JPS61291653A - Production of dyestuff of anthraquinonedicarboximide - Google Patents

Abstract

PURPOSE:To obtain industrially advantageously the titled compound useful as pigment, etc., by carrying out a two-stage reaction in one reactor, by condensing successively an aromatic dicarboxylic acid with an aromatic diamine and an anthraquinone dicarboxylic acid anhydride. CONSTITUTION:Firstly, in a polar aprotic solvent, an aromatic dicarboxylic acid (anhydride) shown by the formula I (Y is benzene, naphthalene, etc. which may be replaced) such as phthalic acid, etc., is reacted with 1-1.3 mol aromatic diamine shown by the formula II (R1 and R2 are H, halogen, etc.; n is 1-3 integer) such as p-phenylene-diamine, etc. Then, the prepared condensation reaction mixture is condensed with a compound shown by the formula III (X1-X6 are H, OH, amino whichmay be replaced with 1-3C alkyl, etc., with the proviso that at least one of X1-X3 and X6 is OH or amino which may be replaced with 1-3C alkyl) such as anthraquinone-2, 3-dicarboxylic acid anhydride, etc., to give the aimed compound shown by the formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing anthraquinone dicarboximide dyes. More specifically, in the general formula C, which is characterized in that an aromatic dicarboxylic acid is condensed with an aromatic amine in a polar aprotic solvent and then reacted with anthraquinone dicarboxylic anhydride, Xl, uniform, for, A, and n are the same as above. ) relates to a method for producing a pigment represented by

The anthraquinone dicarboximide dye obtained by the method of the present invention is suitable as a colorant for hydrophobic polymers such as polyester and polyamide, and as a dye for polarizing films.

That is, this known method uses 1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride in a solvent such as methanol or benzene.

This is a method for producing a 1,4-diaminoanthraquinone 2,3-dicarboximide compound by reacting it with a primary amine.

An invention is about to be made. The purpose of the present inventors is to provide a dye represented by the general formula (Iv) synthesized by combining various unit reactions, which is extremely suitable for use as a pigment or for use in a polarizing film based on a hydrophobic polymer. I discovered something.

The object of the present invention is to provide a method for industrially producing this dye.

Means for Solving the Problems In order to solve the above problems, the present inventors used an aromatic dicarboxylic acid as a starting material and reacted it with an aromatic diamine and anthraquinone dicarboxylic acid anhydride to obtain a compound of the general formula (I).
After intensive study on the method for producing the dye represented by V), the present inventors completed the method of the present invention in which two steps are carried out in one reaction vessel.

Namely, the method of the present invention comprises aromatic dicarboxylic acids represented by the general formula (I) (wherein Y represents a benzene, naphthalene or anthraquinone ring, which may have a substituent), or an anhydride thereof; , with respect to the general formula (wherein R1 and R each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, or a lower alkyl group, and n is 1 to 1,3 molar ratio to this)
It is an integer of ~3. ) is condensed in a polar aprotic solvent, and then the condensation reaction mixture is added to the general formula (m) (wherein, Xl, human, human, X4, and X6 are hydrogen atoms, halogen atoms , is an amine group which may be substituted with a hydroxy group or an alkyl group having 1 to 3 carbon atoms, and among these, at least one of XI, X2. A compound represented by the general formula (1), which is an amino group which may be substituted with an alkyl group, is added and heated to cause a condensation reaction. ., Y, R1 (I R2 and n are the same as above).

The aromatic dicarboxylic acid used in the method of the present invention is represented by the general formula (I), and includes, for example, phthalic acid,
Trimellitic acid, pyromellitic acid, 3-methylphthalic acid, 4-methylphthalic acid, 4-methoxycarbonylphthalic acid, 3-chlorophthalic acid.

3.4.5.6-Tetrachlorophthalic acid, 3.4.5.
Orthophenylenedicarboxylic acids such as 6-titrapromphthalic acid, 3,5.6-dolychloro-4-methylphthalic acid, and 3-nitrophthalic acid, or their anhydrides, naphthalene-2,3-dicarboxylic acid, 6-methyl-naphthalene -2,3-dicarboxylic acid, 6,7-dimethyl-naphthalene-2,3-dicarboxylic acid, 5-chloro-naphthalene-2,3-dicarboxylic acid, and other naphthalene-ortho-dicarboxylic acids or anhydrides thereof; Naphthalene-1,8-dicarboxylic acid, 4-chloro-naphthalene-
1,8-dicarboxylic acid.

4-Methyl-naphthalene-1,8-dicarboxylic acid, 4-
Naphthalene-berry dicarboxylic acids such as nitro-naphthalene-1,8-dicarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, or anhydrides thereof, anthraquinone-2,3-dicarboxylic M, 1.4-diamino-anthraquinone-2,3-dicarboxylic acid, 1-
Amino-4-hydroxy-anthraquinone-2,3-dicarboxylic acid, 6-methyl-anthraquinone-2,3-dicarboxylic acid, 5j8-dimethyl-anthraquinone-2,
3-dicarboxylic acid, 5.8-diamino-anthraquinone-2,3-dicarboxylic acid, 1, 4.5.8-tetraamino-anthraquinone-2,3-dicarboxylic acid, 5,8-
Di(N-methylamino)-anthraquinone-2,3-dicarboxylic acid, 5.6,7.8-thousandthrachloro-anthraquinone-2,3-dicarboxylic acid, 1,4-dihydroxy-anthraquinone-2,3 -dicarboxylic acid, 1.4,5
．． Anthraquinone-2,3-dicarboxylic acids such as 8-tetrahydroxy-anthraquinone-2,3-dicarboxylic acid, 5,6.8-trichloro-7-methyl-anthraquinone-2,3-dicarboxylic acid, or the like; Examples include anhydrous substances.

Further, the aromatic diamine used in the method of the present invention is a compound represented by the general formula (n), and typically includes paraphenylenediamine, 2-chloro-1,4-diaminobenzene, 2-methyl -1,4-diaminobenzene, 2-methyl-5-methoxy-1,4-diaminobenzene, 2-nitro-1,4-diaminobenzene, and other phenylene diamines, benzidine, ortho-tolidine, ortho-anisidine , 0-dichlorbenzidine, meta-tolidine, 6,6'-dichloro-3,3'-dianisidine, etc., i, 4'1-diamino-p-terphenyl, 275'-dimethyl-4 ,4#
-diamino-p-terphenyl, 2'15'-dichloro-4,4''-diamino-p-terphenyl, etc.
Examples include terphenyldiamines.

Further, anthraquinone dicarboxylic acid anhydride represented by the general formula G[[] is specifically anthraquinone-2,3-
dicarboxylic anhydride, 1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride, 1-amino-4-hydroxyanthraquinone-2,3-dicarboxylic anhydride,
l-amino-4-hydroxy-6-promanthraquinone-2,3-dicarboxylic anhydride, 1,4-dihydroxyanthraquinone-2,3-dicarboxylic anhydride, 1,
4-dimethylaminoanthraquinone-2,3-dicarboxylic anhydride, 1-aminoanthraquinone-2,3-dicarboxylic anhydride, 1-amino-4-bromoanthraquinone-2,3-dicarboxylic anhydride, 5, 8-diaminoanthraquinone-2,3-dicarboxylic anhydride, 5,8
-dimethylaminoanthraquinone-2,3-dicarboxylic acid anhydride, 5,8-dipropylaminoanthraquinone-
2,3-dicarboxylic anhydride, 1,4,5.8-tetraaminoanthraquinone-2,3-dicarboxylic anhydride,
Examples include 1,5-diamino-4,8-dihydroxyanthraquinone dicarboxylic anhydride, 1,5-diamino-4,8-dihydroxy-7-bromanthraquinone dicarboxylic anhydride, and the like.

When using these acid anhydrides as raw materials, it is preferable to use recrystallized products from various solvents, particularly those recrystallized from the same solvent as used in the reaction.

The method of the present invention includes the first step of condensing the aromatic dicarboxylic acid represented by the general formula (I) with p-phenylenediamine, and the condensation reaction product and the general formula I.
It consists of a second stage reaction of reacting with acitraquinonedicarboxylic acid represented by (III).

In the first-stage reaction, the amounts of aromatic dicarboxylic acid and para-phenylene diamine to be used are in the range of 1 to 1,3 molar ratio of para-phenylene diamine to aromatic dicarboxylic acid. If the amount of paraphenylenediamine used is too small, the amount of by-products will increase, which is undesirable, and usually a small excess of the equivalent molar amount is used.

This reaction is carried out in a polar aprotic solvent. As the polar aprotic solvent, those whose boiling point is usually within the range of the reaction temperature are preferably used for the reaction operation.

Specifically, such solvents include pyridine, N, N-
Dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, N-methylpyrrolidone, N
, N-dimethylacetamide, N-methylacetamide, sulfolane, N,N-tramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like. These solvents are usually used in an amount of 3 to 50 times, preferably 5 to 20 times, the amount of the raw material.

The reaction temperature is 80=28.0℃, preferably 150-20℃
The dehydration reaction is carried out at a temperature in the range of 0°C, usually around the boiling point of the solvent, and the water produced in the reaction is removed by azeotropy with the solvent to complete the dehydration reaction, followed by cooling if necessary.

Then, the anthraquinonedicarboxylic anhydride represented by the general formula (In) is added to this condensation reaction mixture to carry out the subsequent reaction.

The amount of anthraquinone dicarboxylic anhydride to be used is usually 1 to 1.2 mol based on the aromatic dicarboxylic acid. In this latter reaction, a reaction solvent may be added if necessary.

The reaction temperature ranges from 80 to 280°C, preferably 150°C.
~200°C.

The water produced by the reaction is removed by azeotropy with the solvent to complete the reaction. In this reaction, the desired reaction product is precipitated out of the system, so after the reaction is completed, the product is obtained by heat-filtering.

The product obtained as described above is further purified by a method such as recrystallization and used as a dye for polarizing film.

In the present invention, two-stage reactions can be performed in one reaction vessel to produce pigments represented by the general formula QV) and anthraquinone dicarboximide dyes useful for polarizing films. .

That is, the method of the present invention provides an industrial method for producing a novel dye useful for pigments and polarizing films, and is therefore of great value.

Example The present invention will be illustrated below with examples.

Example-1 Phthalic acid (74.0 IC0,446 mol) was added to 58.4 g of N,N-dimethylformamide, and then paraphenylenediamine 62.8.9 (0,582 mol) was added to 10
and heated to 150°C. At this temperature, reaction product water was removed azeotropically with N,N-dimethylformamide. 5
After a period of time, the temperature of the reaction system was raised to 155°C, and the condensation reaction was completed.

Next, the reaction mixture was cooled to room temperature, and 1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride 1
00, li' (as 100%) was added, warmed and filtered hot. The mixture was washed three times with 100 J of N,N-dimethylformamide at 100°C, then washed with methanol, and dried to obtain 128.55 g of a dye represented by the linear formula.

In order to obtain even higher purity products, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2
- and lolidone in 25 times the amount of the crude product and 150 to 200
After sludge at ℃.

It is heated at 100 to 140°C, washed with methanol, and then dried.

When treated with N,N-dimethylformamide, the yield was 109.3° and the yield was 85°.

Example-2 Naphthalene-2,3-dicarboxylic acid 96.4&(0,4
46 mol) to N,N-dimethylformamide 584! j
In addition to paraphenylene diamine 62.89 (
0.5 turbidity (2 mol) was added and heated to 150°C. At this temperature, the water produced by the reaction was removed azeotropically with N.N-dimethylformamide.

After 5 hours, the temperature of the reaction system was raised to 155°C, and the condensation reaction was completed. The reaction mixture was then cooled to room temperature and added with 100 J of 1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride (asdry).

0.325 mol) and heated to 150°C under reflux for 10
Allowed time to react. The reaction mixture in which the target product has been precipitated is
The temperature was lowered to 00°C and filtered hot.

Washed three times with N,N-dimethylformamide at 100° C., iooog, then with methanol and dried.

A dye 131N represented by the following formula was obtained. Further, purification treatment was performed in the same manner as in Example-1, yielding 105.9. Example-3 Anthraquinone 2,3-dicarboxylic acid 132.0g (0
,,446 mol) to N-methyl-2-pyrrolidone 584
g, and then paraphenylenediamine 62.8.
9 (0,582 mol) and heated to 150°C. At this temperature, the water produced by the reaction was distilled out of the system.

After 5 hours, the temperature of the reaction system was raised to 155°C, and the condensation reaction was completed. The reaction mixture was then cooled to room temperature and added with 1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride 91.6, li' (as dry).

0.298 mol) and heated under reflux at 150°C for 10
Allowed time to react.

Washed three times with methyl-2-pyrrolidone, then methanol and dried.

Dye 127.2.9 represented by the following formula was obtained. Purification treatment was performed in the same manner as in Example-1 to obtain purified product 108. IJi', yield was 85.

Example-4 Naphthalene-2,3-dicarboxylic acid 96.4# (Q,
446 mol) of N,N-dimethylformamide 584I
In addition to that, paraphenylenediamine was 62.8!
i (0,582 mol) and heated to 150°C. At this temperature, reaction product water was removed azeotropically with N,N-dimethylformamide.

After 5 hours, the temperature of the reaction system was raised to 155°C, and the condensation reaction was completed. The reaction mixture was then cooled to room temperature, and 1-amino-4-hydroxyanthraquinone-2,
3-dicarboxylic anhydride 100.4.9 (0,325
1 mole) was heated under reflux at 150°C in m×1 liter.
The reaction was allowed to proceed for 0 hours. The reaction mixture in which the target product had precipitated was cooled to 100°C and filtered hot.

Washed three times with 1009 N,N-dimethylformamide at 100°C, then with methanol and dried.

The following formula A dye 130.4.9 represented by was obtained.

Further, purification treatment was performed using the method of Example-1, yielding 1111
4.8.9 was obtained. The yield was 88%.

Example-5 Naphthalene-2,3-dicarboxylic acid 96.4g (0,4
46 mol) was added to 5841 N,N-dimethylformamide, then 62.29 (0
, 582 mol) and heated to 150°C. At this temperature, reaction product water was removed azeotropically with N,N-dimethylformamide.

After 5 hours, the temperature of the reaction system was raised to 155°C, and the condensation reaction was completed. Next, the reaction mixture was cooled to room temperature, and 109.9.9 (0,325 mol) of 1.4.5.8-tetraamino-2,3-dicarboxylic anhydride was added thereto.
The mixture was heated to 50° C. and reacted for 10 hours under reflux. The reaction mixture in which the target product had precipitated was cooled to 100°C and filtered hot. 100'C was washed three times with 1100 g of N,N-dimethylformamide and dried to obtain dye 123.6.9 represented by the following formula.

Further, purification treatment was performed by the method of Example-1, yielding 1i8
6.5g was obtained. The yield was 70% Example-6 Phthalic acid 74.0.9 (0,446 mol) was mixed with N, N-
In addition to 584 g of dimethylformamide, 62.81 (0,582 mol) of para-phenylenediamine was then added and heated to 150°C. At this temperature, the water produced by the reaction is
- After 55 hours of azeotropic removal with dimethylformamide, the temperature of the reaction system was raised to 155°C, and the condensation reaction was completed.

Next, the reaction mixture was cooled to room temperature, 100.8.9 (0,325 mol) of 1,4-dihydroxyanthraquinone-2,3-dicarboxylic anhydride was added thereto, and the mixture was heated to 150°C.
The mixture was reacted under heating under reflux for 10 hours.

The reaction mixture in which the target product had precipitated was cooled down to ioo'c and heated.

It was washed three times with 100 J of N,N-dimethylformamide at 100°C, then washed with methanol and dried.

The following formula A dye 120.311 represented by was obtained.

Further purification was performed using the recipe of Example-1, and the obtained yield was 96.2
1 yield was 80%.

Patent source Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Y represents a benzene, naphthalene or anthraquinone ring which may have a substituent.) Aromatic dicarboxylic acids or their anhydrides represented by general formula (II) with a molar ratio of 1 to 1.3 ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) (In the formula, R_1 and R_2 are (each independently represents a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, or a lower alkyl group, and n is an integer of 1 to 3) are reacted in a polar aprotic solvent. Then, the condensation reaction mixture has the general formula (III) ▲Mathematical formula, chemical formula, table, etc.▼(III) (wherein, X_1, X_2, X_3, X_4, X_5 and X_6 are hydrogen atoms, halogen atoms, hydroxy groups or It is an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, and at least one of X_1, X_2, X_3 and X_6 is a hydroxy group or an alkyl group having 1 to 3 carbon atoms.
It is an amino group which may be substituted with ~3 alkyl groups. General formula (IV) characterized by adding a compound represented by ) and causing a condensation reaction ▲ There are mathematical formulas, chemical formulas, tables, etc. and Y, R_1, R_2 and n are the same as above.) A method for producing an anthraquinone dicarboximide dye.