JP2001040234A - New coloring compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new coloring compound having at least one 4-membered ring derived from squaric acid and also having at least one basic nucleus with a nitrogen atom, wherein oxidation potential is greatly improved without largely changing its spectroscopic absorption characteristics. SOLUTION: This new coloring compound is such one as to have at least one 4-membered ring derived from squaric acid and also at least one basic nucleus with a nitrogen atom; wherein at least one nitrogen atom of the basic nucleus is substituted with at least one alkyl group with fluorine atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel dye compound.

[0002]

2. Description of the Related Art Dyes that absorb light in the visible region are used in a wide variety of applications such as dyes, inks, recording materials and display elements. For such purposes, dye compounds having various desired spectral absorption characteristics have been developed. Squarylium cyanine, a dye compound having a 4-membered ring derived from squaric acid, also has a sharp absorption waveform and a large molecular extinction coefficient, and is useful as a dye that emits strong fluorescence. Having the desired spectral absorption characteristics is the first requirement for a dye, but often it is necessary to have various additional requirements required for practical use.

For example, it is required that they do not change over time. Oxidation can be considered as one of the changes with time. One method for suppressing oxidation is to increase the oxidation potential of the dye compound. In order to achieve this, an electron-withdrawing substituent is introduced into a dye molecule. In general, introduction of an electron-withdrawing substituent into a benzene ring of a basic nucleus has a great effect on spectral absorption characteristics and association. In addition, an electron-withdrawing substituent has been introduced into a nitrogen atom present in a basic nucleus. However, a dye compound having a four-membered ring derived from squaric acid showed a great effect by this method. The compound was not yet known.

[0004]

Accordingly, an object of the present invention is to have at least one four-membered ring derived from squaric acid,
It is another object of the present invention to provide a dye compound having at least one basic nucleus having a nitrogen atom and having a significantly increased oxidation potential without significantly changing spectral absorption characteristics.

[0005]

As a result of intensive studies, the present inventor has found that the object of the present invention can be achieved as follows. (1) A dye compound having at least one 4-membered ring derived from squaric acid, having at least one basic nucleus having a nitrogen atom, and having at least one nitrogen atom of the basic nucleus. A dye compound which is substituted with an alkyl group having at least one fluorine atom. (2) The dye compound according to (1), wherein the dye compound is a methine dye. (3) The dye compound according to (1) or (2), wherein the dye compound is a cyanine dye or a merocyanine dye. (4) The dye compound according to any one of (1) to (3), wherein the basic nucleus is derived from an indolenine derivative. (5) The dye compound according to (1), represented by the general formula (1).

[0006]

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In the formula, R ¹ and R ² each represent a substituted or unsubstituted alkyl group, at least one of which is an alkyl group having at least one fluorine atom. R ³ , R ⁴ , R ⁵ and R ⁶ each represent an alkyl group. W ¹ and W ² each represent a substituent, and a plurality of substituents may be linked to form a condensed ring. m and n each represent an integer of 0 to 4. (6) The dye compound according to (5), wherein in the general formula (1), R ³ , R ⁴ , R ⁵ and R ⁶ are a methyl group.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Examples of the dye having a four-membered ring derived from squaric acid in the present invention include squarylium cyanine having a basic nucleus on both sides of squaric acid, a merocyanine dye having a basic nucleus on only one side of squaric acid, and Japanese Patent Application No. And methine dyes such as bis-squarylium cyanine described in US Pat. Further, the carbonyl group derived from squaric acid may be converted to a thiocarbonyl group or an imino group, and may be further converted to a methylidene type described in Japanese Patent Application No. 11-92795.

Regarding the basic nucleus having a nitrogen atom in the present invention, for example, FM Harmer (FM Harmer)
By Heterocycli, Heterocyclic Compounds-Cyanine Soybeans and Related Compounds
c Compounds-Cyanine Dyes and Related Compound
s) ", John Wiley and Sons
& Sons)-New York, London, 1964,
Heterocyclic Compound Special Topics in Heterocyclic Chemistry by DMSturmer
Compounds-Special topics in heterocyclic chemistr
y) ", Chapter 18, Section 14, 482-515, John Wiley & Sons
Company-New York, London, 1977.

Specific examples include, for example, indole, quinolino [2,3-d] thiazole, indolenine, naphtho
[2,3-d] thiazole, imidazo [4,5, -b] quinoxalin, pyrazole, thiazoline, benzoxazole, benzoselenazole, benzothiazole, 1,
3,4-oxadiazole, imidazo [4,5-b] pyrazine, naphtho [2,1-d] thiazole, 1,3,4-
Thiadiazole, naphtho [1,2-d] thiazole, imidazole, phenanthreno [9,10-d] thiazole,
2-quinoline, tetrazole, oxazole, imidazoline, imidazo [4,5, -b] quinoline, thiazole, 4-quinoline, acenaphthyleno [1,2-d] thiazole, imidazo [4,5-b] pyridine, naphtho
[2,3-d] imidazole, benzimidazole, 2-
The nucleus derived from pyridine, 4-pyridine, or isoquinoline, and those in which a substituent is introduced, and those in which a ring is fused are exemplified. Among these, an indolenine nucleus or a derivative thereof is particularly preferred. Here, as the substituent, C.I.
Hansch, A .; Leo, R .; W. Taft, Chemical Review (Chem. Rev.) 1991, 9
1, pp. 165-195 (American Chemical Society). Representative specific examples of the substituent include the following.

A substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, 2-chloroethyl, 3-methoxyethyl, Methoxyethoxyethyl, 2
-Hydroxyethyl, 3-hydroxypropyl), alkoxy group (for example, methoxy group, ethoxy group, n-propoxy group or n-butoxy group), alkenyl group, alkynyl group, aryl group (for example, phenyl, 1-naphthyl,
2-naphthyl, tolyl), halogen atom, cyano group, nitro group, hydroxy group, aryloxy group, alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, alkylamino group, arylamino group, carbonamido group , Sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, ureido group, acyl group, oxycarbonyl group, carbamoyl group,
Carboalkoxy group, sulfonyl group, sulfinyl group,
An oxysulfinyl group or a sulfamoyl group, a heterocyclic ring (for example, pyridyl group, pyrimidyl group, triazinyl group, thienyl group, furyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, triazolyl group, thiazolyl group,
Imidazolyl, oxazolyl, thiadialyl, oxadiazolyl, quinolyl, isoquinolyl, tetrahydrofuryl) and combinations thereof.

The dye compound of the present invention has one or more basic nuclei having the above-mentioned nitrogen atom. At least one nitrogen atom of the basic nucleus (the basic nucleus has two nitrogen atoms) If it contains more than one, at least one nitrogen atom)
Is substituted with an alkyl group having one or more fluorine atoms (that is, the substituent bonded to the nitrogen atom is an alkyl group having at least one fluorine atom). As the alkyl group substituted by the fluorine atom, a catalog of Daikin Chemicals Sales Co., Ltd. can be referred to, for example, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,3,
3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,1,3,3,3-hexafluoro-2-propyl, 2,2,3,3,4,4 ,
4-heptafluorobutyl.

Among the dye compounds of the present invention, compounds represented by the following general formula (1) are particularly preferred.

[0014]

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In the formula, R ¹ and R ² represent a substituted or unsubstituted alkyl group, and at least one of them is an alkyl group having at least one fluorine atom. R ¹ ,
Examples of the substituent of R ² include the above-described substituents of the basic nucleus. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group. The alkyl group may be linear or branched. R ^{3 to} R ⁶ are preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. W ¹ and W ² each independently represent the above-mentioned substituent, and a plurality of substituents may be connected to each other to form a condensed ring.
m and n each represent an integer of 0 to 4. Examples of the condensed ring formed include benzene, naphthalene,
Examples include pyridine, pyrimidine, thiophene, furan, tetrahydrobenzene, and dihydrofuran.

Hereinafter, specific examples of the compound of the present invention will be shown, but the scope of the present invention is not limited thereto. The following structural formulas represent only one of a plurality of possible resonance structures or tautomeric structures.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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These compounds are generally described in FM Harmer, Heterocyclic Compounds-Cyanine Dyes and Reynolded Compounds.
Related Compounds), John Willie and
Johns Wiley & Sons, New York, London, 1964, "Rodd's Chemistry of Carbon Co.
mpounds) "2nd.Ed.vol.IV, partB, 1977, No.15
Chapters, 369-422, Elsevier Science
Public Company, Inc. (Elsevier Science Pu
blishing Company Inc.), New York, and the like.

[0024]

The present invention will be described below in more detail with reference to the following examples.

Example 1 An example of the synthesis of compound 18 is shown below. Other dyes can be synthesized in the same manner with reference to the above-mentioned literature. (Synthesis of Compound 18) 1) 3,3-Dimethyl-2-methylidene-1- (2,3
Synthesis of 2,2-trifluoroethyl) naphtho [1,2-d] pyrroline 2,3,3-trimethylnaphtho [1,2-d] -3H-
2.09 g (10 mmol) of pyrrole, 2,2,2-
10 mL of acetone was added to 8.45 g (30 mmol) of trifluoroethyl = trichloromethanesulfonate, and the mixture was stirred under reflux for 15 hours. Ethyl acetate (50 ml) and ice water (50 ml) were added to the reaction mixture, and the mixture was separated with a separating funnel to obtain an ethyl acetate layer. This was washed with water and dried over anhydrous sodium sulfate. Separation and purification were performed by silica gel column chromatography using a mixed solvent of hexane / ethyl acetate = 9/1 as an eluent to obtain the desired product. Yield 2.60 g (89% yield)

2) Synthesis of compound 18 1.16 g (3.99 mmol) of the methylidene compound obtained in 1) and 0.91 g (7.98 mmol) of squaric acid were added to 10 ml of butanol and 10 ml of toluene. Was added and the mixture was stirred under reflux for 15 minutes. The reaction mixture was cooled on ice, and the precipitated white crystals were separated by filtration. The filtrate was separated by silica gel column chromatography using a mixed solvent of hexane / ethyl acetate = 2/1 as an eluent. After distilling off the solvent, acetonitrile was added for crystallization. The crystals collected by filtration are methanol / methylene chloride = 1.
The filtrate obtained by dissolving in 100 ml of a mixed solvent of / 1 and filtering off insolubles was substantially distilled off methylene chloride at normal pressure.
The resulting crystals left at room temperature were collected by filtration to give Compound 18. Yield 510 mg (19.3% yield)

¹ H-NMR (δin DMSO-d ₆ ):
1.98 (s, 12H), 5.47 (bs, 4H),
6.15 (bs, 2H), 7.50 (t, 2H), 7.
68 (t, 2H), 7.82 (d, 2H), 8.05
(M, 4H), 8.29 (d, 2H) λmax (ε) =
654 nm (2.79 × 10 ⁵ ) in methanol

[Example 2] (Comparison of the maximum absorption wavelength) The maximum absorption wavelength in methanol was compared. Compounds A, B and C shown below were used as comparative compounds. Table 1 shows the results. The compound of the present invention has a smaller change from the comparative compound A as a reference than the other comparative compounds B and C. In particular, the change is remarkably small as compared with B in which a substituent is introduced into the benzene ring.

[0029]

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[0030]

[Table 1]

Example 3 (Comparison of Oxidation Potential) The oxidation potential was measured to compare the stability to oxidation. The results are shown in Table 2. The values shown are Ag / N / N-dimethylformamide solution.
It is a measured value at an AgCl electrode (supporting electrolyte: tetrabutylammonium = perchlorate).

[0032]

[Table 2]

Dye A having a relatively small difference in absorption maximum wavelength,
Compared with C, the oxidation potential of the compound of the present invention is clearly large and shows a noble potential, and high stability against oxidation is expected.

[0034]

According to the present invention, there is provided a method of providing a dye which is hardly oxidized with little change in spectral absorption characteristics.

[Procedure amendment]

[Submission date] November 1, 1999 (1999.11.
1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

The basic nucleus having a nitrogen atom in the present invention is described, for example, in FM Hamer .
By Heterocycli, Heterocyclic Compounds-Cyanine Soybeans and Related Compounds
c Compounds-Cyanine Dyesand Related Compounds),
John Wiley & Sons
-New York, London, 1964, DMSturmer, Heterocyclic Compounds, Special Topics in Heterocyclic Compounds.
s-Specialtopics in heterocyclic chemistry)
Chapter 8, section 14, pages 482-515, John Wiley & Sons, Inc.-New York, London, 1977.

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[Correction method] Change

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Specific examples include, for example, indole, quinolino [2,3-d] thiazole, indolenine, naphtho
[2,3-d] thiazole, imidazo [4,5 - b] quinoxalin, pyrazole, thiazoline, benzoxazole, benzoselenazole, benzothiazole, 1,3
4-oxadiazole, imidazo [4,5-b] pyrazine, naphtho [2,1-d] thiazole, 1,3,4-thiadiazole, naphtho [1,2-d] thiazole, imidazole, phenanthreno [9, 10-d] thiazole, 2-
Quinoline, tetrazole, oxazole, imidazoline, imidazo [4,5 - b] quinoline, thiazole,
-Quinoline, acenaphthyleno [1,2-d] thiazole, imidazo [4,5-b] pyridine, naphtho [2,3
[D] imidazole, benzimidazole, 2-pyridine, 4-pyridine, nuclei derived from isoquinoline, and those in which a substituent is introduced and those which are condensed. Among these, an indolenine nucleus or a derivative thereof is particularly preferred. Here, as the substituent, C.I. Hans
ch. Leo, R .; W. Taft, Chem. Rev., 1991, 91, 1
65-195 (American Chemical Society). Representative specific examples of the substituent include the following.

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A substituted or unsubstituted alkyl group (for example,
Chill, ethyl, n-propyl, isopropyl, cyclopropyl
Ropyl, n-butyl, pentyl, hexyl, cyclohexyl
Syl, heptyl, octyl, nonyl, 2-chloroethyl
3-methoxyethyl, methoxyethoxyethyl, 2
-Hydroxyethyl, 3-hydroxypropyl), alcohol
Xy group (for example, methoxy group, ethoxy group, n-propo group)
Xy or n-butoxy)), alkenyl, alkyl
Nil group, aryl group (for example, phenyl, 1-naphthyl,
2-naphthyl, tolyl), a halogen atom, a cyano group,
Toro, hydroxy, aryloxy, alkylthio
O group, arylthio group, acyloxy group, sulfonyluo group
Xy group, amino group, alkylamino group, arylamino
Group, carbonamido group, sulfonamido group, oxycal
Bonylamino group, oxysulfonylamino group, ureido
Group, acyl group, oxycarbonyl group, carbamoyl group,
Carboalkoxy group, sulfonyl group, sulfinyl group,
Oxysulfinyl group or sulfamoyl group, heterocycle
(For example, pyridyl group, pyrimidyl group, triazinyl
Group, thienyl group, furyl group, pyrrolyl group, pyrazoLil
Group, imidazolyl group, triazolyl group, thiazolyl group,
Imidazolyl group, oxazolyl group, thiadialyl group,
Oxadiazolyl, quinolyl, isoquinolyl, tet
Lahydrofuryl group) and combinations thereof.
You.

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[0021]

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[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0023

[Correction method] Change

[Correction contents]

These compounds are generally described in FM Hamer, Heterocyclic Compounds-Cyanine Dyes and Reynolded Compounds.
Related Compounds), John Willie and
Johns Wiley & Sons, New York, London, 1964, "Rodd's Chemistry of Carbon Co.
mpounds) "2nd.Ed.vol.IV, partB, 1977, No.15
Chapter, pp. 369 422, Elsevier Science
Public Company, Inc. (Elsevier Science Pu
blishing Company Inc.), New York, and the like.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0030

[Correction method] Change

[Correction contents]

[0030]

[Table 1]

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Example 3 (Comparison of Oxidation Potential) The oxidation potential was measured to compare the stability to oxidation. The results are shown in Table 2. The values shown are Ag / N / N-dimethylformamide solution.
AgCl electrode (supporting electrolyte: tetrabutylammonium Niu arm
It is a measure of the in Pas Kurorato).

Claims (5)

[Claims] 1. A method according to claim 1 wherein at least one squaric acid-derived 4
A dye compound having a membered ring, having at least one basic nucleus having a nitrogen atom, and wherein at least one nitrogen atom of the basic nucleus is substituted with an alkyl group having at least one fluorine atom. A dye compound characterized in that: 2. The dye compound according to claim 1, wherein the dye compound is a cyanine dye or a merocyanine dye. 3. The dye compound according to claim 1, wherein the basic nucleus is a nucleus derived from an indolenine derivative. 4. The dye compound according to claim 1, wherein the dye compound is a compound represented by the general formula (1). Embedded image In the formula, R ¹ and R ² each represent a substituted or unsubstituted alkyl group, and at least one of them is an alkyl group having at least one fluorine atom. R ³ ,
R ⁴ , R ⁵ and R ⁶ each represent an alkyl group. W ¹
And W ² each represent a substituent, and a plurality of substituents may be connected to each other to form a condensed ring. m and n
Represents an integer of 0 to 4, respectively. 5. In the general formula (1), R ³ , R ⁴ ,
4. dye compound of wherein the R ⁵ and R ⁶ are methyl groups.