JPH0619035B2 - Method for producing quinophthalone dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a dichroic dye for color liquid crystal (for example, JP-A-59).
-36181, JP-A-58-53979), dyes for polarizing plates (for example, JP-A-62-270664), dyes for sublimation transfer recording, and a process for producing a quinophthalone dye.

[Conventional technology and problems]

Formula (IV) [In the formula (IV), Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ each independently represent a hydrogen atom, an alkyl group, an amino group, an alkylamino group, a hydroxyl group, an alkoxy group or a halogen atom, and R Represents a substituted or unsubstituted alkyl group, cyclic alkyl group, aryl group or heterocycle. The method for producing a dye represented by the following is, as shown in JP-A-62-275163 and JP-A-63-30563, methanol, butanol,
Alcohol solvent such as ethylene glycol, benzene,
In an aromatic aprotic solvent such as chlorobenzene or nitrobenzene, or an amide solvent at a temperature of 50 to 200 ° C., the following formula (I) [In the formula (I), Y ¹ , Y ² , Y ³ , Y ⁴ , and Y ⁵ are the formulas
It has the same meaning as Y ¹ , Y ² , Y ³ , Y ⁴ and Y ^{5 in} (IV). A quinophthalone-dicarboxylic acid anhydride represented by the following formula (I
I) R-NH ₂ (II) [In the formula (II), R represents the same meaning as R in the formula (IV). ] The method of reacting the amine shown by is taken. However, the quinophthalone-dicarboxylic acid anhydride as a raw material is insoluble in the above-mentioned solvent, and the reaction activity is low in the above-mentioned solvent, a large amount of unreacted substances remain, or a large amount of by-products are generated when a high temperature reaction is carried out. There was a drawback.

[Means for Solving the Problems]

The present inventors, as a result of earnest study, the following formula (III) [In the formula (III), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom, an alkyl group or a halogen atom. ] In the presence or absence of quinoline, isoquinoline, pyridine, monoalkylpyridine, dialkylpyridine, or trialkylpyridine with a phenol represented by the formula as a solvent and a quinophthalone-dicarboxylic anhydride of the formula (I) The present invention has been accomplished by finding that a quinophthalone dye of formula (IV) can be obtained in a high yield by reacting an amine of II).

In the formula (I), examples of the substituents represented by Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ include H; -CH ₃ , -C ₂ H ₅ ,-(CH ₂ ) ₂ C.
_{H 3, -CH (CH 3)} 2, - (CH 2) 3 CH 3, -CH 2 CH (CH 3) 2, -CH (CH 3) C
₂ H ₅ ,-(CH ₂ ) ₄ CH ₃ ,-(CH ₂ ) ₅ CH ₃ ,-(CH ₂ ) ₆ CH ₃ ,-(CH ₂ ) ₇ CH
Alkyl group having ₃ or the _{like; -OCH 3, -OC 2 H 5} , -O (CH 2) 2 CH 3, -O (CH
₂ ) ₃ CH ₃ , alkoxy groups such as -O (CH ₂ ) ₄ CH ₃ ; Cl, Br, I,
_{F, -NHCH 3, -NHC 2 H} 5, -N (CH 3) 2, etc. -N (C ₂ H _{5) 2} and the like.

Examples of the substituted or unsubstituted alkylamine represented by the formula (II) include methylamine, ethylamine, propylamine, butylamine, octylamine, γ-methoxyamine, ethoxyethoxyethylamine, β-chloroamine, β-methoxycarbonylethylamine. , N, N-dimethylamine ethylamine and the like, and examples of the substituted or unsubstituted cycloalkylamine include cyclohexylamine, 4-tert-butylcyclohexylamine, 4
-Trans-amylcyclohexylamine, cyclopentylamine and the like, and examples of the substituted or unsubstituted arylamine include aniline, toluidine, ethylaniline, methoxycarbonylaniline, nitroaniline,
p-nonylaniline, cetylaminocarbonylaniline, benzidine, benzoxazoylaniline, aminoazobenzene, benzothiazolylaniline, tolidine,
Aniline derivatives such as N, N-diethylaminoaniline, octyloxycarbonylphenylaniline, benzoxazoylbiphenylamine and biphenylamine, condensed polycyclic amines such as naphthylamine, alkylnaphthylamine, aminoanthraquinone and aminoanthracene, and heterocyclic rings. Examples of amines include thiophene amine, benzothiazole amine, nitrothiazole amine, benzoxazole amine, pyridine amine, methyl pyridine amine and the like.

Examples of the phenol derivative represented by the formula (III) include phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol and m.
-Cresol, p-cresol, ethylphenol, butylphenol and the like.

The reaction conditions are as follows: 1 mol of the quinophthalone-dicarboxylic acid anhydride represented by the general formula (I) is used and 0.7 of amines is used.
The amount of the phenol derivative used as a solvent is preferably from 5 to 2000 mol, and when quinoline, isoquinoline, pyridine and their derivatives are used as a catalyst, it is preferably from 0.005 to 5 mol.

The reaction temperature is preferably 50 to 200 ° C., and the reaction time is preferably 1 to 30 hours.

When quinoline, isoquinoline and pyridines are used as the catalyst, intermolecular imidization is suppressed and a higher purity compound (IV) can be obtained. The effect is particularly remarkable in the case of imides of arylamines and heterocyclic amine derivatives.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to examples.

Example 1 359 g of an acid anhydride represented by the following formula, A mixture of 143 g of 2-aminonaphthalene, 130 g of isoquinoline and 15 of metacresol 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 is I
The following compounds were identified by R and NMR, and were found to be 95% pure by liquid chromatography.

Example 2 438 g of an acid anhydride represented by the following formula, 167 g of p-phenylaniline, 100 g of quinoline and o-
The mixture of chlorophenol 15 was heated and stirred at 200 ° C. for 6 hours. The reaction solution was cooled to room temperature and the precipitated crystals were filtered,
It was washed with methanol and dried. Yield 450g. This crystal was a compound of the following formula and had a purity of 96%.

Examples 3 to 15 The compounds of X and R shown in Table 1 were synthesized according to the following general formula. The results are shown in Table 1.

Claims (1)

[Claims] 1. The following formula (I) [In the formula (I), Y ¹ , Y ² , Y ³ , Y ⁴ , and Y ⁵ each independently represent a hydrogen atom, an alkyl group, an amino group, an alkylamino group, a hydroxyl group, an alkoxy group, or a halogen atom. A quinophthalone-dicarboxylic acid anhydride represented by the following formula (I
I) R-NH ₂ (II) [In the formula (II), R represents a substituted or unsubstituted alkyl group, a cyclic alkyl group, an aryl group or a heterocycle. ] The amines represented by the following formula (III) [In the formula (III), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom, an alkyl group or a halogen atom. ] In the phenol derivative represented by, quinoline, isoquinoline, pyridine, monoalkyl pyridine, dialkyl pyridine, or in the absence of the presence of trialkyl pyridine, the following formula (IV) characterized by heating reaction In [Formula ^{(IV), Y 1, Y} 2, Y 3, Y 4 and ^{Y 5} means ^{Y 1, Y 2, Y 3} , Y 4 and ^{Y 5} the same group of the formula (I), R Represents the same meaning as R in formula (II). ] The manufacturing method of the quinophthalone dye shown by these.