JPH0513992B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is applicable to disperse dyes (for example, CIDisperse
Blue 60), near-infrared absorbers (for example, JP-A-62
-54761), dichroic dyes for color liquid crystals (for example, "Special Functional Dyes" by Ikemori, published by CMC, pp. 49-51), dyes for polarizing plates (for example, JP-A-63-30563 and 62-
275163), relates to a method for producing anthraquinone dyes used in sublimation transfer recording dyes, etc. [Conventional technology and issues] The following formula () [In formula (), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom, an amino group, an alkylamino group, a hydroxyl group, an alkoxy group or a halogen atom,
R represents a substituted or unsubstituted alkyl group, cyclic alkyl group, aryl group or heterocycle. ] The method for producing the dye represented by
and methanol as shown in Japanese Patent Application Laid-open No. 63-30563,
At a temperature of 50 to 200℃ in alcohol solvents such as butanol and ethylene glycol, aromatic aprotic solvents such as benzene, chlorobenzene, and nitrobenzene, and amide solvents, the following formula () [In formula (), Y ¹ , Y ² , Y ³ and Y ⁴ are in formula ()
It has the same meaning as Y ¹ , Y ² , Y ³ and Y ⁴ . ] Anthraquinone-2,3-dicarboxylic acid anhydride represented by the following formula () R-NH ₂ () [In the formula (), R represents the same meaning as R in the formula (). ] A method has been adopted in which an amine represented by the following is reacted. However, the raw material anthraquinone-2,3-dicarboxylic anhydride is insoluble in the above solvent,
In addition, the reaction activity is low in the above solvent, leaving a large amount of unreacted substances, and when the reaction is carried out at a high temperature, a large amount of by-products are produced. [Means for solving the problem] As a result of intensive study, the present inventors have determined that the following formula () [In formula (), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydroxyl atom, an alkyl group or a halogen atom. ] Anthraquinone-2,3-dicarboxylic anhydride of the formula () using a phenol represented by as a solvent in the presence or absence of quinoline, isoquinoline, pyridine, monoalkylpyridine, dialkylpyridine, or trialkylpyridine. Reacting amines of formula () with formula () gives high yields of formula ()
It has been discovered that anthraquinone dyes can be obtained, and the present invention has been achieved. Specific examples of compounds represented by formula () include:
1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride, 1,4-dihydroxyanthraquinone-2,3-dicarboxylic anhydride, 1-amino-4-hydroxyanthraquinone-2,3-dicarboxylic anhydride, 1,4-diamino-5-hydroxyanthraquinone-2,3-dicarboxylic anhydride, 1,4-diamino-5,8-dihydroxyanthraquinone-2,3-dicarboxylic anhydride,
1,4,5-triaminoanthraquinone-2,3
-dicarboxylic anhydride, 1,4,5,8-tetraaminoanthraquinone-2,3-dicarboxylic anhydride, 1,5-diamino-4,8-dihydroxyanthraquinone-2,3-dicarboxylic anhydride,
Examples include 1,8-diamino-4,5-dihydroxyanthraquinone-2,3-dicarboxylic anhydride and 1-amino-4-bromoanthraquinone-2,3-dicarboxylic anhydride. Examples of substituted or unsubstituted alkylamines represented by formula () include methylamine, ethylamine, propylamine, butylamine, octylamine, γ-methoxyamine, ethoxyethoxyethylamine, β-chloramine, β-methoxycarbonylethylamine. , N,N-dimethylaminoethylamine, etc. Examples of substituted or unsubstituted cycloalkylamines include cyclohexylamine, 4-tert-butylcyclohexylamine, 4-tert-amylcyclohexylamine,
Examples of substituted or unsubstituted arylamines include aniline, toluidine, ethylaniline, methoxycarbonylaniline, nitroaniline, p-nonylaniline, cetylaminocarbonylaniline, benzidine, benzoxazoylaniline, Aniline derivatives such as aminoazobenzene, benzothiazolylaniline, tolidine, N,N-diethylaminoaniline, octyloxycarbonyl phenylaniline, benzoxazoylbiphenylamine, biphenylamine, naphthylamine, alkylnaphthylamine, aminoanthraquinone, diaminoanthraquinone, amino Examples include fused polycyclic amines such as anthracene, and examples of heterocyclic amines include thiophene amine, benzothiazole amine, nitrothiazole amine, benzoxazole amine, pyridine amine, and methylpyridine amine. Further, examples of the phenol derivative represented by the formula () include phenol, o-chlorophenol,
m-chlorophenol, p-chlorophenol,
Examples include o-cresol, m-cresol, p-cresol, ethylphenol, and butylphenol. The reaction conditions are preferably 0.7 to 2.0 mol of amines per 1 mol of anthraquinone-2,3-dicarboxylic anhydride represented by the general formula ();
In addition, the phenol derivative used as a solvent is 5-
2000 mol is preferred, and when using quinoline, isoquinoline, pyridine and their derivatives as catalysts, it is preferred to use a molar ratio of 0.005 to 5. The reaction temperature is preferably 50 to 200°C, and the reaction time is preferably 1 to 30 hours. Incidentally, when quinoline, isoquinoline and pyridine are used as catalysts, intermolecular imidization is suppressed and a higher purity compound () can be obtained. The effect is particularly remarkable in the case of imides of arylamine and heterocyclic amine derivatives. [Example] Hereinafter, the present invention will be explained in detail with reference to Examples. Example 1 308 g of 1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride, 2-aminonaphthalene
143g, isoquinoline 130g and metacresol
The mixture of 15 was heated and stirred at 150°C for 4 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were filtered, washed with methanol, and dried. Yield: 400g. This crystal was identified as the following compound by IR and NMR, and was found to have a purity of 95% by liquid chromatography. Example 2 A mixture of 340 g of 1,4-diamino-5,8-dihydroxyanthraquinone dicarboxylic acid anhydride, 167 g of p-phenylaniline, 100 g of quinoline, and 15 o-chlorophenol was heated and stirred at 200° C. for 6 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were filtered, washed with methanol, and dried. Yield: 450g. This crystal was a compound of the following formula and had a purity of 96%. Example 3 A mixture of 309 g of 1-amino-4-hydroxyanthraquinone dicarboxylic acid anhydride, 169 g of 2,6-diaminoanthraquinone, 60 g of isoquinoline, and 3000 g of p-cresol was heated and stirred at 200° C. for 10 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were filtered, washed with methanol, and dried. Yield 400
g. This crystal is a compound of the following formula, and the purity is 94%
It was hot. Examples 4 to 19 According to the following general formula, Y ¹ , Y ² shown in Table 1,
Compounds Y ³ , Y ⁴ and R were synthesized. Table 1 shows the results.
It is written in

【table】

【table】

Claims (1)

[Claims] 1. The following formula () [In formula (), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom, an amino group, an alkylamino group, a hydroxyl group, an alkoxy group, or a halogen atom. ] Anthraquinone-2,3-dicarboxylic acid anhydride represented by the following formula () R-NH ₂ () [In the formula (), R is a substituted or unsubstituted alkyl group, cyclic alkyl, aryl group or heterocycle represents. ] The amines represented by the following formula () [In formula (), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom, an alkyl group or a halogen atom. ] The following formula () is characterized by a heating reaction in the presence or absence of quinoline, isoquinoline, pyridine, monoalkylpyridine, dialkylpyridine, or trialkylpyridine in the phenol derivative represented by [In formula (), Y ¹ , Y ² , Y ³ and Y ⁴ are
It means the same group as Y ¹ , Y ² , Y ³ and Y ⁴ , and R has the same meaning as R in formula (). ] A method for producing an anthraquinone dye represented by: