JPS6241267A - Anthracene derivative - Google Patents

Abstract

PURPOSE:To provide an anthracene derivative of a specified structural formula, which can be isolated as a leuko compd. and can be oxidized in a bath without using any special oxidizing agent to thereby well develop a color and dye fibers. CONSTITUTION:An anthracene derivative represented by the formula can be obtd. by reducing 1-anilino-4-hydroxyanthraquinone with a reducing agent such as sodium dithionate in the presence of an alkali such as potassium hydroxide, sodium hydroxide or sodium carbonate in water, an alcohol or a mixture of water and an alcohol, or in the presence of zinc in an aq. hydrochloric soln. When 0.1-2.0wt% ammonia, benzyl alcohol or a mixture of ammonia and benzyl alcohol is present in a bath in dyeing fibers with said anthracene derivative, the fibers can be well dyed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to novel anthracene derivatives that are valuable as dyes and pigments or intermediates thereof.

[Prior art] Conventional vat dyes for textiles are made by converting the dye into leuco bodies using a reducing agent in a bath, and while the fibers are immersed in the bath, the leuco bodies are oxidized in the air to develop color and are adsorbed onto the fibers. It is the type of thing that makes you

For example, indigo, a typical vat dye, has the following formula (
If), the fibers are immersed in a solution containing indigo, an alkali, and a reducing agent for dyeing. Under the above conditions, indigo becomes a leuco substance of the following formula (III), and it is thought that this substance undergoes air oxidation, develops color, and at the same time dyes fibers.

In addition, there are other vat dyes such as indasthrene dyes and anthraquinone dyes, which are also thought to be dyed by a similar mechanism.

(The following is a blank space) 0 H [Problems to be solved by the invention] However, these leuco bodies are extremely unstable and are immediately oxidized when exposed to air, so a large amount of reducing agent must be added to the bath. They must coexist, creating harsh conditions for the fibers. Furthermore, since the reduction was carried out under alkaline conditions, it caused even more damage to the fibers.

He1indon developed by Ca5sella
YellowR is a naphthoquinone dye with a fused Carbazole ring, and is a yellow vat dye for wool.
It is well known that it was not commercially available because it required a strong alkaline bath for reduction.

On the other hand, the sulfate ester of the leuco form of indigo is too stable and cannot be colored without using a strong oxidizing agent, such as potassium permanganate, which is also not a good condition for fibers. do not have.

In view of the above-mentioned circumstances, the present inventor has conducted intensive research to find out whether it is possible to obtain a leuco compound that has appropriate stability, that is, can be isolated as a leuco compound, and which develops a strong color when oxidized under mild conditions. I was able to complete it.

[Means for Solving the Problems] That is, the present invention is an anthracene derivative represented by the following general formula (1).

(Leaving space below) Q NHPh The above anthracene derivative is produced by converting 1-anilino-4-hydroxyanthraquinone into water, alcohol, or water using a reducing agent such as sodium dithionate in the presence of an alkali such as potassium hydroxide, sodium hydroxide, or sodium carbonate. - Obtained by reduction in an alcohol mixed solution or an aqueous hydrochloric acid solution in the presence of zinc. Suitable reaction conditions are anaerobic reaction at room temperature to reflux temperature for 1 to 7 hours.

When dyeing with the anthracene derivative of the present invention, 0.1 to 2.0% by weight of ammonia is allowed to coexist in the bath, or benzyl alcohol or an ammonia-benzyl alcohol mixture of the same amount is allowed to coexist in the bath. , moreover, the fibers are well dyed.

[Effect of the invention] As described above, the anthracene derivative of the present invention can be prepared under anaerobic conditions.
It can be isolated as a leuco form from the reaction system, coexist stably, and can be oxidized in a bath without using a special oxidizing agent to develop good color and dye fibers.

With conventional vat dyes, sufficient dyeing could not be expected unless the concentration was 5% or higher, but the anthracene derivative of the present invention has a concentration of 0.5% or higher.
Demonstrates practical dyeing power from concentrations of around 1%.

The anthracene derivative of the present invention can be used not only as a dye for textiles but also as a hair dye for hair.
When used as a hair dye, it is particularly preferable to use it under mild conditions.

[Synthesis Example] Hereinafter, the present invention will be explained in more detail by giving examples of the synthesis of the anthracene derivative of the present invention.

1-anilino-4-hydroxyanthraquinone 0.91
8 g was dispersed in 50 mg of water together with 0.912 g of sodium carbonate and 2.010 g of sodium dithionate, and the mixture was stirred at 80° C. for 6 hours under an argon atmosphere. After the reaction was completed, it was filtered and the crystals were thoroughly washed with degassed water. All these operations were performed under an argon atmosphere. The crystals were dried under reduced pressure to obtain 668.5 mg of yellowish brown crystals, which were further recrystallized from ethanol under an argon atmosphere.

There are several possible tautomers of this compound, but as seen in the 'H-NMR data below, there is one hydroxy proton, four methylene protons, and the corresponding chemical shifts of the carbonyl group in CNMR. Since it is observed on the lower magnetic field side than that of quinones, it is thought that a methyl group or methylene group exists adjacent to the carbonyl group, and 1-anilino-10-hydroxy-2,3
-dihydroanthracene-4,9-dione.

Elemental analysis value C75,81 (calculated value 75.70)H
4,62 (calculated value 4.76) N 4.16 (calculated value 4.41) T L
C(Si02, Cs Hs) RfO,58λm
ax (E t OH) 461 nm, 4
35nm nuclear magnetic resonance spectrum (CDC13, δ, pp
m)'H-NMR8,32(2,H% aroma
, , m), 7.59 (2H, arom, , m)
, 7.16 (5H, NHPh.

m), 13.78 (IH, OH, S), 2
．． 89 (4H1(CH2) 2-1m) 13C-NMR carbonyl group, 20
0.6.165.4 [Example 2 Next, an example of staining using the anthracene derivative of the present invention will be shown.

Example 1 1-anilino-10-hydroxy-2,3 obtained in the synthesis example
-dihydroanthracene-4,9-dione 20 mg,
100 mg of each was dissolved in 20 g of water, and wool muslin test fibers manufactured by Shirosensha Co., Ltd. were added to the solution in a bath ratio of 1/1.
40° C. and shaking dyeing at a temperature of 30° C. or 40° C. for 45 minutes, in each case a bright purple wool muslin was obtained. At this time, ammonia, benzyl alcohol, and ammonia benzyl alcohol mixed solution were added to 0.
When 1% to 2.0% by weight of these coexist, dyeing can be carried out even better.

Example 2 According to Example 1, 1.0 g of gray hair purchased from Abeille Co., Ltd. was immersed in the solution and heated at 3°C for 4 hours.
Mock staining was carried out for 5 minutes. Thereafter, the dyed hair was washed with 200° C. of water for 5 minutes at 30° C. to obtain hair with no gray hair at all.

The obtained dyed hair was washed using a commercially available shampoo,
Although it was further rinsed, no change in color tone was observed.

According to Example 1, test multi-fiber manufactured by Shirosensha Co., Ltd. (consisting of 17 types of fibers. Acetate is beige,
(others were white) to obtain bright purple dyed fibers depending on the presence or absence and amount of ammonia, benzyl alcohol, and ammonia-benzyl alcohol mixed solution.

Claims (1)

[Claims] (1) Anthracene derivative represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I)