JP3238265B2 - Novel quinizarin compound, method for producing the same, and visible light absorbing material comprising the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel quinizarin compound, a method for producing the same, and a visible light absorbing material comprising the compound. The novel quinizarin compound of the present invention has absorption in the orange to red to blue range of 480 nm to 700 nm and is excellent in solubility, and is also excellent in light resistance or heat resistance. Display materials or recording materials having absorption in the visible region of the so-called visible light absorbing materials, for example, dyes for sublimation transfer, ink for inkjet, color separation filters used for imaging tubes, color filters for liquid crystal displays, color filters for optics, Excellent effect when used for color toner, tamper-proof and anti-counterfeit barcode ink, dichroic dye for guest-host type liquid crystal display, dichroic dye for polarizing plate, optical recording media for compact discs, etc. Demonstrate. Particularly, when used in a dye for magenta or cyan sublimation transfer, an excellent effect is exhibited.

Further, the present invention provides a high-grade coloring agent having excellent solubility and high fastness in the orange-red-blue range, for example, dyeing of fibers, paints for automobiles, paints for building materials, colorants for printing materials, inks for writing implements. It has excellent effects when used as a colorant for glass flakes, a colorant for eyeglass lenses, and the like.

[0003]

2. Description of the Related Art In recent years, organic dyes have been
In the information recording field, as the colorization of information display images or their hard copies progresses, their functions are paid attention to, and as display materials or recording materials, for example, dyes for sublimation transfer, ink for ink jet, color separation used for imaging tubes Absorbs in the visible region of filters, color filters for liquid crystal displays, color filters for optics, color toners, barcode inks for preventing tampering and counterfeiting, dichroic dyes for guest-host type liquid crystal displays, dichroic dyes for polarizing plates, etc. There is an increasing demand for the development of so-called visible light absorbing functional dyes.

In particular, there is an increasing demand for development of yellow dyes, magenta dyes and cyan dyes having high performance as coloring materials used in sublimation type thermal transfer recording, which are expected to have the greatest potential in the field of full color victoral. For example, styryl dyes, pyridone azo dyes, pyrazole azo dyes for yellow dyes, anthraquinone dyes for magenta dyes, tricyanostyryl dyes, heteroazo dyes, benzene azo dyes and cyan dyes for anthraquinone dyes, naphthoquinone dyes, and India Aniline dyes have been proposed, but at present there is no dye capable of simultaneously satisfying physical properties required as a dye for sublimation transfer, such as absorption wavelength, solubility, and light resistance.

[0005] Among them, anthraquinone-based compounds which are originally stable to light, heat, temperature, etc. and are excellent in robustness are to be controlled to an absorption wavelength required according to the application and to be controlled according to the application. Many studies have been made to dissolve it in the required solvent or resin.

For example, JP-A-60-122192,
JP-A-60-131293, JP-A-60-15909
No. 1, JP-A-61-227093, JP-A-60-25
No. 3595, JP-A-62-25092, JP-A-62-25092
97886, JP-A-61-227093, JP-A-62-27093
3-288787, JP-A-63-288788, JP-A-63-288789, JP-A-1-174490
No. 1-amino-4-
Magenta dyes having various functional groups introduced at the 2-position of the hydroxy-anthraquinone compound are disclosed. However, although some have solubility, the absorption wavelength or light resistance is not satisfactory.

JP-A-59-227948, JP-A-59-227948
-227948, JP-A-60-53563, JP-A-60-131294, JP-A-60-131292,
JP-A-61-57391, JP-A-62-138291
JP-A-1-183584, JP-A-1-25559
4, JP-A-1-258995, JP-A-2-4309
No. 3, JP-A-2-132462 and JP-A-2-16
No. 4,589, discloses a cyan dye in which various functional groups are introduced at the 3- or 4-position of a skeleton having an amino group substituted or unsubstituted with an alkyl group at the 1- and 4-positions of anthraquinone. However, although some have solubility, the absorption wavelength or light resistance is not satisfactory.

In Japanese Patent Application Laid-Open Nos. 60-172591, 60-193887, 61-284489 and 61-284489, an amino-substituted compound is introduced at the 5- and 8-positions of the quinizarin skeleton. Anthraquinone-based cyan dyes are disclosed. However, they have the disadvantage of poor solubility.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances of the prior art. That is,
It is an object of the present invention to control the absorption wavelength according to the purpose in the absorption wavelength range of 480 to 700 nm, to have excellent solubility in a solvent or resin according to the application, and to have excellent light resistance in visible light absorption. It is an object of the present invention to provide a novel quinizarin compound which is a kind of anthraquinone compound as a material. Another object of the present invention is to provide a method for efficiently producing the quinizarin compound.

[0010]

In order to solve the above-mentioned problems, the present invention provides the following general formula (I):

[0011]

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Wherein A is independently a carboxyl group,
Methoxycarbonyl group, ethoxycarbonyl group, butoxy
Cycarbonyl group, octyloxycarbonyl group, -CN
Or an -NO _2; B represents an alkyl group having 1 to 4 carbon atoms, the number 6-10 cycloalkyl group having a carbon atom, 1 to 4 alkoxy groups or halogen carbon atoms; R ^1, R ² and R ³ each independently represent a hydrogen atom or a carbon atoms 1-12 alkyl group; a, b and c are each an integer of independently 0 to 3; d, e and f are 0 An integer of 5, provided that a + d, b + e, and c +
f is an integer of 0 to 5) . And a quinizarine compound represented by the formula: Further, the present invention provides the following general formula (I):

[0013]

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Wherein A is independently a carboxyl group,
Methoxycarbonyl group, ethoxycarbonyl group, butoxy
Cycarbonyl group, octyloxycarbonyl group, -CN
Or —NO ₂ ; B represents an alkyl having 1 to 4 carbon atoms.
Kill group, cycloalkyl group having 6 to 10 carbon atoms, carbon
Represents an alkoxy group having 1 to 4 element atoms or halogen
R ¹ , R ² and R ³ each independently represent a hydrogen atom or a carbon atom;
Represents an alkyl group having 1 to 12 elementary atoms; a, b and
c is each independently an integer from 0 to 3; d, e and f are
An integer from 0 to 5, provided that a + d, b + e, and c +
f is an integer of 0 to 5). Is represented by
A quinizarin-based compound is provided. The present invention further comprises the aforementioned
Method for producing quinizarin compound represented by general formula (I)
Having the following general formula (II):

[0015]

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(Wherein R ⁰ represents a halogen atom)
The halogen-containing quinizarin compound represented by the following general formula
Formula (III):

[0017]

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Wherein A, B, R ¹ , R ² , R ³ , a,
b, c, d, e and f are as defined above)
Reacting with any one of the compounds represented or
Or a plurality of compounds of the formula (III) in order or
Reacting simultaneously.
The present invention further provides a quinine represented by the general formula (I).
A method for producing a zaline-based compound,
V):

[0019]

Embedded image

Wherein W, X, Y and Z are as defined above.
Wherein the phthalic anhydride derivative represented by the formula is reacted with hydroquinone or 1,4-dimethoxybenzene. The novel quinizarin compound represented by the above general formula (I) is 480 nm to 700 nm.
The present inventors have found that they have various absorption wavelengths in the nm range and are excellent in solubility, light resistance, and heat resistance, so that they can be effectively used as visible light absorbing materials, and completed the present invention.

[0021]

DETAILED DESCRIPTION In the present invention, an alkyl group having 1 to 4 carbon atoms means a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Means 1 to 1 carbon atoms
The two alkyl groups include, in addition to the above-mentioned alkyl groups, a linear or branched pentyl group, a linear or branched hexyl group, a linear or branched heptyl group, a linear or branched It includes a branched octyl group, a straight or branched nonyl group, a straight or branched decyl group, a straight or branched undecyl group, and a straight or branched dodecyl group.

The alkoxy group having 1 to 4 carbon atoms means
It means a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, and a tert-butyloxy group.
Halogen means a fluorine atom, a chlorine atom or a bromine atom, and is preferably a fluorine atom. Particularly, by imparting a fluorine atom, the effect on the solubility in a solvent or a resin can be promoted.

The novel quinizarin compound of the present invention has a quinizarin skeleton in which substituents represented by W, X, Y and Z in the general formula (I) are introduced at the 5, 6, 7 and / or 8 positions. The substituent is specifically exemplified below. By appropriately containing the following substituents and halogen atoms (preferably fluorine atoms) at the 5, 6, 7 and / or 8 positions of the quinizarin skeleton, the problems of conventional materials as visible light absorbing materials can be solved.

[0024] (a) Type anilino group, o- ethoxycarbonyl anilino group, p-
Ethoxycarbonylanilino group, m-ethoxycarbonylanilino group, o-butoxycarbonylanilino group, p
-Butoxycarbonylanilino group, m-butoxycarbonylanilino group, o-cyanoanilino group, p-cyanoanilino group, m-cyanoanilino group, o-nitroanilino group, p-nitroanilino group, m-nitroanilino group, o
-Methoxyanilino group, p-methoxyanilino group, m-
A methoxyanilino group, an o-methylanilino group, a p-methylanilino group, an m-methylanilino group,

O-tert-butylanilino group, p-tert-butylanilino group, m-tert-butylanilino group, o-fluoroanilino group, p-fluoroanilino group, m-fluoroanilino group , 2,3,5,6-tetrafluoroanilino group, 4-cyano-2,3,5,6-
Tetrafluoroanilino group, amino group, 2-methyl-6
A cyanoanilino group, a 2-methyl-6-nitroanilino group, a 2-methyl-6-carboxyanilino group, a 2-methyl-6-methoxycarbonylanilino group,

2-methyl-4-cyanoanilino group, 2-
Methyl-4-nitroanilino group, 2-methyl-4-carboxyanilino group, 2-methyl-4-methoxycarbonylanilino group, 2-butyl-4-nitroanilino group, 2
-Butyl-4-carboxyanilino group, 2-methoxy-
4-cyanoanilino group, 2-methoxy-4-nitroanilino group, 2-methoxy-4-carboxyanilino group, 2
-Methoxy-4-methoxycarbonylanilino group;

(B) type phenylthio, o-ethylphenylthio, p-ethylphenylthio, m-ethylphenylthio, o-methoxyphenylthio, p-methoxyphenylthio,
m-methoxyphenylthio group, o-hydroxyphenylthio group, p-hydroxyphenylthio group, m-hydroxyphenylthio group, o-fluorophenylthio group, p-
Fluorophenylthio, m-fluorophenylthio, 6-tetrafluorophenylthio, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, tert-butylthio,

O-cyanophenylthio, p-cyanophenylthio, m-cyanophenylthio, o-nitrophenylthio, p-nitrophenylthio, m-nitrophenylthio, o-carboxyphenylthio Group, p
-Carboxyphenylthio group, m-carboxyphenylthio group, o-ethoxycarbonylphenylthio group, p-
An ethoxycarbonylphenylthio group, an m-ethoxycarbonylphenylthio group, a 2,3,5,6-tetrafluorophenylthio group,

4-cyano-2,3,5,4-carboxy-2,3,5,6-tetrafluorophenylthio, octylthio, nonylthio, methylamino, ethylamino, butylamino, hexyl An amino group, a nonylamino group, a cyclohexylamino group;

(C) Type 2,6-dimethylanilino group, 2,6-diethylanilino group, 2,6-dipropylanilino group, 2,6-diisopropylanilino group, 2,6-dibutylaniline Lino group,
2,6-diisobutylanilino group, 2,6-di-tert-butylanilino group, 2,6-dimethoxyanilino group,
2,6-diethoxyanilino group, 2,6-dipropoxyanilino group, 2,6-diisopropoxyanilino group,
2,6-dibutoxyanilino group, 2,6-isobutoxyanilino group, 2,6-ditert-butoxyanilino group, 2,6-dichloroanilino group, 2-chloro-6-methylanilino group,

4-cyano-2,6-dimethylanilino group, 4-cyano-2,6-diethylanilino group, 4-cyano-2,6-dipropylanilino group, 4-cyano-
2,6-diisopropylanilino group, 4-cyano-2,
6-dibutylanilino group, 4-cyano-2,6-diisobutylanilino group, 4-cyano-2,6-di-tert-butylanilino group, 4-cyano-2,6-dimethoxyanilino group, 4- Cyano-2,6-diethoxyanilino group, 4-cyano-2,6-dipropoxyanilino group, 4
-Cyano-2,6-diisopropoxyanilino group, 4-
Cyano-2,6-dibutoxyanilino group, 4-cyano-
2,6-diisobutoxyanilino group, 4-cyano-2,
A 6-ditabutoxyanilino group,

4-nitro-2,6-dimethylanilino group, 4-nitro-2,6-diethylanilino group, 4-nitro-2,6-dipropylanilino group, 4-nitro-
2,6-diisopropylanilino group, 4-nitro-2,
6-dibutylanilino group, 4-nitro-2,6-diisobutylanilino group, 4-nitro-2,6-ditert-butylanilino group, 4-nitro-2,6-dimethoxyanilino group, 4- Nitro-2,6-diethoxyanilino group, 4-nitro-2,6-dipropoxyanilino group, 4
-Nitro-2,6-diisopropoxyanilino group, 4-
Nitro-2,6-dibutoxyanilino group, 4-nitro-
2,6-diisobutoxyanilino group, 4-nitro-2,
6-tert-butoxyanilino group,

4-ethoxycarbonyl-2,6-dimethylanilino group, 4-ethoxycarbonyl-2,6-diethylanilino group, 4-diethoxycarbonyl-2,6-
Dipropylanilino group, 4-ethoxycarbonyl-2,
6-diisopropylanilino group, 4-ethoxycarbonyl-2,6-dibutylanilino group, 4-ethoxycarbonyl-2,6-diisobutylanilino group, 4-ethoxycarbonyl-2,6-ditert-butylanilino group ,
4-ethoxycarbonyl-2,6-dimethoxyanilino group,

4-ethoxycarbonyl-2,6-diethoxyanilino group, 4-ethoxycarbonyl-2,6-dipropoxyanilino group, 4-ethoxycarbonyl-2,
6-diisopropoxyanilino group, 4-ethoxycarbonyl-2,6-dibutoxyanilino group, 4-ethoxycarbonyl-2,6-diisobutoxyanilino group, 4-ethoxycarbonyl-2,6-ditacial Butoxyanilino group;

(D) Type phenoxy, o-methylphenoxy, p-methylphenoxy, o-methoxyphenoxy, p-methoxyphenoxy, methoxy, ethoxy, n-propoxy, isopropoxy, butoxy Group, isobutoxy group, tert-butoxy group, hexyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group.

The present inventors have added the above-mentioned (a) to (d) type substituents to the quinizarin skeleton 5, 6, 7 and / or It has been found that this is possible by introducing the compound at the 8-position and preferably containing a fluorine atom at the remaining position.

That is, the substituents of the (a) and (b) types are preferably used mainly for the purpose of shifting the absorption wavelength to the longer wavelength side (especially, the (a) type is preferably used). The width of the shift can be changed depending on the type of the substituent or the number of the substituents. That is, 480
The absorption wavelength can be controlled by the type of the substituent or the number of the substituents in the range of the absorption wavelength from nm to 700 nm.

The substituent (c) is preferably introduced for the purpose of imparting high solubility at the same time as controlling the absorption wavelength. The (d) type substituent is preferably introduced mainly when it is used for the purpose of greatly improving the solubility. By using these, it can be dissolved in a ketone-based solvent such as acetone and methyl ethyl ketone, a hydrocarbon-based solvent such as benzene, toluene and xylene, and a halogen-based solvent such as chloroform and dichloroethane at a high concentration. As for the number of substituents, the larger the number, the greater the effect of solubility.

Thus, by simultaneously introducing the (a) type substituent and the (d) type substituent, or by introducing the (c) type substituent, a ketone solvent such as acetone or methyl ethyl ketone, benzene, It can be dissolved in a high concentration in a hydrocarbon solvent such as toluene, xylene, or a halogen solvent such as chloroform or dichloroethane, and at the same time, the type of the substituent or the type of the substituent in the absorption wavelength range of 480 nm to 700 nm. The absorption wavelength can be controlled by the number. In particular, in the case of obtaining a red-colored visible-range substance, usually, a combination of one (a) type substituent and one or two (d) type substituents is introduced, or (c) It is preferred to introduce one type of substituent.

In particular, when a visible light in the blue range is to be obtained, usually, a combination of two (a) type substituents and one or two (d) type substituents is introduced. Alternatively, it is preferable to introduce two (c) type substituents. Specific examples of the quinizarine compound of the general formula (I) include:

A) Type (Aromatic and aliphatic amino functional groups are introduced one at the 6-position of the quinizarin skeleton, red system) A-1. 6-anilino-5,7,8-trifluoroquinizarin A-2. 6- (o-ethoxycarbonylanilino)-
5,7,8-trifluoroquinizarin A-3. 6- (p-ethoxycarbonylanilino)-
5,7,8-trifluoroquinizarin A-4. 6- (m-ethoxycarbonylanilino)-
5,7,8-trifluoroquinizarin A-5. 6- (o-butoxycarbonylanilino)-
5,7,8-trifluoroquinizarin

A-6. 6- (p-butoxycarbonylanilino) -5,7,8-trifluoroquinizarin A-7. 6- (m-butoxycarbonylanilino)-
5,7,8-trifluoroquinizarin A-8. 6- (m-octyloxycarbonylanilino) -5,7,8-trifluoroquinizarin A-9. 6- (o-cyanoanilino) -5,7,8-
Trifluoroquinizarin A-10. 6- (p-cyanoanilino) -5,7,8-
Trifluoroquinizarin

A-11. 6- (o-nitroanilino)-
5,7,8-trifluoroquinizarin A-12. 6- (p-nitroanilino) -5,7,8-
Trifluoroquinizarin A-13. 6-amino-5,7,8-trifluoroquinizarin A-14. 6-ethylamino-5,7,8-trifluoroquinizarin A-15. 6-butylamino-5,7,8-trifluoroquinizarin

A-16. 6-octylamino-5,7,
8-trifluoroquinizarin A-17. 6-Cyclohexylamino-5,7,8-trifluoroquinizarin A-18. 6- (p-tert-butylanilino)-
5,7,8-trifluoroquinizarin A-19. 6- (o-methoxyanilino) -5,7,8
-Trifluoroquinizarin A-20. 6- (p-methoxyanilino) -5,7,8
-Trifluoroquinizarin

A-21. 6- (m-methoxyanilino)
-5,7,8-Trifluoroquinizarin A-22. 6- (2,6-dimethylanilino) -5
7,8-Trifluoroquinizarin A-23. 6- (2,6-diethylanilino) -5
7,8-Trifluoroquinizarin A-24. 6- (2,6-dibutylanilino) -5
7,8-trifluoroquinizarin A-25. 6- (2-methyl-6-nitroanilino)-
5,7,8-trifluoroquinizarin

A-26. 6- (2-Methyl-6-carboxyanilino) -5,7,8-trifluoroquinizarin A-27. 6- (2,6-dichloroanilino) -5
7,8-Trifluoroquinizarin A-28. 6- (2-chloro-6-methylanilino)-
5,7,8-Trifluoroquinizarin A-29. 6- (2,3,5,6-tetrafluoroanilino) -5,7,8-trifluoroquinizarin A-30. 6- (2,6-diisopropylanilino)-
5,7,8-trifluoroquinizarin

B) Type (Aromatic or aliphatic amino functional groups are provided at two positions 6 and 7 of the quinizarin skeleton, or 5, 6, 7
B-1. Introduced in three places and blue system) B-1. 6,7-Dianilino-5,8-difluoroquinizarin B-2. 6,7-bis (m-ethoxycarbonylanilino) -5,8-difluoroquinizarin B-3. 6,7-bis (o-butoxycarbonylanilino) -5,8-difluoroquinizarin B-4. 6,7-bis (p-butoxycarbonylanilino) -5,8-difluoroquinizarin B-5. 6,7-bis (m-butoxycarbonylanilino) -5,8-difluoroquinizarin

B-6. 6,7-bis (o-cyanoanilino) -5,8-difluoroquinizarin B-7. 6,7-bis (p-cyanoanilino) -5
8-Difluoroquinizarin B-8. 6,7-bis (o-nitroanilino) -5
8-Difluoroquinizarin B-9. 6,7-bis (p-nitroanilino) -5
8-Difluoroquinizarin B-10. 6,7-bisbutylamino-5,8-difluoroquinizarin

B-11. 6,7-bis (o-tert-butylanilino) -5,8-difluoroquinizarin B-12. 6,7-bis (p-tert-butylanilino) -5,8-difluoroquinizarin B-13. 6,7-bis (o-methoxyanilino)-
5,8-Difluoroquinizarin B-14. 6,7-bis (p-methoxyanilino)-
5,8-Difluoroquinizarin B-15. 6,7-bis (m-methoxyanilino)-
5,8-difluoroquinizarin

B-16. 6,7-dibutylamino-5
8-Difluoroquinizarin B-17. 6- (m-ethoxycarbonylanilino)-
7-butylamino-5,8-difluoroquinizarin B-18. 6- (p-methoxyanilino) -7-butylamino-5,8-difluoroquinizarin B-19. 6-anilino-7-butylamino-5,8-
Difluoroquinizarin B-20. 6,7-bis (2,6-dimethylanilino)
-5,8-difluoroquinizarin

B-21. 6,7-bis (2,6-diethylanilino) -5,8-difluoroquinizarin B-22. 6,7-bis (2,6-dichloroanilino)
-5,8-Difluoroquinizarin B-23. 5,6,7-tris (butylamino) -8-
Fluoroquinizarin B-24. 6,7-bis (2,3,5,6-tetrafluoroanilino) -5,8-difluoroquinizarin B-25. 6,7-bis (2-chloro-6-methylanilino) -5,8-difluoroquinizarin B-26. 6,7-bis (2,6-diisopropylanilino) -5,8-difluoroquinizarin

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

E) Type (Aromatic and aliphatic amino functional groups at the 5 or 6 position of the quinizarin skeleton and 1 aromatic and aliphatic hydroxy functional groups or aromatic and aliphatic mercapto functional groups at the quinizarin skeleton E-1. One to three were introduced into the red system.) E-1. 7-butoxy-6-anilino-5,8-difluoroquinizarin E-2. 7-butoxy-6- (o-ethoxycarbonylanilino) -5,8-difluoroquinizarin E-3. 7-butoxy-6- (p-ethoxycarbonylanilino) -5,8-difluoroquinizarin E-4. 7-butoxy-6- (m-ethoxycarbonylanilino) -5,8-difluoroquinizarin E-5. 7-octyloxy-6- (o-ethoxycarbonylanilino) -5,8-difluoroquinizarin

E-6. 7-octyloxy-6- (p
-Ethoxycarbonylanilino) -5,8-difluoroquinizarin E-7. 7-octyloxy-6- (m-ethoxycarbonylanilino) -5,8-difluoroquinizarin E-8. 7-octyloxy-6- (o-butoxycarbonylanilino) -5,8-difluoroquinizarin E-9. 7-octyloxy-6- (p-butoxycarbonylanilino) -5,8-difluoroquinizarin E-10. 7-octyloxy-6- (m-butoxycarbonylanilino) -5,8-difluoroquinizarin

E-11. 7-butoxy-6- (o-nitroanilino) -5,8-difluoroquinizarin E-12. 7-butoxy-6- (m-nitroanilino)
-5,8-Difluoroquinizarin E-13. 7-butoxy-6- (p-nitroanilino)
-5,8-Difluoroquinizarin E-14. 7-octyloxy-6- (p-nitroanilino) -5,8-difluoroquinizarin E-15. 7-butoxy-6- (o-cyanoanilino)
-5,8-difluoroquinizarin

E-16. 7-butoxy-6- (m-cyanoanilino) -5,8-difluoroquinizarin E-17. 7-butoxy-6- (p-cyanoanilino)
-5,8-difluoroquinizarin E-18. 7-octyloxy-6- (p-cyanoanilino) -5,8-difluoroquinizarin E-19. 7-methoxy-6- (2,6-dimethylanilino) -5,8-difluoroquinizarin E-20. 7-butoxy-6- (2,6-dimethylanilino) -5,8-difluoroquinizarin

E-21. 7-octyloxy-6-
(2,6-dimethylanilino) -5,8-difluoroquinizarin E-22. 7-methoxy-6- (2,6-diethylanilino) -5,8-difluoroquinizarin E-23. 7-butoxy-6- (2,6-diethylanilino) -5,8-difluoroquinizarin E-24. 7-octyloxy-6- (2,6-diethylanilino) -5,8-difluoroquinizarin E-25. 7-methoxy-6- (2-nitro-6-dimethylanilino) -5,8-difluoroquinizarin

E-26. 7-butoxy-6- (2-nitro-6-dimethylanilino) -5,8-difluoroquinizarin E-27. 7-octyloxy-6- (2-nitro-6
-Dimethylanilino) -5,8-difluoroquinizarin E-28. 7-octyloxy-6- (2-carboxy-6-dimethylanilino) -5,8-difluoroquinizarin E-29. 5-anilino-6,7-dibutoxy-8-fluoroquinizarin E-30. 5-anilino-6,7-dioctoxy-8
-Fluoroquinizarin

E-31. 5- (o-ethoxycarbonylanilino) -6,7-dibutoxy-8-fluoroquinizarin E-32. 5- (p-ethoxycarbonylanilino)-
6,7-dibutoxy-8-fluoroquinizarin E-33. 5- (m-ethoxycarbonylanilino)-
6,7-dibutoxy-8-fluoroquinizarin E-34. 5- (p-butoxycarbonylanilino)-
6,7-dibutoxy-8-fluoroquinizarin E-35. 5- (o-nitroanilino) -6,7-dibutoxy-8-fluoroquinizarin

E-36. 5- (p-nitroanilino)-
6,7-dibutoxy-8-fluoroquinizarin E-37. 5- (m-nitroanilino) -6,7-dibutoxy-8-fluoroquinizarin E-38. 5- (o-cyanoanilino) -6,7-dibutoxy-8-fluoroquinizarin E-39. 5- (p-cyanoanilino) -6,7-dibutoxy-8-fluoroquinizarin E-40. 5- (m-cyanoanilino) -6,7-dibutoxy-8-fluoroquinizarin

E-41. 6- (m-ethoxycarbonylanilino) -5,7-dimethoxy-8-fluoroquinizarin E-42. 6- (m-butoxycarbonylanilino)-
7,8-dibutoxy-5-fluoroquinizarin E-43. 6- (p-butoxycarbonylanilino)-
7,8-dioctyloxy-5-fluoroquinizarin E-44. 6- (m-ethoxycarbonylanilino)-
5,7,8-Tributoxy-fluoroquinizarin E-45. 5-anilino-6,7-diphenylthio-8
-Fluoroquinizarin

E-46. 5- (p-cyanoanilino)-
6,7-diphenylthio-8-fluoroquinizarin E-47. 5- (p-nitroanilino) -6,7-diphenylthio-8-fluoroquinizarin E-48. 5-amino-6,7-diphenylthio-8-
Fluoroquinizarin E-49. 7-methoxy-6- (2,6-dichloroanilino) -5,8-difluoroquinizarin E-50. 7-butoxy-6- (2,6-dichloroanilino) -5,8-difluoroquinizarin

E-51. 7-octyloxy-6-
(2,6-dichloroanilino) -5,8-difluoroquinizarin E-52. 7-methoxy-6- (2-chloro-6-methylanilino) -5,8-difluoroquinizarin E-53. 7-butoxy-6- (2-chloro-6-methylanilino) -5,8-difluoroquinizarin E-54. 7-octyloxy-6- (2-chloro-6
-Methylanilino) -5,8-difluoroquinizarin E-55. 7-methoxy-6- (2,3,5,6-tetrafluoroanilino) -5,8-difluoroquinizarin E-56. 7-butoxy-6- (2,3,5,6-tetrafluoroanilino) -5,8-difluoroquinizarin E-57. 7-octyloxy-6- (2,3,5,6
-Tetrafluoroanilino) -5,8-difluoroquinizarin

F) Type (two aromatic and aliphatic amino functional groups were introduced into the quinizarin skeleton and one or two aromatic, aliphatic hydroxy functional groups or aromatic and aliphatic mercapto functional groups were introduced into the quinizarin skeleton. Blue system) F-1. 6,7-dianilino-5-phenoxy-8-
Fluoroquinizarin F-2. 6,7-dianilino-5-butoxy-8-fluoroquinizarin F-3. 6,7-dianilino-5-octyloxy-
8-Fluoroquinizarin F-4. 6-anilino-7-ethylamino-5 (or 8) -octyloxy-8 (or 5) -fluoroquinizarin F-5. 6-anilino-7-butylamino-8 (or 5) -octyloxy-5 (or 8) -fluoroquinizarin

F-6. 6-anilino-7-butylamino-5,8-dibutoxyquinizarin F-7. 6- (o-ethoxycarbonylanilino)-
7-butylamino-8 (or 5) -octyloxy-5 (or 8) -fluoroquinizarin F-8. 6- (p-ethoxycarbonylanilino)-
7-butylamino-8 (or 5) -octyloxy-5 (or 8) -fluoroquinizarin F-9. 6- (m-ethoxycarbonylanilino)-
7-butylamino-8 (or 5) -octyloxy-5 (or 8) -fluoroquinizarin F-10. 6- (o-cyanoanilino) -7-butylamino-8 (or 5) -octyloxy-5 (or 8) -fluoroquinizarin

F-11. 6- (p-cyanoanilino)-
7-butylamino-8 (or 5) -octyloxy-5 (or 8) -fluoroquinizarin F-12. 6- (m-cyanoanilino) -7-butylamino-8 (or 5) -octyloxy-5 (or 8) -fluoroquinizarin F-13. 6- (o-Nitroanilino) -7-butylamino-8 (or 5) -octyloxy-5 (or 8) -fluoroquinizarin F-14. 6- (p-nitroanilino) -7-butylamino-8 (or 5) -octyloxy-5 (or 8) -fluoroquinizarin F-15. 6- (m-nitroanilino) -7-butylamino-8 (or 5) -octyloxy-5 (or 8) -fluoroquinizarin

F-16. 6- (o-ethoxycarbonylanilino) -7-butylamino-5,8-dibutoxyquinizarin F-17. 6- (p-ethoxycarbonylanilino)-
7-butylamino-5,8-dibutoxyquinizarin F-18. 6- (m-ethoxycarbonylanilino)-
7-butylamino-5,8-dibutoxyquinizarin F-19. 6- (o-cyanoanilino) -7-butylamino-5,8-dibutoxyquinizarin F-20. 6- (p-cyanoanilino) -7-butylamino-5,8-dibutoxyquinizarin

F-21. 6- (m-cyanoanilino)-
7-butylamino-5,8-dibutoxyquinizarin F-22. 6- (o-Nitroanilino) -7-butylamino-5,8-dibutoxyquinizarin F-23. 6- (p-Nitroanilino) -7-butylamino-5,8-dibutoxyquinizarin F-24. 6- (m-nitroanilino) -7-butylamino-5,8-dibutoxyquinizarin F-25. 5,8-Dianilino-6,7-diphenylthioquinizarin

F-26. 5,8-Dianilino-6,7-
Dioctylthioquinizarin F-27. 5,8-bis (p-cyanoanilino) -6
7-diphenylthioquinizarin F-28. 5,8-bis (p-nitroanilino) -6
7-diphenylthioquinizarin F-29. 5,8-Dianilino-6,7-dioctylthioquinizarin F-30. 5,8-bis (p-cyanoanilino) -6
7-dioctylthioquinizarin

F-31. 5,8-bis (p-nitroanilino) -6,7-dioctylthioquinizarin F-32. 5,8-Dianilino-6,7-diphenoxyquinizarin F-33. 5,8-Dianilino-6,7-dibutoxyquinizarin F-34. 5,8-Dianilino-6,7-dioctyloxyquinizarin.

The novel quinizarin compound of the present invention can be produced, for example, by the above two methods. One production method is based on the general formula (II).
A quinizarin substituted at the 7- and 8-positions with a halogen is used as a starting material, and an aromatic amino compound, an aliphatic amino compound, an aromatic hydroxy compound, an aliphatic hydroxy compound, an aromatic mercapto compound or an aliphatic A nucleophilic substance selected from the group-based mercapto compounds is reacted individually or sequentially or simultaneously to cause nucleophilic substitution of a halogen atom.

At this time, the reaction is usually carried out in an organic solvent. Examples of the organic solvent include inert solvents such as nitrobenzene, acetonitrile and benzonitrile, and pyridine, N, N-dimethylacetamide and N-methyl-2-methyl-2-amide.
An aprotic polar solvent such as pyrrolidone, triethylamine, tri-n-butylamine, dimethyl sulfone, and sulfolane can be used. Alternatively, the reaction nucleophile itself such as the above-mentioned amino compound or hydroxy compound can be used as a solvent without using the organic solvent.

As the condensing agent, organic bases such as triethylamine and tri-n-butylamine and inorganic bases such as potassium fluoride, potassium hydroxide, potassium carbonate, sodium hydroxide and sodium carbonate are preferably used.
Alternatively, when an amino compound such as aniline, toluidine, anisidine, n-butylamine, n-octylamine or the like has a property as a condensing agent, the condensing agent is not necessarily used. Alternatively, if the reactivity of the reactive nucleophile itself is strong, a condensing agent is not necessarily required.

The reaction is preferably carried out at a temperature in the range of 40 ° C. to 200 ° C. The starting material, quinizarin, in which the positions 5, 6, 7 and 8 are substituted by halogen, is synthesized by a method discovered by the present inventor when the halogen is a fluorine atom (disclosed in Japanese Patent Application Laid-Open No. 61-12041). ). Other halogens can be synthesized in the same manner as in the case of the fluorine atom.

According to another production method, part or all of the benzene nucleus of phthalic anhydride is a halogen atom or a phthalic anhydride according to a generally well-known Friedel-Craft reaction (for example, JP-A-61-112041). Phthalic anhydride or phthalic acid substituted with a compound selected from an aromatic amino compound, an aliphatic amino compound, an aromatic hydroxy compound, an aliphatic hydroxy compound, an aromatic mercapto compound or an aliphatic mercapto compound (Preferably a derivative of phthalic anhydride) and a hydroquinone such as hydroquinone or dimethoxyhydroquinone (preferably dimethoxyhydroquinone).

Part or all of the benzene nucleus of phthalic anhydride is a halogen atom, an aromatic amino compound, an aliphatic amino compound, an aromatic hydroxy compound, an aliphatic hydroxy compound, an aromatic mercapto compound or an aliphatic Phthalic anhydride or a derivative of phthalic acid substituted with a compound selected from the series mercapto compounds is a halogenated phthalic anhydride or halogenated phthalic acid such as tetrachlorophthalic anhydride, tetrafluorophthalic anhydride or tetrafluorophthalic acid. A desired aromatic amino compound,
An aliphatic amino compound, an aromatic hydroxy compound, an aliphatic hydroxy compound, a reaction nucleophile selected from an aromatic mercapto compound or an aliphatic mercapto compound, alone or sequentially, or a plurality of them. It is produced by simultaneously reacting and substituting nucleophilic substitution for a halogen atom.

The reaction temperature is preferably in the range of 40 ° C. to 200 ° C. At this time, the reaction is usually carried out in an organic solvent. Examples of the organic solvent include an inert solvent such as nitrobenzene, acetonitrile and benzonitrile, pyridine, N, N-dimethylacetamide and N-methyl-2.
Aprotic polar solvents such as -pyrrolidone, triethylamine, tri-n-butylamine, dimethyl sulfone, and sulfolane; Alternatively, the reaction nucleophile itself such as the above-mentioned amino compound or hydroxy compound can be used as a solvent without using the organic solvent.

As the condensing agent, organic bases such as triethylamine and tri-n-butylamine and inorganic bases such as potassium fluoride, potassium hydroxide, potassium carbonate, sodium hydroxide and sodium carbonate are preferably used.
Alternatively, in the case where an amino compound such as aniline, toluidine, anisillin, n-butylamine, or n-octylamine has a property as a condensing agent itself, it is not necessary to use the condensing agent. Alternatively, if the reactivity of the reactive nucleophile itself is strong, a condensing agent is not necessarily required.

Alternatively, part or all of the benzene nucleus of phthalic anhydride may be a halogen atom, an aromatic amino compound, an aliphatic amino compound, an aromatic hydroxy compound, an aliphatic hydroxy compound, an aromatic mercapto compound or an aliphatic amino compound. Phthalic anhydride or a derivative of phthalic acid substituted with a compound selected from aromatic group mercapto compounds are described in Ishikawa et al., Journal of the Society of Organic Synthesis, Vol. 21, No. 8, (1971) 7
92 or a method disclosed in Japanese Patent Application No. 4-28185, in which a part or all of the benzene nucleus of phthalonitrile is previously converted to a desired halogen atom, aromatic amino compound, aliphatic amino compound, or aromatic amino compound. It can be obtained by hydrolyzing a series hydroxy compound, an aliphatic series hydroxy compound, an aromatic series mercapto compound, or phthalonitrile substituted with an aliphatic series mercapto compound according to an ordinary method.

[0085]

As described above, the novel compound of the present invention can be used in the absorption wavelength range of 480 nm to 700 nm by introducing a specific substituent at the 5,6,7,8 position of the quinizarin skeleton. Absorption wavelength control is possible,
In addition, it can provide high solubility in organic solvents, and the quinizarin skeleton originally has excellent light resistance, so it can be used as a visible light absorbing dye even in fields that could not be put into practical use with conventional technology it can. Particularly, when used as a heat-sensitive sublimation transfer dye, it has excellent properties as a magenta dye and a cyan dye, so that it can be effectively used.

[0086]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The dye numbers in the examples are the same as the above-mentioned compound numbers. For example, the dye A-1 is the same as the above-mentioned number A
Same as compound -1. Tables 1 to 11 show the physicochemical properties of the compounds produced in the examples. In these tables, the solubility is indicated by Δ for less than 1% by weight, ○ for about 1 to 3% by weight, and ◎ for 3% by weight or more.

Examples 1 and 2. Dye A-1 and color
Synthesis of element B-1 400 cc of acetonitrile and 3 g of 5,6,7,8-tetrafluoroquinizarin (9.
61 mmol), about 1.8 g (19.3 mmol) of aniline, and 1.34 g (23.1 mmol) of potassium fluoride
Was reacted under reflux for about 24 hours. After completion of the reaction, potassium fluoride was filtered off, and acetonitrile was distilled off. Then, the resultant was poured into an aqueous hydrochloric acid solution, the generated solid was filtered, washed with water and dried to obtain 4.3 g of a crude product. Thereafter, column purification was performed using silica gel (Wakogel C-200), and 1.23 g (yield 33.2 mol%) of dye A-1 and dye B-
0.41 g (yield 9.3 mol%) of Compound 1 was obtained. Dye A-1
Table 1 shows the physical properties of the dye B-1 and the analytical values for specifying the compound, and Table 3 shows the physical properties of the dye B-1 and the analytical values for specifying the compound.

Embodiments 3 and 4. Dye A-5 and color
Synthesis of element B-3 The procedure of Examples 1 and 2 was repeated, except that about 3.7 g (19.1 mmol) of n-butyl o-aminobenzoate was used in place of aniline. hand,
1.47 g (yield 31.5 mol%) of the target dye A-5 and 0.65 g (10.3 mol%) of dye B-3
Obtained. Table 1 shows the physical property values of Dye A-5 and the analysis values specifying the compound, and Table 3 shows the physical property values of Dye B-3 and the analysis values specifying the compound.

Embodiments 5 and 6 Dye A-4 and color
Synthesis of Element B-2 The procedure of Examples 1 and 2 was repeated, except that about 3.2 g (19.4 mmol) of ethyl m-aminobenzoate was used in place of aniline. 1.42 g (yield 32.3 mol%) of the dye A-4 and 0.56 g (9.7 mol%) of the dye B-2 were obtained. Dye A
Table 1 shows the physical property values of -4 and analytical values for specifying the compound,
Table 3 shows the physical property values of Dye B-2 and analysis values for specifying the compound.

Embodiment 7 FIG . Synthesis of Dye A-8 The same procedures as in Examples 1 and 2 were carried out except that about 4.8 g (19.3 mmol) of n-octyl m-aminobenzoate was used in place of aniline. 1.48 g of the target dye A-8 (yield: 28.4 mol%)
Obtained. Table 1 shows the physical property values and analytical values for specifying the compounds.
Shown in

Embodiment 8 FIG . Synthesis of Dye A-6 The procedure of Examples 1 and 2 was repeated except that about 3.7 g (19.1 mmol) of n-butyl p-aminobenzoate was used in place of aniline. hand,
1.53 g (yield 32.8 mol%) of the target dye A-6
Obtained. Table 1 shows the physical property values and analytical values for specifying the compounds.
Shown in

Embodiments 9 and 10 Dyes A-19 and
Synthesis of Dye B-13 In the same manner as in Examples 1 and 2, except that about 2.4 g (19.5 mmol) of o-anisidine was used in place of aniline, the target dye was prepared. A-1
1.34 (yield 33.6 mol%) of dye 9
Was obtained in an amount of 0.40 g (yield 8.0 mol%). Dye A-19
Table 2 shows the physical properties of the dye B-13 and the analytical values for specifying the compound, and Table 4 shows the physical properties of the dye B-13 and the analytical values for specifying the compound.
Shown in

Embodiments 11 and 12 Pigments A-21 and
Synthesis of Dye B-15 In the same manner as in Examples 1 and 2 except that about 2.4 g (19.5 mmol) of m-anisidine was used in place of aniline, the target dye was synthesized. A-2
1.21 g (yield: 30.3 mol%) of dye B-15
Was obtained (yield 10.8 mol%). Dye A-2
Table 3 shows the physical property values of No. 1 and the analysis values specifying the compound, and Table 4 shows the physical property values of Dye B-15 and the analysis values specifying the compound.

Embodiments 13 and 14 Dye A-20
Synthesis of Dye B-14 In Examples 1 and 2, the procedure of Examples 1 and 2 was repeated except that about 2.4 g (19.5 mmol) of p-anisidine was used instead of aniline. A-2
1.39 g (yield: 34.8 mol%) of dye B-14
Was obtained (yield 11.2 mol%). Dye A-2
Table 3 shows the physical properties of the dye B-14 and the analytical values for specifying the compound, and Table 4 shows the physical properties of the dye B-14 and the analytical values for specifying the compound.

Embodiments 15 and 16 Dye A-18
And Synthesis of Dye B-12 In Examples 1 and 2, 4-t was used instead of aniline.
ert. Operating in the same manner as in Examples 1 and 2 except that about 2.9 g (19.4 mmol) of -butylaniline was used,
1.26 g (yield 29.7 mol%) of the target dye A-18 and 0.43 g (7.8 mol%) of dye B-12
Obtained. Table 2 shows the physical property values of Dye A-18 and the analytical values specifying the compound, and Table 4 shows the physical property values of Dye B-12 and the analytical values specifying the compound.

Embodiment 17 FIG . Synthesis of Dye A-15 400 cc of acetonitrile and 3 g of 5,6,7,8-tetrafluoroquinizarin (9.
61 mmol) and about 0.7 g (9.5) of n-butylamine
7 mmol) and 0.67 g (11.5 mmol) of potassium fluoride were reacted at room temperature for about 24 hours. After completion of the reaction, potassium fluoride was filtered off, acetonitrile was distilled off, washed with water and dried to obtain 3.1 g of a crude product. Thereafter, column purification was performed using silica gel (Wakogel C-200) to obtain 2.92 g (yield: 83.2 mol%) of dye A-15. Table 2 shows the physical property values and analytical values for specifying the compound.

Embodiment 18 FIG . Synthesis of Dye B-23 In Example 17, the amount of n-butylaniline was adjusted to about 2.1.
g (28.7 mmol), the amount of potassium fluoride was 2.0
The same operation as in Example 17 was carried out except that the amount was increased to 1 g (34.0 mmol), to obtain 2.27 g (yield: 50.1 mol%) of the target dye B-23. Table 5 shows the physical properties and analytical values for specifying the compound.

Embodiment 19 FIG . Synthesis of Dye A-17 400 cc of acetonitrile and 3 g of 5,6,7,8-tetrafluoroquinizarin (9.
61 mmol) and about 0.95 g of cyclohexylamine
(9.58 mmol) and 0.67 g of potassium fluoride (1
1.5 mmol) and reacted at 50 ° C. for about 24 hours. After completion of the reaction, potassium fluoride was filtered off, acetonitrile was distilled off, washed with water and dried to obtain 3.3 g of a crude product. Thereafter, column purification was performed using silica gel (Wakogel C-200) to obtain 2.02 g of dye A-17 (yield 5).
3.7 mol%). Table 2 shows the physical property values and analytical values for specifying the compound.

Examples 20 and 21. Dye A-10
And Dye B-7 Synthesis 200cc four-necked flask p- aminobenzonitrile 1
00g and 5,6,7,8-tetrafluoroquinizarin 3
g (9.61 mmol) was charged and reacted at 120 ° C. for about 4 hours. After completion of the reaction, the reaction solution
After pouring into a mixed solution of about 500 cc of water and acidifying with concentrated hydrochloric acid, the formed solid was filtered, washed with water and dried to obtain 4.8 g of a crude product. Then silica gel (Wakogel C-2)
00) and 1.21 g of dye A-10 was purified by column purification.
(Yield 30.7 mol%), and 0.45 (9.2 mol% yield) of dye B-7 were obtained. Table 1 shows the physical property values of Dye A-10 and the analytical values for specifying the compound, and Table 4 shows the physical property values of Dye B-7 and the analytical values for specifying the compound.

Embodiment 22 FIG . Synthesis of Dye A-10 (Part 2) 4 g (12.6 mmol) of 4-cyanoanilino-3,5,6-trifluorophthalic anhydride and 4.34 g (31.4 mmol) of p-dimethoxybenzene were added to anhydrous aluminum chloride. 50 g (0.37 mol) and 5 g of sodium chloride were added little by little to a melt (130 to 135 ° C.), and then the temperature was raised and maintained at 180 ° C. for 1 hour with stirring. Next, the reaction mixture was poured into ice water, and then 50 cc of concentrated hydrochloric acid was added. The resulting solid was filtered, washed with water and dried to obtain a crude product 3.2.
g was obtained. Then silica gel (Wakogel C-200)
Was used for column purification to obtain 1.92 g (yield: 37.2 mol%) of dye A-10.

Mass spectrometry spectrum m / e = 410 (M ⁺ , 100) m / e = 391 (M ⁺ -19, 20) Elemental analysis value C (%) H (%) N (%) F (%) ) Theoretical value 61.47 2.21 6.83 13.89 Analysis value 61.52 2.23 6.79 13.82

Embodiment 23 FIG . Synthesis of Dye A-12 In Examples 20 and 21, 100 g of p-nitroaniline was used in place of p-aminobenzonitrile, and the reaction temperature was adjusted to 160 ° C. 1.17 g of dye A-12 (yield 2
8.3 mol%). Table 2 shows the physical property values and analytical values for specifying the compound.

Embodiments 24 and 25. Dye A-23
Synthesis of Dye B-21 The procedure of Examples 20 and 21 was repeated, except that 100 g of 2,6-diethylaniline was used in place of p-aminobenzonitrile. 1.36 g (yield 32.1 mol%) and 0.58 g (yield 10.6 mol%) of dye B-21 were obtained.
Table 3 shows the physical property values of Dye A-23 and the analytical values specifying the compound, and Table 5 shows the physical property values of Dye B-21 and the analytical values specifying the compound.

Embodiment 26 FIG . Synthesis of Dye B-19 400 cc of acetonitrile, 3 g (8.21 mmol) of Dye A-15, about 0.92 g (9.88 mmol) of aniline, and 0.4 g of potassium fluoride in a 500 cc four-necked flask.
57 g (9.81 mmol) was charged and reacted under reflux for about 24 hours. After completion of the reaction, potassium fluoride was filtered off, acetonitrile was distilled off, washed with water and dried to obtain 3.9 g of a crude product. Then silica gel (Wakogel C-2)
00), and 1.20 g of dye B-19 was purified by column purification.
(33.3 mol% yield). Table 5 shows the physical properties and analytical values for specifying the compound.

Embodiment 27 FIG . Synthesis of Dye B-17 In the same manner as in Example 26 except that 1.63 g (9.87 mmol) of ethyl m-aminobenzoate was used in place of aniline, the target dye B-17 was obtained. 1.27 g (yield 30.3 mol%) was obtained. Table 4 shows the physical property values and analytical values for specifying the compound.

Embodiment 28 FIG . Synthesis of Dye B-18 1.31 g of the intended dye B-18 was obtained in the same manner as in Example 26 except that p-anisidine (1.21 g, 9.82 mmol) was used instead of aniline.
(34.1 mol% yield). Table 5 shows the physical properties and analytical values for specifying the compound.

Embodiment 29 FIG . Synthesis of Dye A-13 400 cc of ammonia water (2
9%) and 5,6,7,8-tetrafluoroquinizarin 1
g (3.2 mmol) was charged and reacted at room temperature for about 12 hours. After the completion of the reaction, the resulting solid matter was neutralized with concentrated hydrochloric acid, filtered, washed with water and dried to obtain 0.9 g of a crude product. Thereafter, column purification was performed using silica gel (Wakogel C-200) to obtain 0.08 g (yield 8.1 mol%) of dye A-13. Table 2 shows the physical property values and analytical values for specifying the compound.

Embodiment 30 FIG . Synthesis of Dye C-9 400 cc methanol and 500 cc in a 500 cc four-necked flask
6,7,8-tetrafluoroquinizarin 3 g (9.61
Mmol) and 1.08 g (19.2 mmol) of potassium hydroxide, and reacted under reflux for about 24 hours. After completion of the reaction, the mixture was poured into water, and the generated solid was filtered, washed with water and dried to obtain 3.03 g (93.8 mol%) of a dye C-9. Table 6 shows the physical property values and analytical values for specifying the compound.

Embodiment 31 FIG . Synthesis of Dye C-10 The procedure of Example 38 was repeated except that 400 cc of ethanol was used instead of methanol and the reaction time was about 12 hours.
(Yield 94.0 mol%). Table 6 shows the physical property values and analytical values for specifying the compound.

Embodiment 32 FIG . Synthesis of Dye C-13 400 cc of n-butanol and 3 g of 5,6,7,8-tetrafluoroquinizarin (9.
61 mmol) and 1.08 g (19.2) of potassium hydroxide.
Mmol) and reacted under reflux for about 6 hours. After completion of the reaction, the solution was transferred to a separating funnel, water was added thereto, and the mixture was shaken and separated. Thereafter, n-butanol in the organic layer was distilled off, and the obtained solid was dried to obtain 3.74 g of a dye C-13 (yield: 92.10 g).
6 mol%). Table 6 shows the physical property values and analytical values for specifying the compound.

Embodiment 33 FIG . Synthesis of dye C-4 400 cc of n-butanol and 3 g of 5,6,7,8-tetrafluoroquinizarin (9.
61 mmol) and 0.539 g of potassium hydroxide (9.6)
1 mmol) and reacted under reflux for about 6 hours. After completion of the reaction, the solution was transferred to a separating funnel, water was added thereto, and the mixture was shaken and separated. Thereafter, n-butanol in the organic layer was distilled off, and the obtained solid was dried to obtain 3.1 g of a crude product. Thereafter, column purification was performed using silica gel (Wakogel C-200) to obtain 2.37 g (yield: 67.3 mol%) of a dye C-4.
Table 5 shows the physical properties and analytical values for specifying the compound.

Embodiment 34 FIG . Synthesis of Dye C-5 In the same manner as in Example 33 except that 400 cc of n-hexyl alcohol was used in place of n-butanol and the reaction temperature was set to 120 ° C., the same operation as in Example 33 was carried out to obtain the dye C-5.
Was obtained (yield 65.7 mol%). Table 6 shows the physical property values and analytical values for specifying the compound.

Embodiment 35 FIG . Synthesis of Dye C-6 In the same manner as in Example 33 except that 400 cc of n-octyl alcohol was used instead of n-butanol and the reaction temperature was set to 120 ° C., the same operation as in Example 33 was carried out to obtain dye C-6.
Was obtained (yield 66.3 mol%). Table 6 shows the physical property values and analytical values for specifying the compound.

Embodiment 36 FIG . Synthesis of Dye C-18 400 phenol and 500 cc in a 500 cc four-necked flask
6,7,8-tetrafluoroquinizarin 3 g (9.61
Mmol) and 1.34 g (23.1 mmol) of potassium fluoride and reacted at 150 ° C. for about 6 hours. After completion of the reaction, the solution was poured into a mixture of 2.4 cc of methanol and 400 cc of water, and the resulting solids were filtered, washed with methanol and water, and dried to obtain 2.97 g (67.1 mol%) of dye C-18. Obtained. Table 7 shows the physical property values and analytical values for specifying the compound.

Embodiment 37 FIG . Synthesis of dye C-1 4-methoxy-3,5,6-trifluorophthalic anhydride (4 g, 16 mmol) and p-dimethoxybenzene 5.3
1 g (38.4 mmol) of anhydrous aluminum chloride 65
g (0.49 mol) and 6.5 g of sodium chloride (130 to 135 ° C.) were added little by little, and then the temperature was raised and maintained at 200 ° C. for 30 minutes with stirring. Next, the reaction mixture was poured into ice water, and after adding 65 cc of concentrated hydrochloric acid, the formed solid was filtered, washed with water and dried to obtain 2.9 g of a crude product. Thereafter, column purification was performed using silica gel (Wakogel C-200) to obtain 1.78 g of dye C-1 (yield: 35.50 g).
9 mol%). Table 5 shows the physical properties and analytical values for specifying the compound.

Embodiment 38 FIG . Synthesis of Dye C-8 4 g (15.3 mmol) of 4,5-dimethoxy-3,6-difluorophthalic anhydride and 5.3 g (38.4 mmol) of p-dimethoxybenzene were added to 60 g (0.45 mmol) of anhydrous aluminum chloride. Mol) and 6 g of sodium chloride (130-135 ° C) were added little by little, and then the temperature was raised and maintained at 200 ° C for 30 minutes with stirring. Next, the reaction mixture was poured into ice water, and after adding 60 cc of concentrated hydrochloric acid, a solid content formed was filtered, washed with water and dried to obtain 2.6 g of a crude product. Thereafter, column purification was performed using silica gel (Wakogel C-200), and 1.72 g of dye C-8 was obtained (yield: 36.
5 mol%). Table 6 shows the physical property values and analytical values for specifying the compound.

Embodiment 39 FIG . Synthesis of Dye D-13 400 cc of acetonitrile and 3 g of 5,6,7,8-tetrafluoroquinizarin (9.
61 mmol) and 2.12 g of thiophenol (19.2).
Mmol) and 1.34 g (23.1 mmol) of potassium fluoride and reacted under reflux for about 8 hours. After completion of the reaction, potassium fluoride was filtered off, acetonitrile was distilled off, and then dried, and 4.6 g (97.2 mol%) of Dye D-13 was obtained.
Obtained. Table 6 shows the physical property values and analytical values for specifying the compounds.
Shown in

Embodiment 40 FIG . Synthesis of Dye D-16 In Example 39, 4-mercapto-2,3,5,6-tetrafluorobenzoic acid was used instead of thiophene.
The same operation as in Example 39 was carried out except for using 35 g (19.2 mmol), to obtain 5.45 g (yield: 78.3 mol%) of the target dye D-16. Table 8 shows the physical property values and analytical values for specifying the compound.

Embodiment 41 FIG . Synthesis of Dye D-17 In the same manner as in Example 39 except that 3.98 g (19.2 mmol) of 4-mercapto-2,3,5,6-tetrafluorobenzonitrile was used instead of thiophene. By operation, 4.83 g of target dye D-17 was obtained.
(Yield: 73.2 mol%). Table 8 shows the physical property values and analytical values for specifying the compound.

Embodiment 42 FIG . Synthesis of Dye D-14 In the same manner as in Example 39 except that 2.43 g (19.3 mmol) of p-mercaptophenol was used in place of thiophene, the same procedure as in Example 39 was carried out to obtain the target dye D-1.
4.41 g (yield 87.5 mol%) was obtained. Table 8 shows the physical property values and analytical values for specifying the compound.

Embodiment 43 FIG . Synthesis of Dye D-15 In Example 39, 2.69 g (19.2 mmol) of p-methoxybenzenethiol was used instead of thiophenol.
The same procedure was followed as in Example 39, except that the target dye D was used.
4.52 g (yield: 85.1 mol%) of -15 was obtained. Table 8 shows the physical property values and analytical values for specifying the compound.

Embodiment 44 FIG . Synthesis of Dye D-9 In the same manner as in Example 39 except that 2.28 g (19.2 mmol) of hexanethiol was used instead of thiophene, the same procedure as in Example 39 was carried out to give 4.5 of the intended dye D-9.
1 g (92.3 mol% yield) was obtained. Table 7 shows the physical property values and analytical values for specifying the compound.

Embodiment 45 FIG . Synthesis of Dye D-10 In the same manner as in Example 39 except that 2.81 g (19.2 mmol) of octanethiol was used in place of thiophene, the same procedure as in Example 39 was carried out to obtain the target dye D-10.
91 g (yield 90.5 mol%) was obtained. Table 7 shows the physical property values and analytical values for specifying the compound.

Embodiment 46 FIG . Synthesis of Dye D-8 In Example 39, tert
t. 1.74 g (19.2 mmol) of butylthiol
The same procedure was followed as in Example 39, except that the target dye D was used.
4.02 g (yield 92.3 mol%) of -8 was obtained. Table 7 shows the physical property values and analytical values for specifying the compound.

Embodiment 47 FIG . Synthesis of Dye D-12 Dye D-1 was obtained in the same manner as in Example 39 except that 2.23 g (19.2 mmol) of cyclohexanethiol was used instead of thiophene.
4.54 g (yield 93.6 mol%) of Compound 2 was obtained. Table 8 shows the physical property values and analytical values for specifying the compound.

Embodiment 48 FIG . Synthesis of Dye D-25 In Example 39, 4.24 g (3
8.5 mmol) and 2.68 g of potassium fluoride (4
The same operation as in Example 39 was carried out except that the reaction time was increased to 6.1 mmol), and 5.93 g (yield: 91.7 mol%) of the target dye D-25 was obtained. Table 8 shows the physical property values and analytical values for specifying the compound.

Embodiment 49 FIG . Synthesis of Dye D-22 In the same manner as in Example 48 except that 3.48 g (38.5 mmol) of n-butylthiol was used instead of thiophene, the same procedure was carried out as in Example 48 to obtain 5 of the target dye D-22. 0.09 g (yield 89.3 mol%) was obtained. Table 8 shows the physical property values and analytical values for specifying the compound.

Embodiment 50 FIG . Synthesis of Dye E-9 A 500 cc four-necked flask was charged with 400 cc of octyl alcohol, 3 g (6.18 mmol) of Dye A-6, and 0.347 g (6.18 mmol) of potassium hydroxide.
The reaction was performed at 0 ° C. for about 5 hours. After completion of the reaction, the solution was transferred to a separating funnel, water was added thereto, and the mixture was shaken and separated. Thereafter, octyl alcohol in the organic layer was distilled off, and the obtained solid was dried to obtain 3.55 g (yield 96.4 mol%) of a dye E-9.
Table 9 shows the physical property values and analytical values for specifying the compound.

Embodiment 51 FIG . Synthesis Example of Dye E-7 In Example 50, 3 g (6.
The same procedure as in Example 50 was carried out except that the dye A-4 (56 mmol) and 0.368 g (6.56 mmol) of potassium hydroxide were used, and 3.62 g of the target dye E-7 was used.
(97.2 mol% yield). Table 9 shows the physical property values and analytical values for specifying the compound.

Embodiment 52 FIG . Synthesis Example of Dye E-18 In Example 50, 3 g (7.
Example 5 except that dye A-10 (31 mmol) and 0.41 g (7.31 mmol) of potassium hydroxide were used.
3.66 g of the target dye E-18 was operated in the same manner as in Example 1.
(Yield 96.2 mol%). Table 9 shows the physical property values and analytical values for specifying the compound.

Embodiment 53 FIG . Synthesis Example of Dye E-14 In Example 50, 3 g (6.
Example 5 except that 97 mmol) of dye A-12 and 0.391 (6.97 mmol) of potassium hydroxide were used.
The same operation as in Example 0, 3.61 g of the target dye E-14 was carried out.
(95.8 mol% yield). Table 9 shows the physical property values and analytical values for specifying the compound.

Embodiment 54 FIG . Synthesis Example of Dye E-24 In Example 50, 3 g (6.
80 mmol) of dye A-23, potassium hydroxide 0.3
The procedure of Example 50 was repeated except that 81 (6.80 mmol) was used, to obtain 3.56 g (yield 9) of the target dye E-24.
4.9 mol%). Table 9 shows the physical property values and analytical values for specifying the compound.

Embodiment 55 FIG . Synthesis of Dye E-29 100 g and 3 g of aniline in a 200 cc four-necked flask
(7.14 mmol) of dye C-13 was charged at 120 ° C.
For about 4 hours. After the completion of the reaction, the reaction solution was poured into a mixed solution of about 400 cc of acetone and about 500 cc of water, acidified with concentrated hydrochloric acid, and the resulting solid was filtered, washed with water and dried to obtain 3.4 g of a crude product. . Thereafter, column purification was performed using silica gel (Wakogel C-200) to obtain 0.96 g (yield 27.3 mol%) of dye E-29. Table 9 shows the physical property values and analytical values for specifying the compound.

Embodiment 56 FIG . Synthesis of Dye E-33 The procedure of Example 55 was repeated, except that ethyl m-aminobenzoate was used in place of aniline. Mol%). Table 10 shows the physical property values and analysis values for specifying the compound.

Embodiment 57 FIG . Synthesis of Dye E-34 1.14 g (yield 26.9 mol%) of Example 14 was obtained in the same manner as in Example 55 except that n-butyl p-aminobenzoate was used instead of aniline. The target dye E-34 was obtained. Table 10 shows the physical property values and analysis values for specifying the compound.

Embodiment 58 FIG . Synthesis of Dye E-39 1.06 g (yield: 28.6 mol%) of Example 55 except that p-aminobenzonitrile was used in place of aniline and the reaction temperature was changed to 150 ° C. ) Was obtained. Table 10 shows the physical property values and analysis values for specifying the compound.

Embodiment 59 FIG . Synthesis of Dye E-36 Example 55 was repeated except that p-nitroaniline was used in place of aniline and the reaction temperature was 160 ° C.
In the same manner as in the above, 0.99 g (yield 25.8 mol%) of the target dye E-36 was obtained. Table 10 shows the physical property values and analysis values for specifying the compound.

Embodiment 60 FIG . Synthesis of Dye E-41 In Example 55, 3 g (8.92) of ethyl m-aminobenzoate was used instead of aniline in place of Dye C-13.
1.17 g (yield 2) of the target dye E-41
7.2 mol%). Table 10 shows the physical property values and analysis values for specifying the compound.

Embodiment 61 FIG . Synthesis of Dye E-42 400 cc of n-butanol and 6- (m-butoxycarbonylanilino) -5,7,8 were placed in a 500 cc four-necked flask.
3 g (6.18 mmol) of trifluoroquinizarin and 0.694 g (12.4 mmol) of potassium hydroxide were charged and reacted under reflux for about 6 hours. After completion of the reaction, the solution was transferred to a separating funnel, water was added thereto, and the mixture was shaken and separated. Thereafter, n-butanol in the organic layer was distilled off, and the obtained solid was dried to obtain 3.3 g of a crude product. Thereafter, column purification was performed using silica gel (Wakogel C-200) to obtain 2.36 g (yield: 64.3 mol%) of dye E-42. Table 10 shows the physical property values and analysis values for specifying the compound.

Embodiment 62 FIG . Synthesis of Dye E-43 In Example 61, 6- (p-butoxycarbonylanilino) -5 was used instead of 6- (m-butoxycarbonylanilino) -5,7,8-trifluoroquinizarin.
The same procedure as in Example 61 was repeated, except that 3 g (6.18 mmol) of 7,8-trifluoroquinizarin, n-octyl alcohol was used instead of n-butanol, and the reaction temperature was changed to 120 ° C. 43 (2.43 g, yield 5)
5.7 mol%). Table 11 shows the physical property values and analysis values for specifying the compound.

Embodiment 63 FIG . Synthesis of Dye E-48 400 cc of ammonia water (2
9%) and 3 g (6.09 mmol) of dye D-13 were charged and reacted at room temperature for about 12 hours. After the completion of the reaction, the resulting solid matter was neutralized with concentrated hydrochloric acid, filtered, washed with water and dried to obtain 2.9 g of a crude product. Then silica gel (Wakogel C)
-200), and the dye E-48 was purified by 0.7
2 g (yield 24.1 mol%) was obtained. Table 11 shows the physical property values and analysis values for specifying the compound.

Embodiment 64 FIG . Synthesis of Dye F-5 400 cc of octyl alcohol, 3 g (6.84 mmol) of Dye B-19 and 0.384 g (6.84 mmol) of potassium hydroxide were charged into a 500 cc four-necked flask.
The reaction was performed at 20 ° C. for about 5 hours. After completion of the reaction, the solution was transferred to a separating funnel, water was added thereto, and the mixture was shaken and separated. Thereafter, octyl alcohol in the organic layer was distilled off, and the obtained solid was dried to obtain 3.63 g (yield 96.7 mol%) of a dye F-5. Table 11 shows the physical property values and analysis values for specifying the compounds.
Shown in

Embodiment 65 FIG . Synthesis of Dye F-9 In Example 64, 3 g was used instead of Dye B-19.
The same procedure as in Example 64 was carried out except using (5.88 mmol) of the dye B-17 and 0.33 g (5.88 mmol) of potassium hydroxide, to obtain 3.44 of the target dye F-9.
g (yield 94.3 mol%). Table 11 shows the physical property values and analysis values for specifying the compound.

Embodiment 66 FIG . Synthesis of dye F-25 100 g and 3 g of aniline in a 200 cc four-necked flask
(6.09 mmol) Dye D-13 and 150 ° C.
For about 4 hours. After completion of the reaction, the reaction solution was poured into a mixed solution of about 400 cc of acetone and about 500 cc of water, acidified with concentrated hydrochloric acid, and the resulting solid was filtered, washed with water and dried to obtain 3.2 g of a crude product. . Thereafter, column purification was performed using silica gel (Wakogel C-200) to obtain 1.21 g (yield: 31.1 mol%) of dye F-25. Table 11 shows the physical property values and analysis values for specifying the compound.

Embodiment 67 FIG . Synthesis of Dye F-33 In Example 55, the same procedure as in Example 55 was carried out except that the reaction temperature was changed to 150 ° C., to convert the intended dye F-33 into 0.4.
4 g (10.9 mol% yield) was obtained. Table 11 shows the physical property values and analysis values for specifying the compound.

Examples 68 and 69. Dye A-27
And Synthesis of Dye B-22 In Examples 20 and 21, except that 100 g of 2,6-dichloroaniline was used in place of P-aminobenzonitrile and the reaction temperature was 200 ° C.
1.28 g of target dye A-27 was obtained in the same manner as in Example 1.
(Yield 29.3 mol%), 0.43 g of dye B-22
(Yield 7.51 mol%). Table 3 shows the physical property values of Dye A-27 and the analysis values for specifying the compound, and Table 5 shows the physical property values of Dye B-22 and the analysis values for specifying the compound.

Examples 70 and 71. Dye A-30
And Synthesis of Dye B-26 The procedure of Examples 20 and 21 was repeated except that 100 g of 2,6-diisopropylaniline was used in place of P-aminobenzonitrile. 1.68 g (yield 37.3 mol%) and 0.79 g (yield 13.1 mol%) of dye B-26 were obtained.
Table 3 shows the physical property values of Dye A-30 and the analytical values specifying the compound, and Table 5 shows the physical property values of Dye B-26 and the analytical values specifying the compound.

[0148]

[Table 1]

[0149]

[Table 2]

[0150]

[Table 3]

[0151]

[Table 4]

[0152]

[Table 5]

[0153]

[Table 6]

[0154]

[Table 7]

[0155]

[Table 8]

[0156]

[Table 9]

[0157]

[Table 10]

[0158]

[Table 11]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 255/54 C07C 255/54 255/58 255/58 323/22 323/22 C09B 1/08 C09B 1/08 1/14 1 / 14 1/503 1/503 1/514 1/514 1/515 1/515 1/54 1/54 1/60 1/60 C09K 3/00 C09K 3/00 U (56) References JP 61 -291652 (JP, A) JP-A-62-15260 (JP, A) JP-A-63-268768 (JP, A) JP-A-61-255897 (JP, A) JP-A-61-193887 (JP, A) JP-A-60-172591 (JP, A) JP-A-54-130626 (JP, A) JP-A-47-3438 (JP, A) JP-A-50-37827 (JP, A) 3939 (JP, A) JP-A-48-43017 (JP, A) JP-B-41-15113 (JP, B1) WO 91/15954 (WO, A1) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) C09B 1/51 4 C09B 1/54 C09B 1/60 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. The following general formula (I): ( Wherein A is independently a carboxyl group, a methoxy
Bonyl group, ethoxycarbonyl group, butoxycarbonyl
Group, octyloxycarbonyl group, -CN or -NO
₂ represents; B is alkyl group having 1 to 4 carbon atoms, the number 6-10 cycloalkyl group having a carbon atom, 1 to carbon atoms
R ¹ , R ² and R ³ each independently represent a hydrogen atom or a carbon atom having 1 to 1 carbon atoms;
A, b, and c are each independently an integer from 0 to 3; d, e, and f are integers from 0 to 5, provided that a + d, b + e, and c + f are 0 to 5; Is an integer) . ] The quinizarin type compound represented by these. 2. The following general formula (I): ( Wherein A is independently a carboxyl group, a methoxy
Bonyl group, ethoxycarbonyl group, butoxycarbonyl
Group, octyloxycarbonyl group, -CN or -NO
₂ represents; B is alkyl group having 1 to 4 carbon atoms, the number 6-10 cycloalkyl group having a carbon atom, 1 to carbon atoms
R ¹ , R ² and R ³ each independently represent a hydrogen atom or a carbon atom having 1 to 1 carbon atoms;
A, b and c are each independently an integer from 0 to 3; d, e and f are integers from 0 to 5, provided that a + d, b + e and c + f are 0 to 5 Is an integer) . ] The quinizarin type compound represented by these. 3. The method for producing a quinizarine compound according to claim 1 or 2, wherein the compound has the following general formula (II): (Wherein R ⁰ represents a halogen atom), and a halogen-containing quinizarin compound represented by the following general formula (III): (Where A, B, R ¹ , R ² , R ³ , a, b, c, d, e
And f are as defined above ), or reacting with one of the compounds of the formula (III)
And reacting them sequentially or simultaneously with a plurality of compounds represented by the formula: 4. The method for producing a quinizarine compound according to claim 1, wherein the compound has the following general formula (IV): ( Wherein W, X, Y and Z are as defined above ), and reacting the phthalic anhydride derivative with hydroquinone or 1,4-dimethoxybenzene. 5. A visible light absorbing material comprising the quinizarin compound according to claim 1 or 2.