JPH0528747B2 - - Google Patents

Description

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

[Prior art] Conventional architectural dyes for textiles are produced by converting the dye into a leuco form using a reducing agent in a bath, and while the fiber is immersed in the bath, the leuco form is oxidized in the air to develop color and adsorbed onto the fiber. It is of type.

For example, indigo, which is a typical vat dye, has the structure of the following formula (), and for dyeing, fibers are immersed in a solution containing indigo, an alkali, and a reducing agent. Under the above conditions, indigo becomes a leuco substance of the following formula (), 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.

[Problems to be solved by the invention] However, these leuco bodies are extremely unstable and are immediately oxidized when exposed to air, so it is necessary to coexist a large amount of reducing agent in the bath. This is a harsh condition for fibers. Furthermore, since the reduction was carried out under alkaline conditions, this caused further damage to the fibers.

Helindon Yellow developed by Cassella
R is a naphthoquinone dye having a fused Carbadzle ring, and is a yellow vat dye for wool, but 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 circumstances, the present inventors have investigated whether it is possible to obtain a leuco form that has appropriate stability, that is, can be isolated as a leuco form, and that develops a strong color when oxidized under mild conditions.2- They discovered that the leuco form of alkylaminonaphthazarin derivatives is a compound that satisfies the above conditions, and filed a patent application (for example, Japanese Patent Application No. 79965/1983). However, in the case of alkylamino compounds, even if the number of carbon atoms in the alkyl group is changed to some extent, there is almost no change in their absorption spectra.As expected, there is a limit to the variety of color tones of dyed fibers. It was hot. Therefore, the present inventor conducted extensive research into the possibility of obtaining a leuco compound that satisfies the above-mentioned conditions and has a dark color tone that is difficult to obtain with an alkylamino compound, and as a result, the present invention was completed.

[Means for Solving the Problems] That is, the present invention is a naphthalene derivative represented by the following formula ().

(R represents a methyl group or a chloro group.) The above naphthalene derivative is a 2-substituted anilino-
5,8-dihydroxynaphthoquinone in the presence of stannous chloride using a reducing agent such as sodium dithionate, water, alcohol, water-alcohol mixed solution,
Alternatively, it can be obtained by reduction in an aqueous hydrochloric acid solution in the presence of zinc. Suitable reaction conditions are anaerobic reaction at room temperature to reflux temperature for 10 minutes to 3 hours.

When dyeing using the naphthalene derivative of the present invention, the fibers can be dyed better if 0.1 to 2.0% by weight of ammonia, benzyl alcohol, and ammonia-benzyl alcohol mixture are coexisting in the bath.

[Effect of the invention] As mentioned above, the naphthalene derivative of the present invention has the following properties:
It can be isolated as a leuco form from the reaction system under anaerobic conditions, and can be stored stably.Furthermore, it can be oxidized in a bath without using a special oxidizing agent to develop good color and dye fibers. can.

With conventional vat dyes, sufficient dyeing cannot normally be expected unless the concentration is 5% or higher, but the naphthalene derivative of the present invention exhibits a dyeing power sufficient for practical use at a concentration of about 0.1%.

The naphthalene derivative of the present invention can be used not only as a vat dye for textiles but also as a hair dye for human hair, and when used as a hair dye, it is particularly preferable to use it under mild conditions. recognized as.

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

Synthesis example 1 5,8-dihydroxynaphthoquinone (1 m
mol), boric acid (1 mmol) in ethanol (20 ml)
After dispersing and dissolving in and heating at reflux temperature for 5 minutes,
The mixture was slowly cooled to room temperature, p-toluidine (20 mmol) was added, and the mixture was stirred for 2 hours. After the reaction was completed, the reaction product was poured into a dilute aqueous hydrochloric acid solution, and the precipitate was filtered and dried under reduced pressure. The dried product was subjected to fractional purification by chromatography to isolate 238 mg (yield: 80.7%) of 2-toluidino-5,8-dihydroxynaphthoquinone crystals.

Melting point 179.5-180.0℃ Mass spectrum M ⁺ 295 Elemental analysis value C = 68.90 (calculated value 69.15) H = 4.44 (calculated value 4.44) N = 4.74 (calculated value 4.74) Nuclear magnetic resonance spectrum (DMSO-d ₆ ) ¹ H −NMR 13.39 (1H, OH, S), 11.78 (1H,
OH, S), 9.51 (1H, NH, broad), 7.26
(6H, arom., S), 5.93 (1H, quinone, s)
2.33 (3H, CH ₃ , s) Synthesis Example 2 Dissolve 1000 g of 2-toluidino-5,8-dihydroxynaphthoquinone obtained in Synthesis Example 1 in 60 ml of acetic acid, then add 150 ml of a 4N hydrochloric acid aqueous solution containing 5000 g of stannous chloride. was added. Stirred at reflux temperature for about 10 minutes. The solution changed from reddish brown to yellowish brown, confirming that reflux had progressed sufficiently, and after cooling to room temperature, it was filtered and thoroughly washed with water. The crystals were dried under reduced pressure to obtain 775 mg (76.8%) of the desired product, which was further recrystallized from ethanol under an argon atmosphere.

There are several possible tautomers of this substance, but from the results of the analysis below, 6-toluidino-
It was confirmed to be 2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione.

Melting point 167.0−169.0℃ Mass spectrum M ⁺ 297 Nuclear magnetic resonance spectrum (CDCl ₃ ) ¹ H−NMR 12.59 (1H, OH, S), 12.54 (1H,
OH, S), 7.07-7.28 (4H, arom., m),
6.89 (1H, NH, broad), 6.71 (1H, arom.,
s), 2.94 (4H, -( _CH2 )-, t), 2.34 (3H,
CH ₃ , s) ¹³ C-NMR 202.8n, 197.3ppm (C=0) Synthesis example 3 5,8-dihydroxynaphthoquinone (1 m
mol), boric acid (1 mmol) and ethanol (20
ml), heated at reflux temperature for 5 minutes, slowly cooled to room temperature, and dissolved in p-chloroaniline (20 ml).
mol) and stirred for 2 hours. After reaction treatment,
The reaction solution was poured into a dilute aqueous hydrochloric acid solution, and the precipitate was filtered and dried under reduced pressure. This dried product was subjected to chromatography to fractionate and purify it, resulting in 258 mg of crystals of 2-(p-chloroanilino)naphthazarin (yield: 80.3%).
was isolated.

Melting point 130.0-131.2℃ Mass spectrum M ⁺ 315 Elemental analysis values C = 60.92 (calculated value 60.87) H = 3.16 (calculated value 3.19) N = 4.33 (calculated value 4.44) Nuclear magnetic resonance spectrum (DMSO-d ₆ ) 13.26 (1H ,
OH, S), 11.75 (1H, OH, S), 9.55 (1H,
NH, S), 7.08−7.59 (6H, arom., m), 6.01
(1H, quinone, s) Synthesis Example 4 1.004 g of 2-(p-chloroanilino)naphthazarin obtained in Synthesis Example 3 was dissolved in 60 ml of acetic acid, and then 150 ml of a 4N hydrochloric acid aqueous solution containing 5000 g of stannous chloride was added. . Stirred at reflux temperature for about 10 minutes. The solution changed from reddish brown to yellowish brown, confirming that the reduction had progressed sufficiently, and after cooling to room temperature, it was filtered and thoroughly washed with water. The crystals were dried under reduced pressure to obtain 502 mg (49.7%) of the desired product, which was further recrystallized from ethanol under an argon atmosphere.

There are several possible tautomers of this compound, but from the results of the analysis below, it is 6-(p-chloroanilino)-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione. I confirmed that.

Melting point 187.0−188.0℃ Mass spectrum M ⁺ 319 Nuclear magnetic resonance spectrum (CDCl ₃ ) 12.54 (2H,
OH, S), 7.07-7.45 (4H, arom., m), 6.90
(1H, NH, broad), 6.76 (1H, arom., s),
2.96 (4H, -( _CH2 ) _2- ,t) ^13C -NMR 202.8n, 197.7ppm (>C=0) [Example] Next, an example of staining using the naphthalene derivative of the present invention will be shown.

Example 1 6-Toluidino-2,3-dihydro-5,8-
20mg of dihydroxynaphthalene-1,4-dione
was dissolved in 20 g of water, and a wool muslin test fiber manufactured by Shirozome Co., Ltd. was immersed in the solution at a bath ratio of 1/40 and shake-dyed at a temperature of 30°C or 40°C for 45 minutes to obtain a dark brown color. A wool muslin was obtained.

In addition, at this time, if 0.7 to 2.0% by weight of ammonia is co-present, the dyeing will be performed even better.

Example 2 6-p-chloroanilino2,3-dihydro-
20 mg of 5,8-dihydroxynaphthalene-1,4-dione was dissolved in 20 g of water, and 1.0 g of gray hair purchased from Abeille Co., Ltd. was immersed in the solution and dyed by shaking at 30 DEG C. for 45 minutes. Thereafter, the dyed hair was washed with 200 c.c. of water at 30°C for 5 minutes to obtain hair without any gray hair.

The obtained dyed hair was washed using a commercially available shampoo and further treated using a rinse, but there was no change in color tone.

Example 3 Multi-fiber for testing manufactured by Shirozome Co., Ltd. (consisting of 17 types of fibers. Acetate is beige, others are white) was dyed according to Examples 1 and 2, and dyed according to the presence or absence of ammonia and its amount. A bright dark brown dyed fiber was obtained.

Claims (1)

[Claims] 1. A naphthalene derivative represented by the following formula () (R represents a methyl group or a chloro group.)