JPS60179462A - Production of vat dye - Google Patents

Abstract

PURPOSE:To obtain a vat dye of good quality in a high yield, by chlorinating a specified condensation product obtd. by a reaction in the presence of 1,3-dimethyl-2-imidazolidinone. CONSTITUTION:0.1-10pts.wt. alkaline condensing agent such as KOH and optionally a wetting agent such as an alkali metal naphthalenesulfonate are added to one pt. 1-aminoanthraquinone in the form of a powder or a slurry while introducing an oxidizing agent such as air. A condensation reaction is conducted in the presence of 0.1-10pts.wt. 1,3-dimethyl-2-imidazolidinone at 80-150 deg.C to obtain a condensation reaction product. The product is slurried in water and reduced with hydrotalcite in the presence of an alkali metal hydroxide. The resulting crystal is recovered by filtration and slurried in water. The resulting dianthraquinone-N,N-dihydroamine or the above product is chlorinated in sulfuric acid. The product is recovered by filtration and the filter cake is completely dissolved in 98% sulfuric acid and reduced with Al powder to obtain a vat dye of the formula, wherein n is 1, 2.

Description

DETAILED DESCRIPTION OF THE INVENTION The method of the present invention is to convert the -aminoanthraquinone into 1.3-/
The reaction product obtained by condensation of methyl-2-imidazoli/non and the action of an alkaline condensing agent in the presence of an oxidizing agent is subjected to a post-treatment step to form a conventional indanthrone dye, and the resulting 7-anthraquinone -N.

It is characterized by chlorinating N-dihydroazine (hereinafter abbreviated as indanthrone) or directly chlorinating the condensation reaction product in a sulfuric acid solvent, and then removing impurities by adjusting the sulfuric acid concentration. The vat dye of formula (1), which relates to an industrially advantageous manufacturing method of the vat dye represented by formula (I) [in formula (1), n is 1 or 2] or a mixture thereof, is listed in the color index. of 0.1. Bat Blue 6 or 0.1. It is an important dye known from ancient times as Bat Blue 14. Various methods are known for producing these dyes, including a method in which the bromine atom of an indanthrone bromide is replaced with a chlorine atom;
Although there are methods of condensing chlorinated aminoanthraquinones such as , 3-dichloro-2-aminoanthraquinone, etc., a method of chlorinating indanthrone is widely used industrially.

For example, chlorination of indanthrone in an inert organic solvent such as nitrobenzene (e.g., U.S. Pat. No. 2.205
．． 418), or the method of adding a small amount of manganese dioxide in sulfuric acid and then chlorinating it with chlorine (for example, Yutaka Hosoda, Theoretical Manufacturing Dye Chemistry, p. 699). In all of these chlorination methods, indanthrone isolated at a purity high enough to be used as C,L Vat Blue 4 is usually used as a raw material.

For example, when l-aminoanthraquinone is used as a starting material, it is condensed by the action of an alkaline condensing agent in the presence of a solvent such as dimethyl sulfoxide and an oxidizing agent, and the resulting condensation reaction product is converted into an indanthrone dye. Therefore, it is used after being subjected to the usual post-treatment processes such as reduction purification and air oxidation to achieve high purity.

A method (Japanese Unexamined Patent Publication No. 8455/1983) for obtaining the vat dye of formula (1) by directly chlorinating the condensation reaction product in a sulfuric acid solvent without subjecting it to such a post-treatment step is also known. However, in this method, large i and H impurities are mixed in the dye, so the amount and concentration of sulfuric acid in the purification process must be adjusted in order to obtain the vat dye shown in formula ([) with good quality. Satisfactory yields are not achieved due to the range.

-1, On the other hand, the industrially practiced method for producing indanthrone includes a method in which 2-aminoanthraquinone is condensed into a 17J ring by the action of an alkaline condensing agent, but recently, -aminoanthraquinone is used as the starting material. The method is notable for its ability to obtain indanthrone in high yield, using 1-aminoanthraquinone as a raw material in conjunction with a solvent such as phenol, hexamethylphosphorotriamide or dimethyl sulfoxide at elevated temperatures.
A method of condensation and ring closure by the action of an alkaline condensing agent is known.

However, even in this method, a considerable amount of by-products such as hydroxyanthraquinone are produced, so a satisfactory yield cannot be achieved as in the case of using 2-aminoanthraquinone as a raw material. However, the quality was not sufficient.

The present inventors conducted extensive studies on a method for producing indanthrone by carrying out a condensation reaction of 1-aminoanthraquinone with an alkaline condensing agent in the presence of an oxidizing agent. We discovered that inodantron of very high quality can be obtained in high yields by applying this method.

After that, as a result of further investigation, the condensation reaction product obtained in the presence of 1,3-dimethyl-2-imidazolidinone,
When indanthrone isolated through a normal post-treatment step is chlorinated as a raw material, high yield and high quality formula (I) can be obtained.
It has been found that a dye shown in the formula can be obtained.

Furthermore, the condensation reaction product with the formula (1 ) compound for vat dyeing, it was found that good dyed products with no inferiority could be obtained.
This invention has been achieved.

In the condensation reaction step of the method of the present invention, the 1,3-
0.1 to 10 parts by weight, preferably 0.1 to 4.5 parts by weight per 1 part by weight of dimethyl-2-imidazolidinone traquinone
M parts are used, more preferably 1.0 to 3.0 parts by weight.

In the method of the present invention, such a small amount is sufficient, but if the ratio is less than 0.1 parts by weight, sufficient effects cannot be obtained. At that time, it may also be used in combination with other organic solvents, such as pyridine, toluene, xylene, nitrobenzene, etc.

The alkaline condensing agent used in the shredding is an alkali metal hydroxide, such as potassium hydroxide or sodium hydroxide, with potassium hydroxide being the most suitable. They are used in the form of solids or aqueous solutions, and the amount of alkaline condensing agent used is 0.1 to 10 parts by weight of 1-aminoanthraquinone as potassium hydroxide.
Parts by weight, particularly 0.2 to 2.5 parts by weight, are desirable.

During the reaction, air or oxygen, and an oxidizing agent such as persalt such as alkali metal perborate, nitrate, or chlorate are used to make the reaction proceed smoothly. Oxygen is easy to handle and is industrially advantageous.

In addition, alkali metal hydroxide-resistant wetting agents commonly used in the condensation reaction for indanthrone production, such as naphthalene- or alkylnaphthalene-alkali metal sulfonates or sulfated oleic acid amides, may be added to the reaction medium. You can also do it.

1-aminoanthraquinone may be used in the form of a powder, but it can also be used in the form of a wet mass or slurry by adjusting the amount of water used. Of course, when used as a slurry, part or all of the alkaline condensing agent may be added, or the slurry may be made into fine particles by adding the above-mentioned wetting agent or surfactant.

1.3-Dimethyl-2-imidazolidinone is alkaline and stable, so after the reaction is complete, it can be distilled at normal pressure or under reduced pressure, and it can also be recovered by solvent extraction. .

The condensation reaction temperature varies depending on the amount of 1,3-dimethyl-2-imidazolidinone and the solvent, but is generally between 80°C and 1°C.
A temperature of 50° C. is suitable; if the reaction temperature is high, the main reaction will be accelerated, but side reactions will also proceed, and the purity of the recovered 1-aminoanthraquinone will tend to decrease, while the opposite tendency is observed at low temperatures.

The condensation reaction product of l-aminoanthraquinone obtained in this way may be subjected to a post-treatment step according to a conventional method in order to lead to I/DANOTO/, or without chlorine in order to obtain the dye of formula (J). We will ask you about the conversion process.

When subjecting to the post-treatment process of the fluid leading to the indantron,
After slurrying the separated condensation reaction product with water,
Reduction treatment with hydrozulfite in the presence of an alkali metal hydroxide, such as sodium hydroxide, and the leuco derivative of anthraquinone-N,N'-7 humanroazine)
The IJium salt is crystallized, separated by filtration, and the block is slurried with water and air oxidized to obtain indanthrone. Next, by applying a conventional chlorination method, such as a known method for chlorinating indanthrone in a sulfuric acid solvent (for example, Yutaka Hosoda, Theoretical Manufacturing Dye Chemistry, p. 699), the dye of formula (1) is obtained. can get.

In addition, when directly subjecting to the chlorination step without performing a post-treatment step, the condensation reaction product is diluted with water or an organic solvent and then subjected to a separation operation such as filtration as described in JP-A-56-8455. The resulting mass, wet or dry, is dissolved in sulfuric acid of the order of 92% strength and heated to a temperature of about 50-55°C, analogous to the chlorination of the indanthrone, if necessary in the presence of manganese dioxide. Chlorinate at °C.

After the chlorination is complete, add water to dilute the chlorination reaction mass and adjust the sulfuric acid concentration to about 83%, then completely dissolve the F mass in 98% sulfuric acid near room temperature and reduce with aluminum powder, etc.
A dye of formula (1) can be obtained.

In the present invention, 1,3-dimethyl-2
- By using imidazolidinone as a reaction solvent, the condensation reaction product is improved. Therefore, not only the yield of the dye of formula (1) is improved, but also the impurity content in the condensation reaction product is extremely small. Even if the sulfuric acid is not subjected to a post-treatment purification step, there is no need to adjust the sulfuric acid concentration to a high concentration of 83% for separation as described in JP-A-56-8455 in the purification step after the completion of chlorination. By simply adjusting the sulfuric acid concentration to 80% or less, almost no impurity content remains in the precipitate, so a high separation yield can be maintained.

Example 1 1 in 1,3-dimethyl-2-imidazolidinone 2001
- Add aminoanthraquinone 1007 and heat to raise the temperature,
50% potassium hydroxide aqueous solution 977 was added dropwise over 3 hours while passing air at 300 ml/min at 100 to 105°C. 130-135℃ while distilling water from the reaction system
After reacting for 4 hours, the reaction mass was poured into water, and the resulting precipitate was separated using E. aminoanthraquinone) was obtained. This condensation reaction product was mixed with 98% sulfuric acid 76
After dissolving in water s4. The sulfuric acid concentration was adjusted to 91% and 5% by adding or, and then chlorine was added to about 13
02 was chlorinated for 17 hours. Add water below 50°C to make the sulfuric acid concentration about 80%, cool to 25°C and filter, dissolve the P mass in 98% sulfuric acid 4701, add aluminum powder 2.32% at 50°C and stir. After that, it is drained into water, filtered, washed with water, and dried to produce vat dye (11 of formula (1)
? 2 Ci, 1. equivalent to bat blue 6) lo4r
was gotten. (Chlorine content 13.6%, yield 104%/
1-Aminoanotraquinone) When a cotton fabric was dyed using this in accordance with a conventional vat dyeing method, a dyed fabric with a vivid blue color was obtained.

Comparative Example 1 1-aminoanthraquinone 1007 was added to dimethyl sulfoxide 7-1801, the temperature was raised, and 50% potassium hydroxide aqueous solution 97fi+ was added dropwise over 3 hours while passing air at 300 ml/min from 100 to 105°C. After reacting at 115-120'C for 3 hours while distilling water from the reaction system, a condensation reaction product 91. ．． 7
ii' (yield 91.7%/l-aminoanthraquinone)
I got it. This condensation reaction product was subjected to chlorination, filtration at a sulfuric acid concentration of about 80%, and post-treatment under the same reaction conditions as in Example 1 to obtain a vat dye (corresponding to n = 20.L Vat Blue 6 in formula (1)). ) 86y was obtained. (Chlorine content 13.7
%, yield 86%/1-aminoanthraquinone) This vat dye 11 had a low yield compared to the (4) Garuda dye in Example, and the obtained dyed cloth had a greenish dark color. .

Example 2 1.3-dimethyl-2-imidazolidinone 235! i+
1-aminoanthraquinone】4572 was added to 95
The mixture was heated to ~100°C, and 50% potassium hydroxide aqueous solution 1417 was added dropwise over 3 hours while passing air at a rate of 300 ml per minute.

After the completion of the dropwise addition, a portion of the water was distilled off at 125 to 130° C. over 7 to 8 hours, and the reaction was then kept at a temperature of 1 hour to complete the reaction. The reaction solution was poured into 600 ml of water, and the resulting precipitate was washed door to door.

Warm water 4 in which sodium hydroxide 1537 was dissolved in the above lump F
Hydrosulfide 837 was added at 60°C and stirred for 20 minutes. After lowering the temperature to 50°C and crystallizing the IJium salt (leucoderivative of anthraquinone-N,N'-7) and passing it through at the same temperature, the block was heated with air by a known method. cyantraquinone-N,N'-dihydroazine 130
．． I got Off. The yield was 90% based on the 1-aminoanthraquinone used.

Next, cyanthraquinone-N, N'-7 humantroa 7-13
02 was dissolved in 1365 ml of 91.5% sulfuric acid, 6.57 ml of manganese dioxide was added, and chlorine was chlorinated with 1002 for 12 hours. The reaction mass was poured into 1677% 75% sulfuric acid, 145ml of water was added below 55°C, the mixture was allowed to stand, cooled to 25°C, filtered, and washed with 75% sulfuric acid. Dissolve the P lump in 96% sulfuric acid 3707 and 24% oleum 520g, add 3.0fi' of aluminum powder at 50℃, stir, drain into water, filter, wash with water, dry and vat dye. Dye (2〇) n-
20.1, equivalent to Hat Blue 6) 120 g was obtained. (Chlorine content 13.7%, yield 82.4% ゛/1-
(Aminoanotraquinone) The obtained dyed fabric was good as in the example.

patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 11-Aminoanthraquinone is converted to 1,3-dimethyl-2 using an oxidizing agent and an alkaline condensing agent at elevated temperatures.
Condensation reaction is carried out in the presence of -imidazolidinone, and the resulting condensation reaction product is subjected to a post-treatment step leading to a conventional indanthrone dye, and then chlorinated to form a compound of the formula (1).
) A method for producing vat dyes. [In formula (1), 11 is an integer of 1 to 2] 2 I-aminoanthraquinone is treated at elevated temperature with an oxidizing agent and an alkaline condensing agent in the presence of 3-dimethyl-2-imidacillinone, The condensation reaction product obtained by the condensation reaction is directly chlorinated in a sulfuric acid solvent without being subjected to a post-treatment step for ordinary indanthrone dyes to produce vat dyes represented by formula (1).