JPS6195074A - Naphthalene derivative - Google Patents

Abstract

NEW MATERIAL:A compound of formula. USE:Dyes, pigments and intermediates thereof. PREPARATION:The objective compound can be prepared by the reduction, in the presence of an alkali such as KOH, NaOH or Na2CO3 using a reducing agent such as sodium dithionate, of 2-benzylamino-5,8-dihydroxynaphthoquinone in water, alcohol, water-alcohol mixed solution or Zn-contg. ag. HCl, pref. under an anaerobic condition at room temperature-reflux temperature for 1-5hr.

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 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 (I[r), 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.

(Left below) [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 present in the bath. This creates 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 having 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 circumstances, the present inventors conducted extensive research to find out whether it was 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. The present invention has now been completed.

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

(Left below) 'ゝThe above naphthalene derivative is prepared by adding 2-benzylamino-5,8-dihydroxynaphthoquinone to water using a reducing agent such as sodium dithionate in the presence of an alkali such as potassium hydroxide, sodium hydroxide or sodium carbonate. alcohol,
It can be obtained by reduction in a water-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 5 hours.

When dyeing using the naphthalene derivative of the present invention, the fibers can be dyed better if 0.7 to 2.0% by weight of ammonia is present in the bath.

[Effect of the invention] As mentioned above, the naphthalene derivative of the present invention can be prepared under anaerobic conditions.
It can be isolated as a leuco form from the reaction system, can be stored 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 naphthalene derivative of the present invention has a concentration of 0.1% or higher.
Demonstrates dyeing power that can withstand practical use from a concentration of about 1.9%.

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 hair, and when used as a hair dye, it is particularly preferable to use it under mild conditions. Recognized as a quality.

[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 10 mm of naphthazarin in 20 mmol of benzylamine
80 mff of ethanol solution containing ol was slowly added and stirred at a temperature of 0 to 2°C for 3.5 hours. After the reaction was completed, the reactant was poured into a dilute aqueous hydrochloric acid solution, and the precipitate was filtered and dried under reduced pressure. This dried product was fractionated and purified by column chromatography using silica gel as a filler and benzene as a solvent to obtain 1.257 g of crystals (yield: 42
．． 3%) was obtained and further recrystallized from ethanol. This product was found to be 2-benzylamino-5,8 according to the following analytical values.
- It was confirmed that it was dihydroxynaphthoquinone.

Mass spectrum M+=295 Elemental analysis value C=69.11 (calculated value 69.15
)H=4.44 (calculated value 4.44 >N=4.
68 (calculated value 4.74) Nuclear magnetic resonance spectrum (
CDC13, δ, ppm)' H-NMR13,28
(Ill 0H1S), 11.83 (IH, OHS
S), 7.35 (5L arom,
, 1ike Sun, 7.03-7.26
(2H1arom, ,q) ,6.39 (III
, N.H.

broad), 5.72 (IIISquinon
e, s), 4.36-4.42 (2) ISC
H2ph, d) 13C-NMRcarbonyl
group-, 1B7.2, 183.7 Synthesis Example 5 400 mg of 2-benzylamino-5,8-dihydroxynaphthoquinone obtained in Synthesis Example 1 was added to 400 mg of sodium carbonate.
The mixture was dispersed in 300 g of water together with 1200 g of sodium dithionate, and stirred at reflux temperature for 3 hours under an argon atmosphere. The solution turned yellowish brown to confirm that the reduction had progressed sufficiently, and after cooling to room temperature, 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 355 mg (yield: 88.8%) of the desired product, which was further recrystallized from ethanol under an argon atmosphere.

There are several possible tautomers of this compound, but as shown in the analysis values below, the chemical shift of the carbonyl group in '3C-NMR is significantly lower than that of quinones, so , 6-benzylamino-2,3-dihy, which is thought to have a methyl group or methylene group adjacent to the carbonyl group. -5,8-';b F
. Ah, +7 ke I/7-1.4-U, O, ゛゛ confirmed.

Mass spectrum M+=297 Elemental analysis value C=68.50 (calculated value 68.68
)H=5.00 (calculated value 5.09”)N=4
．． 62 (calculated value 4.71') Nuclear magnetic resonance spectrum (CDC13, δ, ppm) l H-NMR12,
85 (IH, Oll, S'), 12.50 (IH,
OH,S) ,7.32 (5H,arom, ,S
) , 6.22 (IH, arom, , s ) , 5
．． 71 (III, Nil, broad), 4.3
8-4.44 (2H,CH2ph,), 2.93
(4H.

(CH2)-1S) 13C-NMR carbonyl groups 20
2.9.197.2 Next, examples of staining using the naphthalene derivative of the present invention will be shown.

Example 1 6-benzylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione 2 obtained in Synthesis Example 2
0 mg was dissolved in 20 g of water, and a wool muslin test fiber manufactured by Shikisensha 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,
In each case, a bright reddish-purple 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-benzylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione 2 obtained in Synthesis Example 2
0 mg 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° C. for 45 minutes. Thereafter, the dyed hair was washed with 200 d of water at 30° C. for 5 minutes to obtain hair with no gray hairs at all.

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

Example 3 Test multi-fiber manufactured by Shirozome Co., Ltd. (consisting of 17 types of fibers. Acetate is beige, others are white) was dyed according to Example 1, and bright colors were dyed according to the presence or absence of ammonia and its amount. A reddish-purple dyed fiber was obtained.

Claims (1)

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