JP5531586B2 - Compound - Google Patents

Description

  The present invention relates to compounds useful as dyes.

  Conventionally, pigments such as metal complex compounds have been used in various fields (for example, fiber materials, liquid crystal display devices, etc.) for color display using reflected light or transmitted light. For example, Patent Document 1 describes a chromium complex compound represented by the following formula and having an azo compound as a ligand.

JP 55-092768

  Conventional compounds may not have sufficient solubility and spectral density.

Therefore, as a result of intensive studies on the above problems, the present inventors have found that certain compounds are excellent in solubility and spectral concentration, and have reached the present invention.
That is, the present invention is a compound represented by the formula (I).

[In Formula (I), R ¹ and R ² each independently represents a hydroxy group or —NHR ³³ .
R ³³ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group, an alkylcyclohexyl group having 1 to 4 carbon atoms in an alkyl portion, or an aliphatic alkoxy group having 2 to 15 carbon atoms. It represents an alkyl group, —R ³¹ —CO—O—R ³² , —R ³¹ —O—CO—R ³² , or an aralkyl group having 7 to 10 carbon atoms.
R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ^{3 to} R ¹⁸ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a nitro group.
R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a methyl group, an ethyl group or an amino group.
R ^{21 to} R ²⁵ each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. Represent.
R ²⁶ and R ²⁷ each independently represents a hydrogen atom or a methyl group. ]

Further, the present invention is the above compound, wherein R ¹ and R ² are each independently a hydroxy group or NHR ³³ , and R ³³ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

Moreover, this invention is the said compound whose at least 1 is a nitro group among R < ³ > -R < ¹⁸ >.

The present invention, R ²⁵ is the above compound is an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

  The compound of the present invention is excellent in solubility and spectral density.

It is a graph which shows the transmittance | permeability of an Example.

The compound of the present invention is represented by the formula (I).
The compound represented by the formula (I) includes a chromium complex ion in the anion portion and a cation derived from the rhodamine compound in the cation portion.

[In Formula (I), R ¹ and R ² each independently represents a hydroxy group or —NHR ³³ .
R ³³ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group, an alkylcyclohexyl group having 1 to 4 carbon atoms in an alkyl portion, or an aliphatic alkoxy group having 2 to 15 carbon atoms. It represents an alkyl group, —R ³¹ —CO—O—R ³² , —R ³¹ —O—CO—R ³² , or an aralkyl group having 7 to 10 carbon atoms.
R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ^{3 to} R ¹⁸ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a nitro group.
R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a methyl group, an ethyl group or an amino group.
R ^{21 to} R ²⁵ each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. Represent.
R ²⁶ and R ²⁷ each independently represents a hydrogen atom or a methyl group. ]

The compound represented by the formula (I) can have both water solubility and oil solubility by having a sulfo group, a sulfamoyl group, and an N-substituted sulfamoyl group. In order to improve oil solubility, in formula (I), R ¹ and R ² are each independently a hydroxy group or —NHR ³³ , and R ³³ is a hydrogen atom or optionally substituted 1 to 1 carbon atoms. 8 aliphatic hydrocarbon groups are preferred.

The compound represented by Formula (I) can improve heat resistance by having a nitro group. Therefore, in formula (I), it is preferable that at least one of R ^{3 to} R ¹⁸ is a nitro group.

In order to improve the oil solubility of the compound represented by the formula (I), in the formula (I), R ²⁵ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

  Specific examples of the optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an N-butyl group, and a sec-butyl group. Tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, dexyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5 -Dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group and 1,1,5,5-tetramethylhexyl group.

  Examples of the alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl moiety include 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-n-propylcyclohexyl group, 2-isopropylcyclohexyl group, 2-n-butylcyclohexyl group, Examples include 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-n-propylcyclohexyl group, 4-isopropylcyclohexyl group, 4-n-butylcyclohexyl group and the like.

  Examples of the alkoxyalkyl group having 2 to 15 carbon atoms include methoxymethyl group, methoxyethyl group, methoxy-n-propyl group, methoxy-n-butyl group, methoxy-n-pentyl group, 1-ethoxy-n-propyl group, 2-ethoxy-n-propyl group, 1-ethoxy-isopropyl group, 2-ethoxy-isopropyl group, 1-isopropoxy-n-propyl group, 2-isopropoxy-n-propyl group, 1-isopropoxy-isopropyl group , 2-isopropoxy-isopropyl group, octyloxy-n-propyl group, 3-ethoxy-n-propyl group, 3- (2-ethylhexyloxy) propyl group, etc., preferably 1-ethoxy-n-propyl Group, octyloxy-n-propyl group, 3-ethoxy-n-propyl group, 3- (2-ethylhexyl) Oxy) propyl group.

-R ^{31 -CO-O-R 32} and ^{-R 31 -O-CO-R 32} (R 31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon ^{atoms, R 32} is C 1 -C -8 represents a monovalent aliphatic hydrocarbon group having 8 to 8 carbon atoms) and an aliphatic hydrocarbon group having 2 to 9 carbon atoms having a carboxy group and an aliphatic hydrocarbon having 1 to 8 carbon atoms having a hydroxy group. A group having 4 to 10 carbon atoms having an ester bond obtained by dehydration condensation, an aliphatic hydrocarbon group having 1 to 8 carbon atoms having a hydroxy group, and an aliphatic hydrocarbon having 2 to 9 carbon atoms having a carboxy group; Is a group having an ester bond obtained by dehydration condensation. The number of carbon atoms in —R ³¹ —CO—O—R ³² and —R ³¹ —O—CO—R ³² is preferably 4 to 10.
Examples of the C2-C9 aliphatic hydrocarbon having a carboxy group include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, and the like. Preferably, acetic acid, propionic acid, and butyric acid are used.
Examples of the C2-C9 aliphatic hydrocarbon group having a carboxy group include those obtained by removing one hydrogen atom from the C2-C9 aliphatic hydrocarbon having a carboxy group.

Examples of the C1-C8 aliphatic hydrocarbon having a hydroxy group include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, 1 -Methyl-n-butanol, 2-methyl-n-butanol, 3-methyl-n-butanol, n-hexanol, n-heptanol, n-octanol, etc., preferably methanol, ethanol, n-propanol, isopropanol N-butanol, isobutanol, sec-butanol, and tert-butanol.
As for the C1-C8 aliphatic hydrocarbon group which has the said hydroxy group, what remove | excluded one hydrogen atom from the C1-C8 aliphatic hydrocarbon which has the said hydroxy group is mentioned.
4 to 10 carbon atoms having an ester bond obtained by dehydration condensation between the aliphatic hydrocarbon group having 2 to 9 carbon atoms having a carboxy group and the aliphatic hydrocarbon having 1 to 8 carbon atoms having a hydroxy group Groups include propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, heptyl acetate, ethyl butyrate, isopropyl butyrate, butyl butyrate, pentyl butyrate, hexyl butyrate, heptyl butyrate Group, octyl butyrate, methyl valerate, ethyl valerate, isopropyl valerate, isobutyl valerate, pentyl valerate, hexyl valerate, heptyl valerate, methyl caproate, ethyl caproate Group, propyl caproate, butyl caproate, hexyl caproate, methyl enanthate, ethyl enanthate, isopropyl enanthate , Isobutyl enanthate, pentyl enanthate, methyl caprylate, ethyl caprylate, propyl caprylate, isopropyl caprylate, butyl caprylate, isobutyl caprylate, methyl pelargonate, ethyl pelargonate Propyl pelargonate, isopropyl pelargonate, etc., preferably propyl acetate, butyl acetate, ethyl butyrate, butyl butyrate, pentyl butyrate, hexyl acetate, methyl valerate, ethyl valerate Group, isopropyl valerate, isobutyl valerate.

  In the aliphatic hydrocarbon group having 2 to 9 carbon atoms and the aliphatic hydrocarbon having 2 to 9 carbon atoms having a carboxy group, the carboxy group is replaced with a -CO-Cl group. A group having 4 to 10 carbon atoms having an ester bond by dehydrochlorination condensation with an aliphatic hydrocarbon having 1 to 8 carbon atoms having a hydroxy group or an aliphatic hydrocarbon group having 1 to 8 carbon atoms having a hydroxy group. It can also be obtained.

  Examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group, a phenethyl group, and a 1-methyl-3-phenylpropyl group.

  Examples of the optionally substituted aromatic hydrocarbon having 6 to 10 carbon atoms include a phenyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group, and a naphthyl group.

  Among the compounds represented by the formula (I), preferred examples of the pyrazole azo compound that becomes a ligand in the chromium complex of the anion moiety include formulas (I-1) to (I-136).

  Among the compounds represented by the formula (I), preferable examples of the rhodamine compound serving as a cation moiety include formulas (II-1) to (II-146).

  The pyrazole azo compound that becomes the ligand of the compound represented by the formula (I) can be produced by coupling a diazonium salt and a pyrazole compound, as is well known in the dye field. For example, a compound represented by the formula (b) obtained by diazotizing an amine (diazo component) represented by the formula (a) with nitrous acid, nitrite or nitrite is used as the diazonium salt. Can be used.

(In formulas (a) and (b), R ^{11 to} R ¹⁴ represent the same meaning as in formula (I).
X ⁻ represents an inorganic or organic anion. )

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ —COO ⁻ , Ph—COO ^{− and the} like. Preferred are chloride ion, bromide ion, and CH ₃ —COO ^— .

  Then, the diazonium salt represented by the formula (b) and the pyrazole compound (coupling component) represented by the formula (c) are reacted in an aqueous solvent at 20 to 60 ° C. to express the formula (I). A pyrazole azo compound (hereinafter may be referred to as “pyrazole azo compound (I)”) serving as a ligand of the compound to be produced can be produced.

(In formula (c), R ^{1 to} R ⁶ and R ¹⁹ represent the same meaning as in formula (I)).

The pyrazole azo compound (I) having —NHR ³³ in R ¹ can also be produced by using amines (a) having a sulfamoyl group or an N-substituted sulfamoyl group, but amines (a) having a sulfo group can be produced. It is preferable to produce a sulfo group by sulfonamidation after carrying out a coupling reaction. For example, a compound having a sulfo group in formula (I) (hereinafter referred to as “azosulfonic acid (I)”) is synthesized, and the sulfo group (—SO ₃ H) is converted to a sulfonyl halide (—SO ₃ ) with a halogenated thionyl compound. ₂ X; X is a halogen atom) to obtain a sulfonyl halide compound, and then reacting the sulfonyl halide compound with an amine to sulfonamid the sulfo group to produce the pyrazole azo compound (I).

  Preferable examples of azosulfonic acid (I) include compounds represented by formulas (I-1) to (I-5), and particularly preferable examples include formulas (I-1) and (I-2). The compound represented by these is mentioned. Examples of the thionyl halide compound include thionyl fluoride, thionyl chloride, thionyl bromide, thionyl iodide and the like, preferably thionyl chloride and thionyl bromide, and particularly preferably thionyl chloride. The amount of thionyl halide used is, for example, about 1 to 10 moles with respect to 1 mole of azosulfonic acid (I). When water is brought into the reaction system, it is preferable to use an excessive amount of the thionyl halide compound.

  The sulfonyl halide is carried out in a solvent. Examples of the solvent include ethers such as 1,4-dioxane (particularly preferably cyclic ethers); chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, Halogenated hydrocarbons such as amyl chloride and 1,2-dibromoethane can be used. The usage-amount of a solvent is 3 mass parts or more (preferably 5 mass parts or more) with respect to 1 mass part of azosulfonic acid (I), for example, is 10 mass parts or less (preferably 8 mass parts or less).

  In sulfonyl halide formation, it is preferable to use N, N-dialkylformamide (for example, N, N-dimethylformamide, N, N-diethylformamide, etc.) in combination. When N, N-dialkylformamide is used, the amount used is, for example, 0.05 to 1 mol with respect to 1 mol of the thionyl halide compound. When azosulfonic acid (I) and N, N-dialkylformamide are mixed in advance in a solvent and then a thionyl halide compound is added, heat generation can be suppressed.

  The reaction temperature in the sulfonyl halide formation is, for example, 0 ° C. or higher, preferably 30 ° C. or higher and 70 ° C. or lower, preferably 60 ° C. or lower. The reaction time is, for example, 0.5 hours or more, preferably 3 hours or more and 8 hours or less, preferably 5 hours or less.

  The sulfonyl halide compound prepared as described above may be isolated and then reacted with the amine, or may be reacted with the amine in the reaction mixture without isolation. In the case of isolation, for example, the reaction mixture and water may be mixed, and the precipitated crystals may be collected by filtration. The obtained crystals of the sulfonyl halide compound may be washed with water and dried as necessary before the reaction with the amine. In this specification, in order to distinguish this amine from the basic catalyst described later, hereinafter, it may be referred to as a reactive amine.

Examples of the reactive amine include a primary amine, and the primary amine is represented by H ₂ N—R ³³ (R ³³ is the same as described above).
Specific examples of H ₂ N—R ³³ include n-propylamine, n-butylamine, n-hexylamine, dimethylhexylamine (such as 1,5-dimethylhexylamine), tetramethylbutylamine (1,1,3,3). 3-tetramethylbutylamine and the like), ethylhexylamine (such as 2-ethylhexylamine), aminophenylbutane (such as 3-amino-1-phenylbutane), and isopropoxypropylamine. The usage-amount of a reactive amine is 2 mol or more and 10 mol or less with respect to 1 mol of sulfonyl halide compounds, Preferably it is 7 mol or less.

  The order of addition of the sulfonyl halide compound and the reactive amine is not particularly limited, but the reactive amine is often added (dropped) to the sulfonyl halide compound. The reaction between the sulfonyl halide compound and the reactive amine is preferably performed in a solvent. As the solvent, the same solvent as that used for preparing the sulfonyl halide compound can be used.

  The reaction between the sulfonyl halide compound and the reactive amine is preferably performed in the presence of a basic catalyst. Examples of basic catalysts include tertiary amines (aliphatic tertiary amines such as triethylamine and triethanolamine; aromatic tertiary amines such as pyridine), and secondary amines (aliphatic secondary amines such as diethylamine; piperidine, etc. And cycloaliphatic secondary amines). Among these, tertiary amines, particularly aliphatic tertiary amines such as triethylamine are preferable. The usage-amount of a basic catalyst is 1.1 mol or more and 6 mol or less with respect to a reactive amine, Preferably it is 1.1 mol or more and 5 mol or less.

  When the reactive amine and the basic catalyst are added to the sulfonyl halide compound, the timing of adding the basic catalyst is not particularly limited, and may be either before or after the addition of the reactive amine. You may add at the same timing. Further, it may be added after mixing with the reactive amine in advance, or may be added separately from the reactive amine.

  The reaction temperature between the sulfonyl halide compound and the reactive amine is, for example, 0 ° C. or higher and 50 ° C. or lower, preferably 0 ° C. or higher and 30 ° C. or lower. The reaction time is 1 to 5 hours.

  The method for obtaining the target pyrazole azo compound (I) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, the reaction mixture is preferably mixed with an acid (acetic acid) and water, and the precipitated crystals are collected by filtration. It is preferable that the acid and water are prepared in advance as an aqueous acid solution, and then the reaction mixture is added to the aqueous solution. The temperature at which the reaction mixture is added is 10 ° C or higher, preferably 20 ° C or higher and 50 ° C or lower, preferably 30 ° C or lower. Moreover, after addition, it is preferable to stir at the same temperature for 0.5 to 2 hours. The crystals collected by filtration are washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  The chromium complex salt which becomes the anion part of the compound represented by the formula (I) can be produced by reacting the pyrazole azo compound (I) and the chromium compound at 70 to 100 ° C. in an aqueous solvent. It is preferable to react the pyrazole azo compound (I) and the chromium compound in a molar ratio of 2: 1 to 4: 1.

  As said chromium compound, chromium formate, chromium acetate, chromium chloride, chromium fluoride, etc. are mentioned, Preferably chromium formate, chromium acetate, etc. are mentioned.

  The compound represented by the formula (I) can be produced by subjecting a chromium complex salt of an anion portion and a rhodamine compound of a cation portion to a salt exchange reaction in a solvent. It is preferable to react the chromium complex salt of the anion portion and the rhodamine compound of the cation portion in a molar ratio of 1: 1 to 1: 4.

  As a compound represented by Formula (I), the compound of a following formula is mentioned, for example.

The compound represented by the formula (I) exhibits high solubility in a solvent. Examples of the solvent include water and organic solvents. As the organic solvent, there are various types. For example, a solvent having a carbonyl group or a solvent having a hydroxy group is preferably used. Examples of the solvent having a carbonyl group include ethyl pyruvate, ethyl acetoacetate, diacetone alcohol, and preferably diacetone alcohol. Examples of the solvent having a hydroxy group include methanol, ethanol, 1-propanol, and isopropanol, and preferably methanol.
Since the compound represented by the formula (I) exhibits high solubility and high spectral density, it can be used for fiber materials, liquid crystal display devices, and the like that perform color display using reflected light or transmitted light.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited by the following Examples. In the examples and comparative examples, “%” and “parts” are mass% and mass parts unless otherwise specified.

Example 1
After adding 80 parts of water to 10.5 parts of 2-amino-4-nitrophenol represented by the formula (a-1), 16.3 parts of 35% hydrochloric acid was added little by little under ice cooling, and dissolved. 24.7 parts of a 20% aqueous sodium nitrite solution was added and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  After adding 65 parts of water and 3 parts of sodium hydroxide to 19 parts of 3-methyl-1- (4-sulfophenyl) -5-pyrazolone represented by the formula (c-1), 10% acetic acid was added under ice cooling. 100 parts of an aqueous sodium solution was added to obtain a pyrazolone solution.

  The following operations were performed under ice cooling. While stirring the pyrazolone solution, the suspension containing the diazonium salt was added dropwise by a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a dark solution. 20 parts of purified salt (sodium chloride) was added to the reaction solution and stirred for 1 hour. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 27.1 parts (yield 95%) of the azo compound represented by the formula (I-5).

  After 150 parts of water and 100 parts of dimethylformamide are added and dissolved in 18.2 parts of the azo compound represented by the formula (I-5), 2.8 parts of chromium formate is added and heated at 100 ° C. for 5 hours. And a dark solution was obtained by stirring. After cooling to 25 ° C, 12 parts of a 20% aqueous sodium hydroxide solution was added, and after stirring for 30 minutes, 60 parts of purified salt (sodium chloride) was added to the reaction solution and stirred for 30 minutes. The dark solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 13.0 parts (yield 95%) of a chromium complex salt represented by the formula (d-1).

  200 parts of methanol and 100 parts of dimethylformamide are dissolved in 9.1 parts of the chromium complex salt represented by the formula (d-1), and then 4.8 parts of a rhodamine compound represented by the formula (II-113). And stirred for 30 minutes to obtain a dark red solution. Concentration at 50 ° C. under reduced pressure gave a dark solid. 250 parts of water was added to the obtained dark solid, and the dark solid obtained by filtration was dried at 60 ° C. under reduced pressure, and 10.6 parts (yield 76%) of the compound represented by the formula (e-1) Obtained. The transmittance of the compound represented by the formula (e-1) was measured using an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). FIG. 1 is a graph showing the transmittance of the compound represented by the formula (e-1). The vertical axis represents transmittance (%), and the horizontal axis represents wavelength (nm).

The structure of the compound represented by the formula (e-1) was determined by elemental analysis. As an analytical instrument, an ICP emission analyzer (ICPS-8100; manufactured by Shimadzu Corporation) was used.
C58.0 H5.1 N9.7 Cr1.11

Example 2
The formula (a) was changed in the same manner as in Example 1 except that 2-amino-4-nitrophenol represented by formula (a-1) was replaced by 2-amino-5-nitrophenol represented by formula (a-2). The compound represented by e-2) was obtained. The transmittance of the compound represented by the formula (e-2) was measured using an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). FIG. 1 is a graph showing the transmittance of the compound represented by the formula (e-2). The vertical axis represents transmittance (%), and the horizontal axis represents wavelength (nm).

The structure of the compound represented by the formula (e-2) was determined by elemental analysis. As an analytical instrument, an ICP emission analyzer (ICPS-8100; manufactured by Shimadzu Corporation) was used.
C53.1 H4.1 N9.0 Cr3.18

Comparative Example 1
Dissolve 0.35 g of the compound represented by the formula (d-1) described in Patent Document 1 in ethyl lactate to a volume of 250 cm ^3, and dilute 2 cm ³ with ion-exchanged water to a volume of 100 cm ^3. (Concentration: 0.028 g / L), an absorption spectrum was measured using an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm).

[Spectral density]
The compounds obtained in Examples 1 and 2 and Comparative Example 1 were dissolved in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with water to a volume of 100 cm ³ (concentration: 0.028 g / L ), An ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) [quartz cell, cell length is 1 cm], and the absorption spectrum was measured. The results are shown in Table 1.

[Solubility]
The solubility of the compounds obtained in Examples 1 and 2 and Comparative Example 1 in diacetone alcohol (hereinafter sometimes abbreviated as DAA) was determined as follows:
In a 50 mL sample tube, each compound was mixed with DAA so as to have a mixing ratio of 1% (W / V) and 3% (W / V) respectively, and after being sealed, an ultrasonic shaker was used at 40 ° C. for 10 minutes. Shake with. Then, after standing at room temperature for 30 minutes, the mixture was filtered, and the filtrate was visually checked for the presence of insolubles.
1% (W / V) adjusted mixed solution with insolubles is less than 1% solubility x, 1% (W / V) adjusted mixed solution has no insolubles and 3% (W / V) V) If the mixed solution with the insoluble matter in the adjusted mixed solution has a solubility of less than 1 to 3%, Δ, and if the mixed solution with 3% (W / V) adjusted does not have an insoluble matter, the solubility should be 3% or more. expressed. The results are shown in Table 1.

  From the results in Table 1, it can be seen that the compounds of Examples have both high spectral density and solubility.

  The compound of the present invention is excellent in solubility and spectral density.

Claims (4)

A compound represented by formula (I).

[In Formula (I), R ¹ and R ² each independently represents a hydroxy group or —NHR ³³ .
R ³³ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group, an alkylcyclohexyl group having 1 to 4 carbon atoms in an alkyl portion, or an aliphatic alkoxy group having 2 to 15 carbon atoms. It represents an alkyl group, —R ³¹ —CO—O—R ³² , —R ³¹ —O—CO—R ³² , or an aralkyl group having 7 to 10 carbon atoms.
R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ^{3 to} R ¹⁸ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a nitro group.
R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a methyl group, an ethyl group or an amino group.
R ^{21 to} R ²⁵ each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. Represent.
R ²⁶ and R ²⁷ each independently represents a hydrogen atom or a methyl group. ] ^2. The compound according to claim 1, wherein R ¹ and R ² are each independently a hydroxy group or —NHR ³³ , and R ³³ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. The compound according to claim 1 or 2, wherein at least one of R ^{3 to} R ¹⁸ is a nitro group. The compound according to claims 1 to 3, wherein R ²⁵ is an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

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