable because of ease of synthesis.

In general formulas (1) to (3), examples of the acyl group represented by R ² and R ⁴ include an acetyl group, a pivaloyl group, and a benzoyl group.

In the general formulas (1) to (3), as the silyl group of R ² and R ⁴ , a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a t-butyldimethylsilyl group; A diphenylsilyl group etc. are mentioned.

In general formulas (1) to (3), examples of the halogen atom represented by R ³ and R ⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Moreover, as a C1-C6 alkyl group, linear or branched may be sufficient and a cycloalkyl group and a bicycloalkyl group are also contained. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group and the like.
When there are a plurality of R ³ or R ⁸ , they may be the same or different.

  Although the compound represented by General formula (1) can be synthesize | combined according to a previous report (nonpatent literature 3), the following compounds (1-1)-(1-20) are specifically mentioned, for example. .

A compound represented by the general formula (2) and a compound represented by the general formula (1) in an amount of 2 to 3 times equivalent, preferably about 2 times equivalent to the compound represented by the general formula (2); And react in the presence of a condensing agent. Here, the condensing agent is not particularly limited, but sulfuric acid, hydrochloric acid, phosphoric acid, polyphosphoric acid, sulfonic acid, methanesulfonic acid, ethanesulfonic acid, toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid. , Bistrifluoromethanesulfonimide, aluminum trichloride, zinc chloride, phosphoryl chloride, iron chloride, zirconium chloride, lanthanum chloride, bismuth trifluoromethanesulfonate, zinc trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, copper trifluoromethanesulfonate, Examples thereof include tin trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, and neodymium trifluoromethanesulfonate. Among these, methanesulfonic acid and ethanesulfonic acid are preferable, and methanesulfonic acid is particularly preferable.
The reaction temperature is appropriately selected depending on the reaction substrate, the condensing agent, and the type of solvent used, but is usually about room temperature to 200 ° C, preferably room temperature to 150 ° C. Although the reaction time depends on the reaction temperature, it is usually about 10 minutes to 3 days, and the same conditions apply when heating. After completion of the reaction, the reaction solution is neutralized and purified to obtain the compound represented by the general formula (3).

The compound represented by the general formula (3) can have the following three structures of a neutral type, a monocation type, and a dication type by the exchange of hydrogen ions.

  In the present invention, the compound represented by the general formula (3) includes these three structures.

In the present invention, at least one of R ² and R ⁴ is a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group, in order to obtain a compound represented by the general formula (3) in a high yield. The two R ⁴ are preferably the same.
That is, when R ² is a hydrogen atom, the two R ⁴ are preferably groups selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. When R ² is a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group, two R ^{4 s} are both hydrogen atoms or both are an alkyl group, an acyl group, a silyl group, and a tetrahydropyrani group. It is preferably a group selected from the following groups.

In the present invention, by thus protecting at least one of R ² and R ^{4 with} a group selected from an alkyl group, an acyl group, a silyl group and a tetrahydropyranyl group, the production of rhodol as a by-product is suppressed, The yield of the compound represented by the general formula (3) can be improved.

Next, the manufacturing method of the compound represented by General formula (7) is demonstrated.
In this method, the compound represented by the general formula (1) and the compound represented by the general formula (2) are reacted in the presence of a condensing agent to obtain a compound represented by the general formula (4). The compound represented by the general formula (4) and the compound represented by the general formula (5) are reacted in the presence of a condensing agent to obtain a compound represented by the general formula (6). The compound represented by 6) is cyclized.

[In General Formulas (1) to (2) and (4) to (7), R ¹ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Or two R ^{1 s} or two R ^{5 s} may be bonded to form a ring, or a heterocycle may be formed together with the nitrogen atom to which R ¹ or R ⁵ is bonded. . R ² , R ⁴ and R ⁶ each independently represent a hydrogen atom or a group selected from an alkyl group, an acyl group, a silyl group and a tetrahydropyranyl group. However, at least one of R ² and R ⁴ is a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. R ³ and R ⁷ are each independently a halogen atom or an alkyl group or a carboxyl group having 1 to 6 carbon atoms, may form a ring plurality of R ³ s or more R ⁷ are bonded to each other . R ⁸ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but R ¹ and R ⁸ may be bonded to form a ring. R ⁹ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group, but R ⁵ and R ⁹ may be bonded to form a ring. m shows the number of 0-3. n shows the number of 0-4. o shows the number of 0-3. p shows the number of 0-4. ]

In general formulas (1) and (4) to (7), the alkyl group having 1 to 6 carbon atoms of R ¹ and R ⁵ may be linear or branched, and includes a cycloalkyl group and a bicycloalkyl group. It is. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group and the like.

In general formulas (1) and (4) to (7), the aryl group having 6 to 14 carbon atoms of R ¹ and R ⁵ may be monocyclic or polycyclic, and may be a benzene ring. Alternatively, a group in which two or more condensed rings are bonded via a single bond, a group bonded via a divalent organic group (for example, an alkenylene group such as vinylene group), and a heteroaryl group are also included. Specifically, phenyl group, alkylphenyl group, alkoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 2-biphenyl group, 3-biphenyl group 4-biphenyl group, thienyl group, pyridyl group, indolyl group and the like. The hydrogen atom of the aryl group may be substituted with a halogen atom or the like. Among these, a phenyl group is preferable.

When two R ^{1 s} or two R ^{5 s} are bonded to form a ring, the two R ^{1 s} or the two R ^{5 s} may be bonded via a hetero atom such as an oxygen atom or a sulfur atom. . Examples of the case where two R ^{1 s} or R ^{5 s} are bonded to form a ring include the following structures when represented together with the nitrogen atom to which R ¹ or R ⁵ is bonded.

As a case where a heterocycle is formed together with the nitrogen atom to which R ¹ or R ⁵ is bonded, for example, the following structures can be cited when expressed together with the nitrogen atom to which R ¹ is bonded.

In the general formulas (1) and (4) to (7), two R ¹ and two R ⁵ may be the same or different. Examples of the case where two R ¹ or two R ⁵ are different include, for example, a structure in which one is an alkyl group and the other forms a heterocycle with the nitrogen atom to which R ¹ or R ⁵ is bonded. It is done.

In general formulas (1) to (2) and (4) to (7), examples of the alkyl group of R ² , R ⁴ and R ⁶ include those having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, It may be linear or branched and includes a cycloalkyl group and a bicycloalkyl group. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group and the like.
Further, R ^2, an alkyl group of R ⁴ and R ⁶ may have a substituent. Examples of the substituent include alkoxy groups such as methoxy group and ethoxy group; aryl groups such as phenyl group; alkoxyaryl groups such as methoxyphenyl group and ethoxyphenyl group.
Of those described above, a methyl group, a methoxymethyl group, a benzyl group, a methoxybenzyl group, and the like are preferable, and a methyl group is particularly preferable because of ease of synthesis.

In general formulas (1) to (3), examples of the acyl group represented by R ² , R ^4, and R ⁶ include an acetyl group, a pivaloyl group, and a benzoyl group.

In the general formulas (1) to (2) and (4) to (7), as the silyl group of R ² , R ⁴ and R ⁶ , trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, t-butyldimethylsilyl A trialkylsilyl group such as a group; t-butyldiphenylsilyl group and the like.

In general formulas (1) and (4) to (7), examples of the halogen atom for R ³ , R ⁷ , R ^8, and R ⁹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Moreover, as a C1-C6 alkyl group, linear or branched may be sufficient and a cycloalkyl group and a bicycloalkyl group are also contained. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group and the like.
When there are a plurality of R ³ , R ⁷ , R ⁸ or R ⁹ , they may be the same or different.

  Examples of the compound represented by the general formula (1) include the same compounds as those exemplified in the method for producing the compound represented by the general formula (3).

The compound represented by the general formula (1) and the compound represented by the general formula (2) are mixed in approximately equimolar amounts and reacted in the presence of a condensing agent. The condensing agent is not particularly limited, but sulfuric acid, hydrochloric acid, phosphoric acid, polyphosphoric acid, sulfonic acid, methanesulfonic acid, ethanesulfonic acid, toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, bistrifluoromethane. Methanesulfonimide, aluminum trichloride, zinc chloride, phosphoryl chloride, iron chloride, zirconium chloride, lanthanum chloride, bismuth trifluoromethanesulfonate, zinc trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, copper trifluoromethanesulfonate, trifluoromethanesulfone Examples thereof include tin oxide, lanthanum trifluoromethanesulfonate, and neodymium trifluoromethanesulfonate. Among these, methanesulfonic acid and ethanesulfonic acid are preferable, and methanesulfonic acid is particularly preferable.
At this time, the reaction may be performed in the presence of a solvent such as dichloromethane.
The reaction temperature is appropriately selected depending on the reaction substrate, the condensing agent, and the type of solvent used, but is usually about room temperature to 200 ° C, preferably room temperature to 150 ° C. Although the reaction time depends on the reaction temperature, it is usually about 10 minutes to 3 days, and the same conditions apply when heating. After completion of the reaction, the reaction solution is neutralized and purified to obtain the compound represented by the general formula (4).

  Examples of the compound represented by the general formula (4) include the following compounds (4-1) to (4-20).

  The compound represented by the general formula (4) includes a compound represented by the general formula (7) described later, a compound in which two nitrogen atoms of the xanthene ring structure have an asymmetric substituent, and two phenyl ring structures. Is useful when synthesizing a compound having an asymmetric substituent.

  Next, the compound represented by the general formula (4) and the compound represented by the general formula (5) are mixed in approximately equimolar amounts and reacted in the presence of a condensing agent.

Similarly to the compound represented by the general formula (1), the compound represented by the general formula (5) can also be synthesized according to a report (Non-patent Document 3). Specifically, compounds similar to the above compounds (1-1) to (1-20) (provided that R ² in compounds (1-1) to (1-20) is replaced with R ⁶ ).

Examples of the condensing agent include those similar to those used for the synthesis of the compound represented by the general formula (4) exemplified above, and at this time, the reaction may be performed in the presence of a solvent such as dichloromethane. .
The reaction temperature at this time is also appropriately selected depending on the reaction substrate, the condensing agent, and the type of solvent used, but is usually about room temperature to 200 ° C, preferably room temperature to 150 ° C. Although the reaction time depends on the reaction temperature, it is usually about 10 minutes to 3 days, and the same conditions apply when heating. After completion of the reaction, the reaction solution is neutralized and purified to obtain the compound represented by the general formula (6).

Furthermore, the compound represented by the general formula (7) can be obtained by cyclizing the compound represented by the general formula (6). Examples of the cyclization method at this time include a dealkylating agent such as boron tribromide when R ² , R ⁴ and R ⁶ are alkyl groups. In the cyclization when R ² , R ⁴ and R ^{6 use} an alkyl group or other protective group, hydrochloric acid, acetic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, trifluoroacetic acid, methanesulfone Acid, diisobutylaluminum hydride, 2,3-dichloro-5,6-dicyano-p-benzoquinone and the like can be used. After completion of the reaction, the reaction solution is neutralized and purified to obtain the compound represented by the general formula (7).

  The compound represented by the general formula (7) can have the following three structures of a neutral type, a monocation type, and a dication type by the exchange of hydrogen ions.

  In the present invention, the compound represented by the general formula (7) includes these three structures.

In the present invention, at least one of R ² and R ⁴ is a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group, in order to obtain a compound represented by the general formula (7) in a high yield. The two R ⁴ are preferably the same.

In the compound represented by the general formula (7), R ¹ and R ⁵ , R ³ and R ⁷ , and R ⁸ and R ⁹ may be the same or different from each other. Compounds in which at least one set of R ¹ and R ⁵ , R ³ and R ⁷ and R ⁸ and R ⁹ is different cannot be synthesized by a conventional synthesis method in which R ² and R ⁴ are hydrogen atoms. In the method of the present invention, at least one of R ² and R ⁴ is protected with a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group, whereby two nitrogen atoms of the xanthene ring structure are asymmetric ( It is possible to synthesize aminobenzopyranoxanthene-based (ABPX) dye compounds having substituents (different from each other) and aminobenzopyranoxanthene-based (ABPX) dye compounds having substituents with asymmetric two phenyl ring structures.
In addition, ABPX with symmetric substituents has the same electronic environment (for example, acidity and nucleophilicity) of the two spiro rings that are antenna sites for external stimuli such as proton addition. The structure was quickly converted from the sex type to the dicationic type, and it was difficult to obtain the contrast of color development and luminescence. On the other hand, ABPX, which has asymmetric substituents with different electron-donating and electron-accepting properties in the xanthene ring structure or phenyl ring structure, differs in the electronic environment of the two spiro rings. The opening and closing of the spiro ring site occurs in stages. As a result, the structural conversion from the neutral type to the monocation type through the dication type becomes stepwise and reversible, and the contrast of the color development and luminescence color derived from each of the three equilibrium species becomes stronger. Due to this property, ABPX is a single dye molecule, and becomes a dye compound having the characteristics of white light emission and black color.

  An aminobenzopyranoxanthene dye (ABPX) dye compound in which two nitrogen atoms of the xanthene ring structure have an asymmetric substituent, and an aminobenzopyranoxane xanthene system in which two phenyl ring structures have an asymmetric substituent ( Examples of the ABPX) dye compound include the following compounds (7-1) to (7-139).

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not restrict | limited to the following example.

¹ H-NMR and ¹³ C-NMR were measured using a Varian NMR System 600 (manufactured by Agilent Technologies).
The MS spectrum was measured using JMS-700 MStation (manufactured by JEOL Ltd.).
The absorption spectrum was measured using JASCO V-570 (manufactured by JASCO Corporation).
The fluorescence spectrum was measured using Hitachi F-4500 (manufactured by Hitachi High-Tech Science).

[Example 1]
2- (2-hydroxy-4-pyrrolidinylbenzoyl) benzoic acid (1-A, 0.28 mmol, literature: synthesized by the method described in Kamino et al., Org. Lett., 2014, 16, 258.) and 1 , 3-Dimethoxybenzene (2-B, 0.14 mmol, purchased from Wako Pure Chemical Industries, Ltd.) was added to methanesulfonic acid (0.7 mL), stirred for 24 hours at 110 ° C, and then the reaction mixture was saturated with sodium bicarbonate. The solution was made basic by adding an aqueous solution and extracted with chloroform. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX105-a and compound ABPX105-b. At this time, compound ABPX105-a flowed out first, and then compound ABPX-105-b flowed out. The yield was 73% for both ABPX105-a and ABPX105-b. The reaction formula is shown below.

Data for compound ABPX105-a:
600 MHz ¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 7.79 (2H, d), 7.60 (2H, d), 7.51 (2H, d), 7.13 (1H, s), 7.10 (2H, d ), 6.51 (2H, d), 6.37 (2H, d), 6.23 (2H, dd), 6.05 (1H, s), 3.25 (8H, m), 2.0 (8H, m).
600 MHz ¹³ C-NMR (CDCl ₃ / TMS) δ (ppm): 169.2, 153.1, 152.6, 152.2, 149.6, 135.1, 129.7, 128.6, 127.7, 126.6, 124.6, 123.9, 116.3, 108.9, 105.1, 104.2, 97.9 , 83.6, 47.6, 29.7, 25.5.
LR-MS (FAB), Found: 661.
UV / Vis: λ _max = 595 nm (dicationic type, pH 2.2-0.2 M sodium hydrogen phosphate / 5 M hydrochloric acid mixed solution).

Data for compound ABPX105-b:
600 MHz ¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 7.81-7.80 (2H, m), 7.43-7.40 (4H, m), 7.13 (1H, s), 6.91-6.90 (2H, m) , 6.50 (d, 2H), 6.37 (d, 2H), 6.22 (2H, dd), 5.98 (1H, s), 3.27 (8H, m), 2.10-1.99 (8H, m).
600 MHz ¹³ C-NMR (CDCl ₃ / TMS) δ (ppm): 168.9, 153.2, 152.8, 152.3, 149.6, 134.1, 129.3, 128.5, 128.5, 127.2, 124.9, 123.4, 116.3, 108.8, 105.3, 104.3, 98.0 , 83.3, 47.6, 29.7, 25.5.
LR-MS (FAB), Found: 661.

[Example 2]
2- (2-Methoxy-4-pyrrolidinylbenzoyl) benzoic acid (1-B, 0.34 mmol, literature: synthesized by the method described in Kamino et al., Org. Lett., 2014, 16, 258.) and resorcinol (2-A, 0.18 mmol, purchased from Kanto Chemical Co., Inc.) was added to methanesulfonic acid (1.0 mL) and stirred for 24 hours at 110 ° C. And extracted with chloroform. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX105-a and compound ABPX105-b. At this time, compound ABPX105-a flowed out first, and then compound ABPX105-b flowed out. The yield was 73% for both ABPX105-a and ABPX1-5-b. The reaction formula is shown below.

Data for compound ABPX105-a:
600 MHz ¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 7.79 (2H, d), 7.60 (2H, d), 7.51 (2H, d), 7.13 (1H, s), 7.10 (2H, d ), 6.51 (2H, d), 6.37 (2H, d), 6.23 (2H, dd), 6.05 (1H, s), 3.25 (8H, m), 2.0 (8H, m).
600 MHz ¹³ C-NMR (CDCl ₃ / TMS) δ (ppm): 169.2, 153.1, 152.6, 152.2, 149.6, 135.1, 129.7, 128.6, 127.7, 126.6, 124.6, 123.9, 116.3, 108.9, 105.1, 104.2, 97.9 , 83.6, 47.6, 29.7, 25.5.
LR-MS (FAB), Found: 661.

Data for compound ABPX105-b:
600 MHz ¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 7.81-7.80 (2H, m), 7.43-7.40 (4H, m), 7.13 (1H, s), 6.91-6.90 (2H, m) , 6.50 (d, 2H), 6.37 (d, 2H), 6.22 (2H, dd), 5.98 (1H, s), 3.27 (8H, m), 2.10-1.99 (8H, m).
600 MHz ¹³ C-NMR (CDCl ₃ / TMS) δ (ppm): 168.9, 153.2, 152.8, 152.3, 149.6, 134.1, 129.3, 128.5, 128.5, 127.2, 124.9, 123.4, 116.3, 108.8, 105.3, 104.3, 98.0 , 83.3, 47.6, 29.7, 25.5.
LR-MS (FAB), Found: 661.

[Comparative Example 1]
2- (2-hydroxy-4-pyrrolidinylbenzoyl) benzoic acid (1-A, 163 mmol, literature: synthesized by the method described in Kamino et al., Org. Lett., 2014, 16, 258.) and resorcinol (2-A, 83 mmol, purchased from Kanto Chemical Co., Inc.) was added to methanesulfonic acid (0.7 mL), stirred for 4 hours at 120 ° C, and then basified with saturated aqueous sodium hydrogen carbonate solution. And extracted with chloroform. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX105-a and compound ABPX105-b. At this time, compound ABPX105-a flowed out first, and then compound ABPX105-b flowed out. The yield was 35% for both ABPX105-a and ABPX105-b. The reaction formula is shown below. Even when the reaction time was 10 hours, the combined yields of the compounds ABPX105-a and ABPX105-b remained at 36%.

  The yields (total values) of the compounds ABPX105-a and ABPX105-b of Examples 1 and 2 and Comparative Example 1 and the yield of by-product rhodol are summarized in Table 1 below.

  The yields of the target compounds ABPX105-a and ABPX105-b by the production method of the present invention were improved more than twice compared with Comparative Example 1. Moreover, it turned out that the production | generation ratio of the rhodol with respect to compound ABPX105-a and ABPX105-b falls.

[Example 3]
2- (2-hydroxy-4-pyrrolidinylbenzoyl) benzoic acid (1-A, 0.17 mmol, literature: synthesized by the method described in Kamino et al., Org. Lett., 2014, 16, 258.) and 1 , 3-Diethoxybenzene (2-C, 0.081 mmol, literature: Kamino et al., Biorg. Med. Chem. Lett., 2008, 18, 4380.) After stirring at 110 ° C. for 24 hours, the reaction mixture was basified with saturated aqueous sodium hydrogen carbonate solution and extracted with chloroform. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX105-a and compound ABPX105-b. At this time, compound ABPX105-a flowed out first, and then compound ABPX105-b flowed out. The yield was 56% for both ABPX105-a and ABPX105-b. The reaction formula is shown below.

Data for compound ABPX105-a:
¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 7.79 (2H, d), 7.60 (2H, d), 7.51 (2H, d), 7.13 (1H, s), 7.10 (2H, d), 6.51 (2H, d), 6.37 (2H, d), 6.23 (2H, dd), 6.05 (1H, s), 3.25 (8H, m), 2.0 (8H, m).
¹³ C-NMR (CDCl ₃ / TMS) δ (ppm): 169.2, 153.1, 152.6, 152.2, 149.6, 135.1, 129.7, 128.6, 127.7, 126.6, 124.6, 123.9, 116.3, 108.9, 105.1, 104.2, 97.9, 83.6 , 47.6, 29.7, 25.5.
LR-MS (FAB), Found: 661.

Data for compound ABPX105-b:
600 MHz ¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 7.81-7.80 (2H, m), 7.43-7.40 (4H, m), 7.13 (1H, s), 6.91-6.90 (2H, m) , 6.50 (d, 2H), 6.37 (d, 2H), 6.22 (2H, dd), 5.98 (1H, s), 3.27 (8H, m), 2.10-1.99 (8H, m).
600 MHz ¹³ C-NMR (CDCl ₃ / TMS) δ (ppm): 168.9, 153.2, 152.8, 152.3, 149.6, 134.1, 129.3, 128.5, 128.5, 127.2, 124.9, 123.4, 116.3, 108.8, 105.3, 104.3, 98.0 , 83.3, 47.6, 29.7, 25.5.
LR-MS (FAB), Found: 661.

[Example 4]
2- (2-hydroxy-4-pyrrolidinylbenzoyl) benzoic acid (1-A, 0.015 mmol, literature: synthesized by the method described in Kamino et al., Org. Lett., 2014, 16, 258.) and 1 , 3-diisopropoxybenzene (2-D, 0.074 mmol, literature: synthesized by the method described in Kamino et al., Biorg. Med. Chem. Lett., 2008, 18, 4380.) 5 mL), and after stirring for 24 hours at 110 ° C., the reaction mixture was basified with a saturated aqueous sodium hydrogen carbonate solution and extracted with chloroform. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX105-a and compound ABPX105-b. At this time, compound ABPX105-a flowed out first, and then compound ABPX105-b flowed out. The yield was 74% for both ABPX105-a and ABPX105-b. The reaction formula is shown below.

Data for compound ABPX105-a:
600 MHz ¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 7.79 (2H, d), 7.60 (2H, d), 7.51 (2H, d), 7.13 (1H, s), 7.10 (2H, d ), 6.51 (2H, d), 6.37 (2H, d), 6.23 (2H, dd), 6.05 (1H, s), 3.25 (8H, m), 2.0 (8H, m).
600 MHz ¹³ C-NMR (CDCl ₃ / TMS) δ (ppm): 169.2, 153.1, 152.6, 152.2, 149.6, 135.1, 129.7, 128.6, 127.7, 126.6, 124.6, 123.9, 116.3, 108.9, 105.1, 104.2, 97.9 , 83.6, 47.6, 29.7, 25.5.
LR-MS (FAB), Found: 661.

Data for compound ABPX105-b:
600 MHz ¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 7.81-7.80 (2H, m), 7.43-7.40 (4H, m), 7.13 (1H, s), 6.91-6.90 (2H, m) , 6.50 (d, 2H), 6.37 (d, 2H), 6.22 (2H, dd), 5.98 (1H, s), 3.27 (8H, m), 2.10-1.99 (8H, m).
600 MHz ¹³ C-NMR (CDCl ₃ / TMS) δ (ppm): 168.9, 153.2, 152.8, 152.3, 149.6, 134.1, 129.3, 128.5, 128.5, 127.2, 124.9, 123.4, 116.3, 108.8, 105.3, 104.3, 98.0 , 83.3, 47.6, 29.7, 25.5.
LR-MS (FAB), Found: 661.

[Reference Example 1]
Compound ABPX105-a and compound ABPX105-b were synthesized under the same conditions as in Example 4 except that the reaction temperature was changed from room temperature to 130 ° C. Although formation of compound ABPX105-a and compound ABPX105-b was confirmed at any reaction temperature, it was found that compound ABPX105-a and compound ABPX105-b were obtained with the highest yield at a reaction temperature of 110 ° C.

[Example 5]
2- (2-hydroxy-4-piperidinylbenzoyl) benzoic acid (1-C, 0.17 mmol, literature: synthesized by the method described in Kamino et al., Org. Lett., 2014, 16, 258.) and 1 , 3-diisopropoxybenzene (2-D, 0.081 mmol, synthesized by the method described in Kamino et al., Biorg. Med. Chem. Lett., 2008, 18, 4380.) 5 mL), and after stirring for 24 hours at 110 ° C., the reaction mixture was basified with a saturated aqueous sodium hydrogen carbonate solution and extracted with chloroform. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX106-a and compound ABPX106-b. At this time, compound ABPX106-a flowed out first, and then compound ABPX106-b flowed out. The yield was 53% in total for compound ABPX106-a and compound ABPX106-b. The reaction formula is shown below.

Data for compound ABPX106-a:
¹ H-NMR (CDCl ₃ , 600 MHz): δ 7.81-7.84 (m, 2 H), 7.63 (ddd, 2 H, J = 7.8, 7.8, 1.2 Hz), 7.54 (ddd, 2 H, J = 7.8 , 7.8, 0.6 Hz), 7.15 (s, 1 H), 7.10-7.13 (m, 2 H), 6.73 (d, 2 H, J = 2.4 Hz), 6.59 (dd, 2 H, J = 8.4, 1.8 Hz), 6.54 (d, 2 H, J = 9.6 Hz), 6.53 (d, 2 H, J = 9.1 Hz), 3.25-3.27 (m, 8 H), 1.67-1.71 (m, 8 H), 1.58 -1.64 (m, 4 H).
¹³ C-NMR (CDCl ₃ , 600 MHz): δ 169.19, 153.50, 153.08, 153.07, 152.41, 152.15, 135.16, 129.80, 128.36, 127.75, 126.35, 124.67, 123.91, 116.27, 112.21, 107.81, 104.31, 101.76, 82.95 , 49.32, 25.40, 24.30.
LRMS (ESI) Found 668.

Data for compound ABPX106-b:
¹ H-NMR (CDCl ₃ , 600 MHz): δ 7.82-7.86 (m, 2 H), 7.43-7.48 (m, 4 H), 7.18 (s, 1 H), 6.90-6.94 (m, 2 H) , 6.75 (m, 2 H), 6.57-6.60 (m, 4 H), 6.04 (s, 1 H), 3.86-3.87 (m, 8 H), 3.21-3.23 (m, 8 H).
¹³ C-NMR (CDCl ₃ , 600 MHz): δ 168.76, 153.11, 153.04, 152.54, 152.10, 134.28, 129.49, 128.54, 128.50, 126.86, 125.09, 123.28, 116.35, 111.68, 109.46, 104.47, 101.85, 82.25, 66.63 , 48.25, 29.73
LRMS (ESI) Found 688.

[Example 6]
2- (2-hydroxy-4-morpholinylbenzoyl) benzoic acid (1-D, 0.17 mmol, literature: synthesized by the method described in Kamino et al., Org. Lett., 2014, 16, 258.) and 1 , 3-diisopropoxybenzene (2-D, 0.080 mmol, synthesized by the method described in Kamino et al., Biorg. Med. Chem. Lett., 2008, 18, 4380.) 5 mL), and after stirring for 24 hours at 110 ° C., the reaction mixture was basified with a saturated aqueous sodium hydrogen carbonate solution and extracted with chloroform. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX107-a and compound ABPX107-b. At this time, compound ABPX107-a flowed out first, and then compound ABPX107-b flowed out. The yield was 66% in total for compound ABPX107-a and compound ABPX107-b. The reaction formula is shown below.

Data for compound ABPX107-a:
¹ H-NMR (CDCl ₃ , 600 MHz): δ 7.82-7.84 (m, 2 H), 7.64 (ddd, 2 H, J = 7.2, 7.2, 1.2 Hz), 7.56 (ddd, 2 H, J = 7.8 , 7.8, 1.2 Hz), 7.17 (s, 1 H), 7.11-7.12 (m, 2 H), 6.75 (d, 2 H, J = 0.6 Hz), 6.58-6.62 (m, 4 H), 6.12 ( s, 1 H), 3.86-3.87 (m, 8 H), 3.22-3.24 (m, 8 H).
¹³ C-NMR (CDCl ₃ , 600 MHz): δ 160.03, 152.96, 152.30, 152.12, 135.26, 129.93, 128.55, 127.78, 124.79, 123.82, 116.36, 111.73, 104.42, 101.81, 66.63, 48.23.
LRMS (ESI) Found 692.

Data for compound ABPX107-b:
¹ H-NMR (CDCl ₃ , 600 MHz): δ 7.84-7.88 (m, 2 H), 7.44-7.49 (M, 4), 7.56 (ddd, 2 H, J = 7.8, 7.8, 1.2 Hz), 7.17 (s, 1 H), 7.11-7.12 (m, 2 H), 6.75 (d, 2 H, J = 0.6 Hz), 6.58-6.62 (m, 4 H), 6.12 (s, 1 H), 3.86- 3.87 (m, 8 H), 3.22-3.24 (m, 8 H).
¹³ C-NMR (CDCl ₃ , 600 MHz): δ 160.03, 152.96, 152.30, 152.12, 135.26, 129.93, 128.55, 127.78, 124.79, 123.82, 116.36, 111.73, 104.42, 101.81, 66.63, 48.23.
LRMS (ESI) Found 692.

[Example 7]
8- (2-Carboxymethylbenzoyl) -7-hydroxy-1,1-dimethyl-N-methylquinoline (1-E, 0.17 mmol, literature: Kamino et al., Org. Lett., 2014, 16, 258. And 1,3-diisopropoxybenzene (2-D, 0.082 mmol, literature: Kamino et al., Biorg. Med. Chem. Lett., 2008, 18, 4380. ) Was added to methanesulfonic acid (5 mL), stirred at room temperature for 12 hours, then stirred for 12 hours at 110 ° C., basified with saturated aqueous sodium hydrogen carbonate solution, and extracted with chloroform. did. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure. The resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX101-a and compound ABPX101-b. At this time, compound ABPX101-a flowed out first, and then compound ABPX101-b flowed out. The yield was 62% in total for compound ABPX101-a and compound ABPX101-b. The reaction formula is shown below.

Data for compound ABPX101-a:
¹ H-NMR (CDCl ₃ , 500 MHz): δ 7.79 (d, 2H, J = 7.4 Hz), 7.61 (ddd, 2H, J = 7.5, 7.5 Hz, 1.2 Hz), 7.52 (ddd, 2H, J = 7.5, 7.5, 1.2 Hz), 7.12 (d, 2H, J = 7.5 Hz), 7.09 (s, 1H), 6.38 (s, 2H), 6.37 (s, 2H), 5.97 (s, 1H), 3.13- 3.23 (m, 4H), 2.96 (s, 6H), 1.64 (t, 4H, 5.8 Hz), 1.04 (s, 6H), 0.95 (s, 6H).
¹³ C-NMR (CDCl ₃ , 500 MHz): δ169.25, 153.13, 152.04, 151.06, 147.32, 134.91, 129.59, 128.43, 127.53, 126.69, 124.42, 123.97, 123.92, 116.27, 104.83, 103.96, 96.92, 83.92, 47.27, 39.09, 36.42, 31.60, 30.90, 30.05, 30.03.
LRMS (ESI) Found 359.

Data for compound ABPX101-b:
¹ H-NMR (CDCl ₃ , 500 MHz): δ 7.82 (dd, 2H, J = 6.3, 1.7 Hz), 7.44 (td, 2H, J = 6.9, 1.7 Hz), 7.42 (td, 2H, J = 7.5 , 1.8 Hz), 7.09 (s, 1H), 6.87 (dd, 2H, J = 5.8, 1.7 Hz), 6.38 (s, 2H), 6.37 (s, 2H), 5.91 (s, 1H), 3.32-3.22 (m, 4H), 2.95 (s, 6H), 1.64-1.59 (m, 4H), 1.04 (s, 6H), 0.93 (s, 6H).
¹³ C-NMR (CDCl ₃ , 500 MHz): δ 168.88, 153.17, 152.14, 151.27, 147.30, 133.96, 129.16, 128.39, 128.28, 127.23, 124.81, 123.90, 123.33, 116.26, 104.98, 104.07, 96.96, 83.56, 47.27 , 39.10, 36.43, 31.59, 30.04, 30.01.
LRMS (ESI) Found 359.

[Example 8]
8- (2-Carboxymethylbenzoyl) -9-hydroxy-1,1-dimethyl-N-methylquinoline (1-F, 0.16 mmol, literature: Kamino et al., Org. Lett., 2014, 16, 258. And 1,3-diisopropoxybenzene (2-D, 0.078 mmol, literature: Kamino et al., Biorg. Med. Chem. Lett., 2008, 18, 4380. ) Was added to methanesulfonic acid (5 mL), stirred at room temperature for 12 hours, then stirred for 12 hours at 110 ° C., basified with saturated aqueous sodium hydrogen carbonate solution, and extracted with chloroform. did. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX102-a and compound ABPX102-b. At this time, compound ABPX102-a flowed out first, and then compound ABPX102-b flowed out. The yield of the compound ABPX102-a and compound ABPX102-b was 34%. The reaction formula is shown below.

Data for compound ABPX102-a:
¹ H-NMR (CDCl ₃ , 500 MHz): δ 7.78 (d, 2H, J = 7.5 Hz), 7.60 (ddd, 2H, J = 7.5, 7.5, 1.2 Hz), 7.50 (ddd, 2H, J = 7.5 , 7.5, 1.2 Hz), 7.21 (s, 1H), 7.14 (d, 2H, J = 7.5 Hz), 6.40 (d, 2H, J = 9.2 Hz), 6.30 (d, 2H, J = 8.5 Hz), 6.04 (s, 1H), 3.21 (t, 4H, J = 5.5 Hz), 2.87 (s, 6H), 1.88 (t, 4H, J = 5.4 Hz), 1.64 (s, 12 H).
¹³ C-NMR (CDCl ₃ , 500 MHz): δ 169.09, 153.01, 151.68, 151.13, 148.51, 134.89, 129.61, 126.84, 125.96, 124.63, 123.98, 117.19, 116.37, 108.35, 107.27, 103.71, 84.05, 47.70, 40.54 , 40.15, 32.44, 29.85, 29.73.
LRMS (ESI) Found 359.

Data for compound ABPX102-b:
¹ H-NMR (CDCl ₃ , 500 MHz): δ 7.84-7.80 (m, 2H), 7.46 (m, 2H), 7.45 (m, 2H), 7.22 (s, 1H), 6.98-6.95 (m, 2H ), 6.38 (d, J = 9.2 Hz, 2H), 6.29 (d, J = 9.2 Hz, 2H), 6.01 (s, 1H), 3.26-3.16 (m, 4H), 2.87 (s, 6H), 1.91 -1.86 (m, 4H), 1.65 (s, 6H), 1.62 (s, 6H).
¹³ C-NMR (CDCl ₃ , 500 MHz): δ 168.74, 153.07, 151.69, 151.36, 148.50, 133.97, 129.27, 127.60, 127.42, 125.91, 125.00, 123.48, 117.25, 116.34, 108.30, 107.45, 103.77, 83.74, 47.69 , 40.53, 40.15, 32.43, 29.89, 29.68.
LRMS (ESI) Found 359.

[Example 9]
9- (2-Carboxybenzoyl) -8-hydroxyjulolidine (1-G, 0.17 mmol, literature: synthesized by the method described in Kamino et al., Org. Lett., 2014, 16, 258.) and 1,3 -Diisopropoxybenzene (2-D, 0.078 mmol, literature: Kamino et al., Biorg. Med. Chem. Lett., 2008, 18, 4380.) The mixture was stirred at room temperature for 12 hours and then stirred at 110 ° C. for 12 hours. The reaction mixture was basified with saturated aqueous sodium hydrogen carbonate solution and extracted with chloroform. After drying the organic layer over magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX103-a and compound ABPX103-b. At this time, compound ABPX103-a flowed out first, and then compound ABPX103-b flowed out. The yield was 56% in total for compound ABPX103-a and compound ABPX103-b. The reaction formula is shown below.

Data for compound ABPX103-a:
¹ H-NMR (CDCl ₃ , 500 MHz): δ 7.76 (d, 2H, J = 8.0 Hz), 7.59 (ddd, J = 7.4, 7.4, 1.2 Hz, 2H), 7.49 (ddd, 2H, J = 7.2 , 7.2, 1.2 Hz), 7.17 (s, 1H), 7.12 (d, 2H, J = 7.5 Hz), 6.05 (s, 2H), 5.96 (s, 1H), 3.18 (t, 4H, J = 5.5 Hz ), 3.13 (t, 4H, J = 5.5 Hz), 2.94 (t, 4H, J = 6.6 Hz), 2.54-2.44 (m, 4H), 2.04-2.00 (m, 4H), 1.88-1.84 (m, 4H).
¹³ C-NMR (CDCl ₃ , 500 MHz): δ 169.25, 153.13, 152.00, 147.89, 144.65, 134.88, 129.50, 127.50, 126.80, 124.60, 124.42, 124.05, 117.87, 116.00, 107.28, 104.95, 104.19, 84.26, 49.81 , 49.35, 29.68, 27.27, 21.68, 21.13, 20.95.
LRMS (ESI) Found: 357.

Data for compound ABPX103-b:
¹ H-NMR (CDCl ₃ , 500 MHz): δ 7.80 (d, 2H, J = 6.3 Hz), 7.42 (t, 2H, J = 6.9 Hz), 7.42 (t, 2H, J = 6.9 Hz), 7.18 (s, 1H), 6.90 (d, 2H, J = 5.2 Hz), 6.04 (s, 2H), 5.91 (s, 1H), 3.17 (t, 4H, J = 6.9 Hz), 3.12 (t, 4H, J = 6.9 Hz), 2.99-2.88 (m, 4H), 2.49-2.42 (m, 4H), 2.07-1.97 (m, 4H), 1.89-1.80 (m, 4H):
¹³ C-NMR (CDCl ₃ , 500 MHz): δ 168.87, 153.20, 152.09, 148.11, 144.64, 133.93, 129.09, 128.25, 127.39, 124.82, 124.56, 123.45, 117.85, 116.00, 107.37, 105.10, 104.34, 83.92, 49.82 , 49.37, 27.28, 21.70, 21.14, 20.96.
HRMS (ESI) Found: 357.

[Example 10]
1,1,7,7, -tetramethyl-8-hydroxyjulolidine (1-H, 0.14 mmol, literature: synthesized by the method described in Kamino et al., Org. Lett., 2014, 16, 258.) and A mixture of 1,3-diisopropoxybenzene (2-D, 0.068 mmol, literature: Kamino et al., Biorg. Med. Chem. Lett., 2008, 18, 4380. (5 mL) and stirring at room temperature for 12 hours, followed by stirring for 12 hours at 110 ° C., the reaction solution was basified with saturated aqueous sodium hydrogen carbonate solution, and extracted with chloroform. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX108-a and compound ABPX108-b. At this time, compound ABPX108-a flowed out first, and then compound ABPX108-b flowed out. The yield was 17% in total for compound ABPX108-a and compound ABPX108-b. The reaction formula is shown below.

Data for compound ABPX108-a:
¹ H-NMR (CDCl ₃ , 500 MHz): δ 7.80-8.83 (m, 2H), 7.62 (ddd, 2H, J = 7.8, 7.8, 1.2 Hz), 7.52 (ddd, 2H, J = 7.2, 7.2, 0.6 Hz), 7.18 (s, 1H), 7.17 (d, 2H, J = 7.8 Hz), 6.31 (m, 2H), 5.99 (s, 1H), 3.12-3.19 (m, 8 H), 1.87-1.89 (m, 4H), 1.65-1.67 (m, 16 H), 1.27 (m, 4H), 1.04 (m, 4H), 0.96 (m, 4H).
LRMS (ESI), Found 824.
Data for compound ABPX108-a:
LRMS (ESI), Found 824.

  The yield (total value) of each compound obtained in Examples 3 to 10 and the yield of rhodol as a by-product are summarized in Table 2 below.

Each compound obtained in Examples 5 to 10 and Comparative Example 1 was dissolved in chloroform containing 2.5% by volume of trifluoroacetic acid, and an absorption spectrum and a fluorescence spectrum were measured. In this measurement condition, each compound has a dicationic structure.
The fluorescence quantum yield was calculated by a relative method using rhodamine B in ethanol as a reference substance (Φ _fl = 0.73).

  In particular, in Example 5 and Example 9, a compound having a high fluorescence quantum yield could be obtained.

[Example 11]
2- (4-Diethylamino-2-hydroxybenzoyl) benzoic acid (3-A, 1.0 mmol, literature: synthesized by the method described in Kamino et al., Chem. Commun., 2010, 46, 9013.) and 1,3 -Dimethoxybenzene (2-B, 1.0 mmol, purchased from Wako Pure Chemical Industries, Ltd.) was added to a dichloromethane solution (4.35 mL) containing 8% methanesulfonic acid, and stirred at room temperature for 2 hours. Saturated aqueous sodium hydrogen carbonate solution was added to basify the solution, and the mixture was extracted with chloroform. The organic layer was dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound BF3A2B. The yield was 65%.
Subsequently, 3- [4- (diethylamino) -2-hydroxyphenyl] -3- [2,4-dimethoxyphenyl] -1-isobenzofuranone (BF3A2B, 0.25 mmol) and 2- (2-hydroxy-4- A mixture of pyrrolidinylbenzoyl) benzoic acid (1-A, 0.25 mmmol) was added to a dichloromethane solution (4.0 mL) containing 10% methanesulfonic acid, and the mixture was stirred at room temperature for 2 hours. Was added to make the solution basic and extracted with chloroform. The organic layer was dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX500-b. The yield was 37%.

Structural data for compound BF3A2B:
600 MHz ¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 7.94-7.92 (1H, m), 7.65-7.62 (1H, m), 7.53-7.50 (1H, m), 7.42-7.40 (1H, m), 7.02 (1H, d, J = 8.5 Hz), 6.92 (1H, d, J = 8.8 Hz), 6.40 (1H, m), 6.38 (1H, dd, J = 8.5, 2.3 Hz), 6.34 ( 1H, dd, J = 7.0, 2.6 Hz), 6.13 (1H, dd, J = 8.8, 2.6 Hz), 3.76 (3H, s), 3.41 (3H, s), 3.33 (4H, q, J = 7.3 Hz ), 1.15 (6H, t, J = 7.3 Hz).
600 MHz ¹³ C-NMR (CDCl ₃ / TMS) δ (ppm): 169.4, 161.9, 159.1, 156.6, 151.5, 149.7, 133.1, 130.5, 128.6, 127.2, 125.4, 124.1, 119.2, 111.3, 103.9, 103.0, 100.8 , 100.2, 91.8, 55.5, 55.3, 44.3, 12.6.
LR-MS (FAB), Found: 434.

Structural data for compound ABPX500-b:
600 MHz ¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 7.82-7.80 (2H, m), 7.44-7.40 (4H, m), 7.14 (1H, s), 6.93-6.90 (2H, m) , 6.50-6.47 (3H, m), 6.37 (1H, d, J = 2.3 Hz), 6.31 (1H, dd, J = 8.8, 2.5 Hz), 6.22 (1H, dd, J = 8.8, 2.3 Hz), 5.98 (1H, s), 3.36 (4H, q, J = 7.0 Hz), 3.30-3.28 (4H, m), 2.02-2.00 (4H, m), 1.16 (6H, t, J = 7.0 Hz).
600 MHz ¹³ C-NMR (CDCl ₃ / TMS) δ (ppm): 168.9, 168.8, 153.2, 153.2, 153.1, 152.8, 152.3, 152.1, 149.7, 149.6, 134.1, 134.0, 129.2, 128.6, 128.5, 127.3, 127.2 , 124.9, 123.4, 123.3, 108.8, 108.4, 105.3, 105.1, 104.3, 97.9, 97.7, 83.3, 83.2, 47.6, 44.5, 25.5, 12.5.
LR-MS (FAB), Found: 663.
UV / Vis: λ _max = 594 nm (dicationic type, pH 2.5-0.2 M sodium citrate / 1 M hydrochloric acid mixed aqueous solution).

[Example 12]
3- [4- (Diethylamino) -2-hydroxyphenyl] -3- [2,4-dimethoxyphenyl] -1-isobenzofuranone (BF3A2B, 0.23 mmol) and 2- (4-dibutylamino-4-methoxybenzoyl) ) Add a mixture of benzoic acid (4-A, 0.23 mmol, purchased from Kanto Chemical Co., Inc.) to a dichloromethane solution (5.0 mL) containing 10% methanesulfonic acid and stir at room temperature for 2 hours. An aqueous sodium hydrogen solution was added to basify the solution, and the mixture was extracted with chloroform. After drying the organic layer with sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was dissolved in chloroform and subjected to silica gel column chromatography to separate compound ABPX501-b.

Structural data for compound ABPX501-b:
600 MHz ¹ H-NMR (CDCl ₃ / TMS) δ (ppm): 7.82-7.80 (2H, m), 7.44-7.40 (4H, m), 7.14 (1H, s), 6.93-6.90 (2H, m) , 6.48-6.43 (4H, m), 6.31 (1H, m), 6.28 (1H, dd, J = 9.1, 2.3 Hz), 5.97 (1H, s), 3.35 (4H, q, J = 7.0 Hz), 3.30-3.23 (4H, m), 1.59-1.53 (4H, m), 1.37-1.31 (4H, m), 1.16 (6H, t, J = 7.3 Hz), 0.94 (t, 6H, J = 7.3 Hz) .
LR-MS (FAB), Found: 721.

[Reference Example 2]
In Example 1, compounds ABPX105-a and ABPX105-b were obtained in the same manner as in Example 1 except that trifluoromethanesulfonic acid was used instead of methanesulfonic acid as the condensing agent. The yield of the compounds ABPX105-a and ABPX105-b was 9%, and the yield of rhodol was 77%.

By the production method of the present invention, an aminobenzopyranoxanthene (ABPX) dye compound can be obtained in high yield. Aminobenzopyranoxanthene (ABPX) dye compounds fused with a nitrogen moiety of the xanthene ring structure have high luminous efficiency, coloring materials, pigments, various dye materials as dyes, fluorescent imaging dyes, dye-sensitized solar cells It is expected as a useful compound in various fields.
Furthermore, according to the production method of the present invention, it is possible to synthesize an aminobenzopyranoxanthene-based (ABPX) dye compound having a substituent with an asymmetric xanthene ring structure and phenyl ring structure, which could not be synthesized conventionally. ABPX, which has asymmetric substituents with different electron-donating and electron-accepting properties in the xanthene ring structure or phenyl ring structure, differs in the electronic environment of the two spiro rings. Opening and closing of this occurs in stages. As a result, the structural conversion from the neutral type to the monocation type through the dication type becomes stepwise and reversible, and the contrast of the color development and luminescence color derived from each of the three equilibrium species becomes stronger. Due to this property, ABPX is a single molecule of dye, and becomes a dye compound with the characteristics of white light emission and black, and is expected as an optoelectronic material and sensing material.

Claims (4)

A compound represented by the following general formula (3), characterized in that a compound represented by the following general formula (1) and a compound represented by the following general formula (2) are reacted in the presence of a condensing agent. Production method.

[In General Formulas (1) to (3), each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, or two R ¹ bonded to each other. May form a ring, or may form a heterocycle together with the nitrogen atom to which R ¹ is bonded. R ² and R ⁴ each independently represent a hydrogen atom or a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. However, at least one of R ² and R ⁴ is a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. R ³ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but a plurality of R ³ may be bonded to form a ring. R ⁸ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but R ¹ and R ⁸ may be bonded to form a ring. m shows the number of 0-3. n shows the number of 0-4. ] The compound represented by general formula (1) and the compound represented by general formula (2) are reacted in the presence of a condensing agent to obtain a compound represented by general formula (4),
Next, the compound represented by the general formula (4) and the compound represented by the general formula (5) are reacted in the presence of a condensing agent to obtain a compound represented by the general formula (6).
Furthermore, the compound represented by the general formula (6) is cyclized. A method for producing the compound represented by the general formula (7).

[In General Formulas (1) to (2) and (4) to (7), R ¹ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Or two R ^{1 s} or two R ^{5 s} may be bonded to form a ring, or a heterocycle may be formed together with the nitrogen atom to which R ¹ or R ⁵ is bonded. . R ² , R ⁴ and R ⁶ each independently represent a hydrogen atom or a group selected from an alkyl group, an acyl group, a silyl group and a tetrahydropyranyl group. However, at least one of R ² and R ⁴ is a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. R ³ and R ⁷ are each independently a halogen atom or an alkyl group or a carboxyl group having 1 to 6 carbon atoms, may form a ring plurality of R ³ s or more R ⁷ are bonded to each other . R ⁸ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but R ¹ and R ⁸ may be bonded to form a ring. R ⁹ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group, but R ⁵ and R ⁹ may be bonded to form a ring. m shows the number of 0-3. n shows the number of 0-4. o shows the number of 0-3. p shows the number of 0-4. ] The compound represented by General formula (7).

[In the general formula (7), R ¹ and R ⁵ each independently represent a hydrogen atom, or an alkyl group or an aryl group having 6 to 14 carbon atoms having 1 to 6 carbon atoms, the two R ¹ together or two R ⁵ may be bonded to each other to form a ring, or a heterocycle may be formed together with the nitrogen atom to which R ¹ or R ⁵ is bonded. R ³ and R ⁷ are each independently a halogen atom or an alkyl group or a carboxyl group having 1 to 6 carbon atoms, may form a ring plurality of R ³ s or more R ⁷ are bonded to each other . R ⁸ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but R ¹ and R ⁸ may be bonded to form a ring. R ⁹ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group, but R ⁵ and R ⁹ may be bonded to form a ring. However, at least one of R ¹ and R ⁵ , R ³ and R ⁷ and R ⁸ and R ⁹ is different from each other. m shows the number of 0-3. n shows the number of 0-4. o shows the number of 0-3. p shows the number of 0-4. ] The compound represented by General formula (4).

[In General Formula (4), each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, or two R ¹ 's bonded to form a ring. Or may form a heterocycle together with the nitrogen atom to which R ¹ is bonded. R ² and R ⁴ each independently represent a hydrogen atom or a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. However, at least one of R ² and R ⁴ is a group selected from an alkyl group, an acyl group, a silyl group, and a tetrahydropyranyl group. R ³ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group, but a plurality of R ³ may be bonded to form a ring. R ⁸ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group, but R ¹ and R ⁸ may be bonded to form a ring. m shows the number of 0-3. n shows the number of 0-4. ]