Acidochromic dye and method for producing the same

Abstract

To provide an acidochromic dye whose optical properties change depending on pH.SOLUTION: An acidochromic dye comprises a compound represented by the general formula (1). [In the formula, Ar1 represents a condensed aromatic ring having a substituted or unsubstituted amino group. Ar2 represents a condensed aromatic ring.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an acidochromic dye and a method for producing the same. [Background technology]

[0002] A diazo coupling reaction is generally employed for producing azo compounds. In the diazo coupling reaction, an aromatic compound having an amino group is reacted with sodium nitrite under acidic conditions to obtain an aromatic diazonium compound, and then the obtained aromatic diazonium compound is reacted with an aromatic compound having an electron-donating group as a substrate (see, for example, Non-Patent Document 1).

[0003] However, most of the reports of the above diazo coupling reaction require the reaction to be carried out under basic conditions.

[0004] On the other hand, it is known that, for example, an aromatic compound having an amino group is reacted with an aromatic compound having a nitroso group in the presence of a catalyst (see, for example, Non-Patent Document 2). [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Dyes and Pigments 2022, 199, 110050. [Non-patent document 2] Molecules 2023, 28, 6741. Summary of the Invention [Problem to be solved by the invention]

[0006] However, there are very few reports on azo compounds in which fused rings are bonded via azo groups, and there are no reports evaluating the pH dependence of the optical properties of such azo compounds.

[0007] The present invention is intended to solve the above-mentioned problems, and has as its object to provide an acidochromic dye whose optical properties change depending on the pH. [Means for solving the problem]

[0008]

[0006] In view of the above object, the present inventors conducted extensive research and found that when a fused ring compound having an amino group of a specific structure is used as a substrate and reacted with a nitrite compound, preferably under acidic conditions, a diazo compound in which the fused rings are bonded to each other via an azo group can be obtained, and when the compound is dissolved in an organic solvent, it becomes an acidochromic dye whose optical properties change depending on the pH. Based on this finding, the present inventors conducted further extensive research and completed the present invention. That is, the present invention encompasses the following features.

[0009] Term 1. General formula (1):

[0010] [ka] [In the formula, Ar 1 represents a fused aromatic ring having a substituted or unsubstituted amino group. 2 represents a fused aromatic ring.] An acidochromic dye containing a compound represented by the formula:

[0011] Item 2. Said Ar 1 is represented by the general formula (2A), (2B) or (2C):

[0012] [ka] [In the formula, R 1a , R 2a , R 1b , R 2b , R 1c and R 2c are the same or different and represent a hydrogen atom or an alkyl group. 3a , R 4a , R 3b , R 4b , R3c and R 4c R may be the same or different and represent a hydrocarbon group. 5a , R 6a , R 5b , R 6b , R 5c and R 6c are the same or different and represent a hydrogen atom or a hydrocarbon group. 5a and R 6a , R 5b and R 6b , R 5c and R 6c may be joined together with the adjacent carbon atoms to form an aromatic ring. n1, n2, m1, m2, k1 and k2 are the same or different and represent an integer of 0 to 2.] Item 2. The acidochromic dye according to Item 1, wherein the group is represented by the formula:

[0013] Item 3. Said Ar 1 is represented by the general formula (2A1), (2B1) or (2C1):

[0014] [ka] [In the formula, R 1a , R 2a , R 1b , R 2b , R 1c and R 2c are the same or different and represent a hydrogen atom or an alkyl group. 5a , R 6a , R 5b , R 6b , R 5c and R 6c are the same or different and represent a hydrogen atom or a hydrocarbon group. 5a and R 6a , R 5b and R 6b , R 5c and R 6c may be taken together with adjacent carbon atoms to form an aromatic ring. Item 3. The acidochromic dye according to Item 2, wherein the group is represented by the formula:

[0015] Item 4. Said Ar 2is represented by the general formula (3A) or (3B):

[0016] [ka] [In the formula, R 7a , R 8a , R 7b and R 8b R may be the same or different and represent a hydrocarbon group. 9a , R 10a , R 9b and R 10b are the same or different and represent a hydrogen atom or a hydrocarbon group. 9a and R 10a , R 9b and R 10b may be joined together with the adjacent carbon atom to form an aromatic ring. n3 and m3 may be the same or different and represent an integer of 0 to 2. n4 and m4 may be the same or different and represent an integer of 0 to 3. 4. The acidochromic dye according to any one of items 1 to 3, wherein the group is represented by the formula:

[0017] Item 5. Said Ar 2 is represented by the general formula (3A1) or (3B1):

[0018] [ka] [In the formula, R 9a , R 10a , R 9b and R 10b are the same or different and represent a hydrogen atom or a hydrocarbon group. 9a and R 10a , R 9b and R 10b may be taken together with adjacent carbon atoms to form an aromatic ring. Item 5. The acidochromic dye according to item 4, wherein the group is represented by the formula:

[0019] Item 6. The acidochromic dye according to any one of Items 1 to 5, further comprising an organic solvent.

[0020] Item 7. The acidochromic dye according to Item 6, wherein the organic solvent is at least one selected from the group consisting of alcohol compounds, fluorine-containing alcohol compounds, and carboxylic acid compounds.

[0021] Section 8. General formula (1):

[0022] [ka] [In the formula, Ar 1 represents a fused aromatic ring having a substituted or unsubstituted amino group. 2 represents a fused aromatic ring.] A method for producing a compound represented by the formula: General formula (4):

[0023] [ka] [In the formula, Ar 1 is the same as above.] with a nitrite compound. A manufacturing method comprising:

[0024] Item 9. The method according to Item 8, wherein the reaction is carried out under acidic conditions.

[0025] Section 10. General formula (1'):

[0026] [ka] [In the formula, Ar 1 represents a fused aromatic ring having a substituted or unsubstituted amino group. 2 represents a fused aromatic ring.] A compound represented by the formula: The Ar 1 is represented by the general formula (2A), (2B) or (2C):

[0027] [ka] [In the formula, R1a , R 2a , R 1b , R 2b , R 1c and R 2c are the same or different and represent a hydrogen atom or an alkyl group. 3a , R 4a , R 3b , R 4b , R 3c and R 4c R may be the same or different and represent a hydrocarbon group. 5a , R 6a , R 5b , R 6b , R 5c and R 6c are the same or different and represent a hydrogen atom or a hydrocarbon group. 5a and R 6a , R 5b and R 6b , R 5c and R 6c may be joined together with the adjacent carbon atoms to form an aromatic ring. n1, n2, m1, m2, k1 and k2 are the same or different and represent an integer of 0 to 2.] A compound represented by the formula:

[0028] Section 11. General formula (1):

[0029] [ka] [In the formula, Ar 1 represents a fused aromatic ring having a substituted or unsubstituted amino group. 2 represents a fused aromatic ring.] A supramolecule containing a compound represented by the formula: [Effects of the Invention]

[0030] According to the present invention, it is possible to obtain an azo compound in which fused rings are bonded to each other via an azo group, and by using such an azo compound, it is possible to provide an acidochromic dye whose photophysical properties change depending on the pH. [Brief explanation of the drawings]

[0031] [Figure 1] The results of Test Example 1 are shown below, in which Compound 3 obtained in Example 1 was dissolved in hexafluoro-3-propanol (HFIP). [Figure 2] The results of Test Example 1 in which Compound 3 obtained in Example 1 was dissolved in acetic acid are shown below. [Figure 3] The results of Test Example 1 in which Compound 3 obtained in Example 1 was dissolved in tetrahydrofuran (THF) are shown below. [Figure 4] The results of Test Example 1 are shown below, in which Compound 3 obtained in Example 1 was dissolved in dimethyl sulfoxide (DMSO). [Figure 5] The results of Test Example 1 are shown for the case where Compound 6 or 7 obtained in Example 2 was dissolved in hexafluoro-3-propanol (HFIP). [Figure 6] The results of Test Example 1 are shown below, in which Compound 11 obtained in Example 3 was dissolved in hexafluoro-3-propanol (HFIP). [Figure 7] The results of Test Example 1 are shown below, in which Compound 11 obtained in Example 3 was dissolved in dimethyl sulfoxide (DMSO). [Figure 8] The results of Test Example 1 are shown below, in which Compound 10 obtained in Example 3 was dissolved in hexafluoro-3-propanol (HFIP). [Figure 9] 1 shows the results of confocal microscope observation of Test Example 2. [Figure 10] 1 shows the results of dynamic light scattering measurement in Test Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0032] In this specification, the term "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of."

[0033] In addition, in this specification, when a numerical range is expressed as "A to B," it means A or more and B or less.

[0034] 1. Acidochromic dyes The acidochromic dye of the present invention is represented by the general formula (1):

[0035] [ka] [In the formula, Ar 1 represents a fused aromatic ring having a substituted or unsubstituted amino group. 2 represents a fused aromatic ring.] The compound contains a compound represented by the formula:

[0036] The compound contained in the acidochromic dye of the present invention is an azo compound in which condensed rings are bonded to each other via an azo group, and is characterized by having an amino group in part of the compound. 1 is a fused aromatic ring having a substituted or unsubstituted amino group, and Ar 2 is a fused aromatic ring.

[0037] The number of substituents that a substituted or unsubstituted amino group may have is not particularly limited and can be, for example, 1 to 2, and the substituents may be the same or different. Examples of such substituents include a hydroxyl group, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), and an alkyl group as described below. Among these, from the viewpoints of ease of synthesis, acidochromic activity, and the like, it is preferable that the substituents that an amino group may have are 1 to 2 alkyl groups.

[0038] In the general formula (1), Ar 1 and Ar 2 The fused aromatic ring represented by the formula (I) is not particularly limited, but examples thereof include a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a pyrene ring, a chrysene ring, a triphenylene ring, a pentacene ring, a perylene ring, a benzopyrene ring, a coronene ring, and a corannulene ring.

[0039] Ar 1 and Ar 2The fused aromatic ring represented by may have a substituent. The substituent is not particularly limited, and examples thereof include a hydroxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group as described below, an alkoxy group (methoxy group, ethoxy group, n-propoxy group, etc.), an aryl group as described below, an aralkyl group as described below, an alkylaryl group as described below, an alkylaralkyl group as described below, and the amino group described above. That is, Ar 1 may further have an amino group as a substituent, or Ar 2 may have an amino group as a substituent.

[0040] When the fused aromatic ring has these substituents, the number of the substituents is not particularly limited, but from the viewpoints of ease of synthesis, acidochromic activity, etc., it is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 6.

[0041] Such a fused aromatic ring having a substituted or unsubstituted amino group, Ar 1 When the compound has a naphthalene skeleton, it is preferably represented by the general formula (2A), (2B) or (2C) from the viewpoints of ease of synthesis, acidochromic activity, etc.

[0042] [ka] [In the formula, R 1a , R 2a , R 1b , R 2b , R 1c and R 2c are the same or different and represent a hydrogen atom or an alkyl group. 3a , R 4a , R 3b , R 4b , R 3c and R 4c R may be the same or different and represent a hydrocarbon group. 5a , R 6a , R 5b , R 6b , R 5c and R 6c are the same or different and represent a hydrogen atom or a hydrocarbon group. 5a and R6a , R 5b and R 6b , R 5c and R 6c may be joined together with the adjacent carbon atoms to form an aromatic ring. n1, n2, m1, m2, k1 and k2 are the same or different and represent an integer of 0 to 2.] and a group represented by general formula (2A1), (2B1) or (2C1):

[0043] [ka] [In the formula, R 1a , R 2a , R 1b , R 2b , R 1c and R 2c are the same or different and represent a hydrogen atom or an alkyl group. 5a , R 6a , R 5b , R 6b , R 5c and R 6c are the same or different and represent a hydrogen atom or a hydrocarbon group. 5a and R 6a , R 5b and R 6b , R 5c and R 6c may be taken together with adjacent carbon atoms to form an aromatic ring. A group represented by the following formula is more preferred.

[0044] In addition, such fused aromatic rings, Ar 2 When the compound has a naphthalene skeleton, it is preferable to use a compound represented by the general formula (3A) or (3B) from the viewpoints of ease of synthesis, acidochromic activity, etc.

[0045] [ka] [In the formula, R 7a , R 8a , R 7b and R 8b R may be the same or different and represent a hydrocarbon group. 9a , R10a , R 9b and R 10b are the same or different and represent a hydrogen atom or a hydrocarbon group. 9a and R 10a , R 9b and R 10b may be joined together with the adjacent carbon atom to form an aromatic ring. n3 and m3 may be the same or different and represent an integer of 0 to 2. n4 and m4 may be the same or different and represent an integer of 0 to 3. Preferred are groups represented by general formula (3A1) or (3B1):

[0046] [ka] [In the formula, R 9a , R 10a , R 9b and R 10b are the same or different and represent a hydrogen atom or a hydrocarbon group. 9a and R 10a , R 9b and R 10b may be taken together with adjacent carbon atoms to form an aromatic ring. A group represented by the following formula is more preferred.

[0047] In the general formulae (2A), (2B), (2C), (2A1), (2B1) and (2C1), R 1a , R 2a , R 1b , R 2b , R 1c and R 2cThe alkyl group represented by the formula (I) is not particularly limited, but includes any of linear, branched, and cyclic (preferably linear or branched, more preferably linear). The number of carbon atoms in the alkyl group (in the case of linear or branched) is not particularly limited, and is, for example, preferably 1 to 5, and more preferably 1 to 3. The number of carbon atoms in the alkyl group (in the case of cyclic) is not particularly limited, and is, for example, preferably 3 to 7, and more preferably 4 to 6. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and a sec-butyl group.

[0048] R 1a , R 2a , R 1b , R 2b , R 1c and R 2c In the case where the alkyl group represented by the formula (I) has a substituent, examples of the substituent that the alkyl group may have include a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkoxy group (a methoxy group, an ethoxy group, an n-propoxy group, etc.), an aryl group described below, an aralkyl group described below, an alkylaryl group described below, an alkylaralkyl group described below, and the amino group described above.

[0049] In the general formulae (2A), (2B), (2C), (2A1), (2B1), (2C1), (3A), (3B), (3A1) and (3B1), R 3a , R 4a , R 3b , R 4b , R 3c , R 4c , R 7a , R 8a , R 7b , R 8b , R 9a , R 10a , R 9b and R 10bThe hydrocarbon group represented by is not particularly limited, and examples thereof include alkyl groups, aryl groups, and groups formed by any combination thereof (aralkyl groups, alkylaryl groups, alkylaralkyl groups, etc.). Among these, alkyl groups are preferred from the viewpoints of ease of synthesis, acidochromic activity, etc.

[0050] R 3a , R 4a , R 3b , R 4b , R 3c , R 4c , R 7a , R 8a , R 7b , R 8b , R 9a , R 10a , R 9b and R 10b The alkyl group as the hydrocarbon group represented by the formula (I) can be the same as those described above. The same applies to the preferred specific examples and substituents.

[0051] R 3a , R 4a , R 3b , R 4b , R 3c , R 4c , R 7a , R 8a , R 7b , R 8b , R 9a , R 10a , R 9b and R 10b The aryl group as the hydrocarbon group represented by the formula (I) is not particularly limited, but preferably has 6 to 12 carbon atoms, more preferably 6 to 8. The aryl group may be either monocyclic or polycyclic (e.g., bicyclic, tricyclic, etc.), but is preferably monocyclic. Specific examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a pentalenyl group, an indenyl group, an anthranyl group, a tetracenyl group, a pentacenyl group, a pyrenyl group, a perylenyl group, a fluorenyl group, and a phenanthryl group.

[0052] R 3a , R 4a , R 3b , R4b , R 3c , R 4c , R 7a , R 8a , R 7b , R 8b , R 9a , R 10a , R 9b and R 10b The aralkyl group as the hydrocarbon group represented by the formula (I) is not particularly limited, and examples thereof include aralkyl groups in which a hydrogen atom (for example, 1 to 3, preferably 1 hydrogen atom) of a linear or branched alkyl group having 1 to 5 carbon atoms (preferably 1 to 3) is substituted with the above-mentioned aryl group. Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

[0053] R 3a , R 4a , R 3b , R 4b , R 3c , R 4c , R 7a , R 8a , R 7b , R 8b , R 9a , R 10a , R 9b and R 10b The alkylaryl group as the hydrocarbon group represented by the formula (I) is not particularly limited, and examples thereof include alkylaryl groups in which the hydrogen atoms (for example, 1 to 3, preferably 1 hydrogen atom) of the aryl group are substituted with a linear or branched alkyl group having 1 to 5 carbon atoms (preferably 1 to 3). Specific examples of such alkylaryl groups include a tolyl group and a xylyl group.

[0054] R 3a , R 4a , R 3b , R 4b , R 3c , R 4c , R 7a , R 8a , R 7b , R 8b , R 9a , R 10a , R 9b and R 10bThe alkylaralkyl group as the hydrocarbon group represented by the formula (I) is not particularly limited, and examples thereof include alkylaralkyl groups in which a hydrogen atom (for example, 1 to 3, preferably 1 hydrogen atom) on the aromatic ring of the aralkyl group is substituted with a linear or branched alkyl group having 1 to 5 carbon atoms (preferably 1 to 3).

[0055] R 3a , R 4a , R 3b , R 4b , R 3c , R 4c , R 7a , R 8a , R 7b , R 8b , R 9a , R 10a , R 9b and R 10b When the hydrocarbon group represented by the formula (I) has a substituent, examples of the substituent that the hydrocarbon group may have include a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkoxy group (a methoxy group, an ethoxy group, an n-propoxy group, etc.), an aryl group described below, an aralkyl group described below, an alkylaryl group described below, an alkylaralkyl group described below, and the amino group described above.

[0056] When these substituents are present, the number of the substituents is not particularly limited, but can be, for example, 1 to 6, preferably 1 to 4, and more preferably 1 or 2.

[0057] In the general formulae (2A), (2B), (2C), (2A1), (2B1), (2C1), (3A), (3B), (3A1) and (3B1), R 5a and R 6a , R 5b and R 6b , R 5c and R 6c , R 9a and R 10a , R 9b and R 10bWhen these are taken together to form an aromatic ring with the adjacent carbon atom, the aromatic ring formed is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a pyrene ring, a chrysene ring, a triphenylene ring, a pentacene ring, a perylene ring, a benzopyrene ring, a coronene ring, and a corannulene ring.

[0058] In general formulae (2A), (2B), (2C), (3A) and (3B), n1, n2, m1, m2, k1, k2, n3 and m3 are not particularly limited, but are preferably integers of 0 to 2, more preferably 0 or 1, from the viewpoints of ease of synthesis, acidochromic activity and the like.

[0059] In general formulae (3A) and (3B), n4 and m4 are not particularly limited, but are preferably integers of 0 to 3, more preferably integers of 0 to 2, from the viewpoints of ease of synthesis, acidochromic activity, and the like.

[0060] Among the compounds constituting the acidochromic dye of the present invention, the compounds represented by the above general formulae (2A), (2B) and (2C) are novel compounds not described in the literature.

[0061] The acidochromic dye of the present invention may further contain an organic solvent in addition to the above-mentioned compounds.

[0062] Examples of organic solvents that the acidochromic dye of the present invention can contain include alcohol compounds (methanol, ethanol, etc.), fluorine-containing alcohol compounds (hexafluoro-2-propanol), carboxylic acid compounds (acetic acid, etc.), etc. Among these, from the viewpoint of acidochromic properties, fluorine-containing alcohol compounds (hexafluoro-2-propanol), carboxylic acid compounds (acetic acid, etc.), etc. are preferred.

[0063] When the acidochromic dye of the present invention contains an organic solvent, the concentration of the compound represented by the above general formula (1) is not particularly limited, but can usually be about 1 to 1000 mmol / L.

[0064] The acidochromic dye of the present invention is a material whose optical properties change depending on pH, and its color can be adjusted by the type of organic solvent and pH. Such acidochromic dye of the present invention can be used in applications such as pH sensors.

[0065] Furthermore, the compounds constituting the acidochromic dye of the present invention can also form supramolecules. Such supramolecules can be formed by the association of, for example, 2 to 1,000, and particularly 3 to 500, compounds represented by the general formula (1) described above. The supramolecules thus obtained can be made into particles with large particle diameters, for example, with an average particle diameter of, for example, 100 nm to 10 μm, preferably 300 nm to 5 μm. Therefore, the compounds represented by the general formula (1) capable of forming such supramolecules are useful for MOST materials, adhesives, other photochemical materials, and other electrochemical materials.

[0066] 2. Manufacturing method The production method of the present invention comprises reacting a compound represented by general formula (1):

[0067] [ka] [In the formula, Ar 1 represents a fused aromatic ring having a substituted or unsubstituted amino group. 2 represents a fused aromatic ring.] A method for producing a compound represented by the formula: General formula (4):

[0068] [ka] [In the formula, Ar 1 is the same as above.] with a nitrite compound. Equipped with.

[0069] In the general formulas (1) and (4), Ar 1 and Ar 2 The above-mentioned can be adopted.

[0070] The nitrite compound is not particularly limited, but examples thereof include alkali metal nitrites such as sodium nitrite and potassium nitrite. These nitrite compounds can be used alone or in combination of two or more.

[0071] The amount of the nitrite compound used is not particularly limited, but from the viewpoints of the conversion rate of the reaction, the yield of the target product, selectivity, etc., it is preferably 0.7 to 3.0 mol, more preferably 1.0 to 2.0 mol, per mol of the compound represented by general formula (4).

[0072] The reaction can be carried out under basic conditions, but is preferably carried out under acidic conditions in order to prevent the structure of the target product from being destroyed.

[0073] When the reaction is carried out under acidic conditions, the pH of the solution can be adjusted to about 1.0 to 7.0, preferably about 2.0 to 6.9, in which case, for example, an acid such as hydrochloric acid, hexafluoro-2-propanol, sulfuric acid, or hexafluoroboric acid can be added.

[0074] The reaction can usually be carried out in a solvent. The solvent is not limited as long as it does not interfere with the reaction, and examples thereof include amide compounds such as N,N-dimethylformamide; ether compounds such as tetrahydrofuran; halogenated aliphatic hydrocarbon compounds such as chloroform and dichloromethane; aromatic hydrocarbon compounds such as toluene and xylene; nitrile compounds such as acetonitrile; and ketone compounds such as acetone. Furthermore, the solvent can also be a mixture of these organic solvents and water. These solvents can be used alone or in combination of two or more.

[0075] The reaction atmosphere may be an inert atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere.

[0076] The reaction temperature is not particularly limited, but from the viewpoints of the conversion rate of the reaction, the yield of the target product, selectivity, etc., it can usually be set to −30 to 4° C., preferably −20 to 2° C. The reaction time can be set to a time that allows the reaction to be sufficiently completed.

[0077] After the reaction is complete, the reaction mixture may be purified by a conventional method, if necessary. For example, the precipitated solid may be filtered and washed with water, or purified by PTLC, to obtain the compound represented by general formula (1). [Example]

[0078] The present invention will be specifically explained below by way of examples, but the present invention is not limited to these examples.

[0079] Example 1

[0080] [ka]

[0081] 2-Aminoanthracene (96.1 mg, 0.497 mmol) was dissolved in solution A, which consisted of distilled water (0.90 mL), tetrahydrofuran (THF) (0.20 mL), and concentrated hydrochloric acid (0.17 mL), and the solution was cooled to 0°C. Sodium nitrite (36.3 mg, 0.526 mmol) was dissolved in distilled water (1.1 mL) and the solution was cooled to 0°C (solution B). Solution B was added dropwise to solution A. 2-Aminoanthracene (95.7 mg, 0.495 mmol) was dissolved in tetrahydrofuran (THF) (1.9 mL) (solution C), which was cooled to 0°C. Solution C was slowly added to solution A and stirred at 0°C for 1 hour. The precipitated solid was collected by filtration and washed with water (133.7 mg, 67%). 1H NMR (600 MHz, acetone-d6) δ 9.45 (s, 1H), 8.70 (s, 1H), 8.61 (s, 2H), 8.45 (dd, J = 9.3, 1.7 Hz, 1H), 8.38 (s, 1H), 8.23 ​​(d, J = 8.9 Hz, 1H), 8.16 (d, J = 8.2 Hz, 1H), 8.12 (dd, J = 9.5, 2.9 Hz, 2H), 8.02 (d, J = 8.2 Hz, 1H), 7.98 (d, J = 8.9 Hz, 1H), 7.56-7.51 (m, 3H), 7.45-7.43 (m, 1H), 7.46-7.42 (m, 1H), 7.25 (d, J = 8.9 Hz, 1H). HRMS (DART) m / z calculation for C 28 H 20 N3[M+H] + : 398.17, found 398.16395.

[0082] Example 2

[0083] [ka]

[0084] 1-Aminoanthracene (56.1 mg, 0.290 mmol) was dissolved in solution A, which consisted of distilled water (0.50 mL), tetrahydrofuran (THF) (0.12 mL), and concentrated hydrochloric acid (0.10 mL), and the solution was cooled to 0°C. Sodium nitrite (18.4 mg, 0.267 mmol) was dissolved in distilled water (0.62 mL) and the solution was cooled to 0°C (solution B). Solution B was added dropwise to solution A. 1-Aminoanthracene (55.5 mg, 0.287 mmol) was dissolved in tetrahydrofuran (THF) (0.62 mL) (solution C), which was cooled to 0°C. Solution C was slowly added to solution A, and the mixture was stirred at 0°C for 1 hour. The precipitated solid was collected by filtration and washed with water. The crude product was then purified by PTLC (Hexane / CHCl3 = 1 / 1) (13.3 mg, 12%). 1 H NMR (600 MHz, CDCl3) δ 9.47 (s, 1H), 8.61 (s, 1H), 8.52 (s, 1H), 8.37 (s, 1H), 8.21 (d, J = 8.9 Hz, 1H), 8.17-8.13 (m, 1H), 8.11-8.04 (m, 3H), 8.02 (d, J = 8.2 Hz, 1H), 7.81 (d, J = 7.2 Hz, 1H), 7.61-7.50 (m, 5H), 7.48 (d, J = 9.3 Hz, 1H), 6.80 (brs, 2H). LRMS (APCI) m / z calculation for C 28 H 20 N3[M+H] + : 398.17, found 398.1.

[0085] Example 3

[0086] [ka]

[0087] 1-Aminonaphthalene (72.9 mg, 0.510 mmol) was dissolved in solution A, which consisted of distilled water (0.90 mL), tetrahydrofuran (THF) (0.20 mL), and concentrated hydrochloric acid (0.17 mL), and the solution was cooled to 0°C. Sodium nitrite (34.9 mg, 0.506 mmol) was dissolved in distilled water (1.1 mL) and the solution was cooled to 0°C (solution B). Solution B was added dropwise to solution A. 1-Aminonaphthalene (71.9 mg, 0.503 mmol) was dissolved in tetrahydrofuran (THF) (0.21 mL) (solution C), which was cooled to 0°C. Solution C was slowly added to solution A, and the mixture was stirred at 0°C for 1 hour. The precipitated solid was collected by filtration and washed with water. The crude product was then purified by PTLC (CHCl3) (Compound A: 52.4 mg, 35%, Compound B: 8.4 mg, 6%). 1 H NMR (600 MHz, CDCl3) compound A δ 9.18 (d, J = 8.6 Hz, 1H), 9.04 (d, J = 8.6 Hz, 1H), 8.11 (d, J = 8.2 Hz, 1H), 7.98-7.91 (m, 3H), 7.85 (d, J = 8.6 Hz, 1H), 7.70-7.66 (m, 1H), 7.66-7.62 (m, 1H), 7.62-7.55 (m, 3H), 6.89 (d, J = 8.2 Hz, 1H) (52.4 mg, 35% yield). LRMS (APCI) m / z calculation for C 20 H 15 N3[M+H] + : 298.13, found 298.2. compound B δ 8.88 (d, J = 8.6 Hz, 1H), 8.09 (d, J = 8.9 Hz, 1H), 8.01 (d, J = 7.9 Hz, 1H), 7.95-7.91 (m, 2H), 7.85-7.79 (m, 2H), 7.67-7.63 (m, 1H), 7.61-7.56 (m, 3H), 7.55-7.51 (m, 1H), 7.28 (d, J = 8.9 Hz, 1H) (8.4 mg, 6% yield). LRMS (APCI) m / z calculation for C 20 H 15 N3[M+H] + : 298.13, found 298.0.

[0088] Test Example 1: pH Dependence A few milligrams of compound 3 obtained in Example 1, compound 6 or 7 obtained in Example 2, or compound 10 or 11 obtained in Example 3 were dissolved in 7 mL of various organic solvents (hexafluoro-2-propanol, acetic acid, tetrahydrofuran, dimethyl sulfoxide). Then, sodium hydroxide aqueous solution or hydrochloric acid was added in small amounts, and the color was evaluated while changing the pH, and the ultraviolet-visible absorption spectrum was measured. The results are shown in Figures 1 to 8.

[0089] As a result, in hexafluoro-2-propanol and acetic acid, the color and absorption spectrum changed with a change in pH, indicating that it is an acidochromic dye. When compound 3 was dissolved in tetrahydrofuran and dimethyl sulfoxide, the color and absorption spectrum changed only slightly immediately after the pH was changed, but after leaving the solution for a while, the color and absorption spectrum changed significantly. This suggests that multiple compounds 3 associated with each other over time to form supramolecules, resulting in significant changes in the color and absorption spectrum.

[0090] Based on the above results, the type of solvent, the maximum absorption wavelength in the ultraviolet-visible absorption spectrum, and the color of the solution (basic form and acidic form) are shown in Table 1.

[0091] [Table 1]

[0092] Test Example 2: Confocal microscope observation Compound 3 was dissolved in the dimethyl sulfoxide solution (HCl 1.0 mol / L) obtained in Test Example 1, and the solution, which had turned blue after being left to stand for 3 days, was observed under a confocal microscope. The results are shown in Figure 9.

[0093] In Figure 9, the left image is a fluorescence image taken with a 405 nm laser, and the right image is the result of differential interference contrast (DIC) observation. As a result, particles with a large aspect ratio that emit fluorescence in response to 405 nm light were observed, suggesting the formation of supramolecules in which multiple molecules of compound 3 are associated. Although no confocal microscopy was performed on the tetrahydrofuran solvent, a color change was observed over a long period of time when hydrochloric acid was added, similar to when dimethyl sulfoxide was used, suggesting the formation of supramolecules.

[0094] Test Example 3: Dynamic Light Scattering Measurement Compound 3 was dissolved in the dimethyl sulfoxide solution (HCl 1.0 mol / L) obtained in Test Example 1, and the solution turned blue after standing for 3 days. Dynamic light scattering measurement (DLS measurement) was performed on the solution. The results are shown in Figure 10.

[0095] In the blue solution of dimethyl sulfoxide with hydrochloric acid, a particle distribution centered on particle diameters of 395 nm and 805 nm was observed. This also suggests the formation of supramolecules. On the other hand, DLS measurements were also performed on the red solution of compound 3 dissolved in dimethyl sulfoxide alone, and large particle diameters on the order of μm (approximately 1 to 4 μm) were observed.

Claims

1. General formula (1): 【Chemical 1】 [In the formula, Ar １ represents a fused aromatic ring having a substituted or unsubstituted amino group. ２ represents a fused aromatic ring.] An acidochromic dye containing a compound represented by the formula:

2. The Ar １ is represented by general formula (2A), (2B) or (2C): 【Chemistry 2】 [In the formula, R １ａ , R ２ａ , R １ｂ , R ２ｂ , R １ｃ and R ２ｃ are the same or different and represent a hydrogen atom or an alkyl group. ３ａ , R ４ａ , R ３ｂ , R ４ｂ , R ３ｃ and R ４ｃ are the same or different and represent a hydrocarbon group. ５ａ , R ６ａ , R ５ｂ , R ６ｂ , R ５ｃ and R ６ｃ are the same or different and represent a hydrogen atom or a hydrocarbon group. ５ａ and R ６ａ , R ５ｂ and R ６ｂ , R ５ｃ and R ６ｃ may be joined together with adjacent carbon atoms to form an aromatic ring. n1, n2, m1, m2, k1 and k2 are the same or different and represent an integer of 0 to 2.] The acidochromic dye according to claim 1 , wherein the group is represented by the formula:

3. The Ar １ is represented by the general formula (2A1), (2B1) or (2C1): 【Chemistry 3】 [In the formula, R １ａ , R ２ａ , R １ｂ , R ２ｂ , R １ｃ and R ２ｃ are the same or different and represent a hydrogen atom or an alkyl group. ５ａ , R ６ａ , R ５ｂ , R ６ｂ , R ５ｃ and R ６ｃ are the same or different and represent a hydrogen atom or a hydrocarbon group. ５ａ and R ６ａ , R ５ｂ and R ６ｂ , R ５ｃ and R ６ｃ may be taken together with adjacent carbon atoms to form an aromatic ring. The acidochromic dye according to claim 2 , wherein the group is represented by the formula:

4. The Ar ２ is represented by general formula (3A) or (3B): 【Chemistry 4】 [In the formula, R ７ａ , R ８ａ , R ７ｂ and R ８ｂ are the same or different and represent a hydrocarbon group. ９ａ , R １０ａ , R ９ｂ and R １０ｂ are the same or different and represent a hydrogen atom or a hydrocarbon group. ９ａ and R １０ａ , R ９ｂ and R １０ｂ may be joined together with the adjacent carbon atoms to form an aromatic ring. n3 and m3 may be the same or different and represent an integer of 0 to 2. n4 and m4 may be the same or different and represent an integer of 0 to 3. The acidochromic dye according to claim 1 , wherein the group is represented by the formula:

5. The Ar ２ is represented by general formula (3A1) or (3B1): 【Chemistry 5】 R represents a radical. ９ａ and R １０ａ , R ９ｂ and R １０ｂ may be taken together with adjacent carbon atoms to form an aromatic ring. The acidochromic dye according to claim 4 , wherein the group is represented by the formula:

6. The acidochromic dye according to claim 1 , further comprising an organic solvent.

7. 7. The acidochromic dye according to claim 6, wherein the organic solvent is at least one selected from the group consisting of alcohol compounds, fluorine-containing alcohol compounds, and carboxylic acid compounds.

8. General formula (1): 【Chemistry 6】 [In the formula, Ar １ represents a fused aromatic ring having a substituted or unsubstituted amino group. ２ represents a fused aromatic ring.] A method for producing a compound represented by the formula: General formula (4): 【Chemistry 7】 [In the formula, Ar １ is the same as above.] with a nitrite compound. A manufacturing method comprising:

9. The method according to claim 8 , wherein the reaction is carried out under acidic conditions.

10. General formula (1'): 【Chemistry 8】 [In the formula, Ar １ represents a fused aromatic ring having a substituted or unsubstituted amino group. ２ represents a fused aromatic ring.] A compound represented by the formula: The Ar １ is represented by general formula (2A), (2B) or (2C): 【Chemistry 9】 [In the formula, R １ａ , R ２ａ , R １ｂ , R ２ｂ , R １ｃ and R ２ｃ are the same or different and represent a hydrogen atom or an alkyl group. ３ａ , R ４ａ , R ３ｂ , R ４ｂ , R ３ｃ and R ４ｃ are the same or different and represent a hydrocarbon group. ５ａ , R ６ａ , R ５ｂ , R ６ｂ , R ５ｃ and R ６ｃ are the same or different and represent a hydrogen atom or a hydrocarbon group. ５ａ and R ６ａ , R ５ｂ and R ６ｂ , R ５ｃ and R ６ｃ may be joined together with adjacent carbon atoms to form an aromatic ring. n1, n2, m1, m2, k1 and k2 are the same or different and represent an integer of 0 to 2.] A compound represented by the formula:

11. General formula (1): 【Chemistry 10】 [In the formula, Ar １ represents a fused aromatic ring having a substituted or unsubstituted amino group. ２ represents a fused aromatic ring.] A supramolecule containing a compound represented by the formula:

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