JPH0514743B2 - - 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 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, 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 condensed carbazole 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.

In addition, the sulfate ester of the leuco form of indigo is too stable and cannot be colored unless a strong oxidizing agent, such as potassium permanganate, is used, which is also not a good condition for fibers. do not have.

In view of the above-mentioned circumstances, the present inventors have 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. The invention was completed.

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

[In formula (), R represents hydrogen, a lower alkyl group such as methyl or ethyl, and n represents a number from 1 to 3. ] The above naphthalene derivative is prepared by reacting 2-hydroxy (or alkoxy)alkylamino-5,8-dihydroxynaphthoquinone with water, using a reducing agent such as sodium dithionate in the presence of an alkali such as potassium hydroxide, sodium hydroxide, or sodium carbonate. It can be obtained by reduction in alcohol, 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 even 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 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 that it can be used under mild conditions. Recognized as a quality.

[Synthesis example] Synthesis example of a 6-hydroxyalkylaminonaphthalene derivative represented by n=2 and R=H as a representative example of a 6-hydroxyalkylamino group in general formula (), and a representative example of a 6-alkoxyalkylamino group As an example, n=2, R=6 denoted by CH ₃
- Synthesis examples of methoxyethylaminonaphthalene derivatives are shown below.

Synthesis Example 1 80 ml of an ethanol solution containing 10 mmol of naphthazarin in 200 mmol of 2-aminoethanol 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. The dried product was fractionated and purified by column chromatography using silica gel as a filler and benzene as a solvent to obtain 1.571 g (yield: 62.7%) of the desired crystals, which were further recrystallized from ethanol. This product was confirmed to be 2-(2'-hydroxyethylamino-5,8-dihydroxynaphthoquinone) by the following analytical values.

Mass spectrum M = 249 Elemental analysis values C = 57.77 (calculated value 57.83) H = 4.41 (calculated value 4.45) N = 5.58 (calculated value 5.62) Nuclear magnetic resonance spectrum (DMSO-d ₆ , δ,
ppm) ¹ H-NMR 13.60 (1H, OH, S), 11.65 (1H,
OH, S), 7.73 (1H, NH, broad), 7.10−7.40
(2H, arom., m), 5.68 (1H, quinone, s),
4.85 (1H, N( _CH2CH2 ) OH _, broad), 3.10−
3.70 (4H for ethyl group) ¹³ C-NMR carbonyl group 186.1, 183.5 Synthesis Example 2 600 mg of 2-(2'-hydroxyethylamino)-5,8-dihydroxynaphthoquinone obtained in Synthesis Example 1
600mg of sodium carbonate, sodium dithionate
Add 1600mg of ethanol aqueous solution (ethanol
15, dissolved in 35 ml of water 20) under argon atmosphere,
Stirred at reflux temperature for 3 hours. The solution turned yellowish brown, confirming that the reduction had progressed sufficiently, and after cooling to room temperature, it was filtered, and the crystals were thoroughly washed with degassed water. Dry the crystals under reduced pressure to obtain 450mg of the target product.
(yield 75.8%), which was further recrystallized from ethanol under an argon atmosphere.

There are several possible tautomers of this substance, but as seen in the analysis values below, C-NMR
Since the chemical shift of the carbonyl group in is observed to be significantly lower than that of quinones,
It is thought that there is a methyl group or methylene group adjacent to the carbonyl group, and it was confirmed that it is 6-(2'-hydroxyethylamino)-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione. .

Mass spectrum M = 251 Elemental analysis value C = 57.33 (calculated value 57.37) H = 5.28 (calculated value 5.22) N = 5.64 (calculated value 5.58) Nuclear magnetic resonance spectrum (DMSO-d ₆ , δ,
ppm) ¹ H-NMR 13.08 (1H, OH, S), 12.55 (1H,
OH, S), 6.59 (1H, NH, broad), 6.31 (1H,
arom., s), 4.57 (1H, N(CH ₂ CH ₂ ) OH ,
broad), 2.95 (4H, −(CH ₂ ) ₂ −, t), 2.94−3.66
(4H for ethyl group) ¹³ C-NMR carbonyl group 203.8, 197.6 Synthesis example 3 80 ml of ethanol solution containing 10 mmol of naphthazarin in 200 mmol of 2-methoxyethanolamine
was slowly added and stirred at a temperature of 0 to 2°C for 3.5 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 fractionated and purified by column chromatography using silica gel as a filler and benzene as a solvent to obtain 1.6311 g (yield: 61.6%) of the desired crystals, which were further recrystallized from ethanol. This product was confirmed to be 2-(2'-methoxyethylamino)-5,8-dihydroxynaphthoquinone by the following analytical values.

Mass spectrum M = 263 Elemental analysis value C = 59.38 (calculated value 59.31) H = 4.97 (calculated value 4.98) N = 5.28 (calculated value 5.32) Nuclear magnetic resonance spectrum (CDCl ₃ , δ, ppm) ¹ H-NMR 13.33 ( 1H, OH, S), 11.68 (1H,
OH, S), 7.78 (1H, NH, broad), 7.12−7.38
(2H, arom., q), 5.76 (1H, quinone, s),
3.28 (3H, OMe, s), 3.30−3.55 (4H for ethyl
group) ¹³ C-NMR carbonyl group 186.4, 183.6 Synthesis Example 4 1.007 g of 2-(2'-methoxyethylamino)-5,8-dihydroxynaphthoquinone obtained in Synthesis Example 3
was dissolved in 60 ml of an aqueous ethanol solution (20 ml of ethanol, 40 ml of water) along with 1.017 g of sodium carbonate and 2.500 g of sodium dithionate, and the mixture was stirred at reflux temperature for 3 hours under an argon atmosphere. After the reaction was completed, it was filtered and the crystals were thoroughly washed with degassed water. The crystals were dried under reduced pressure to obtain 900 mg of the target product (yield 88.7%).
Further, it was recrystallized from ethanol under an argon atmosphere.

Although several types of tautomers are considered for this compound, C-NMR data etc. indicate that 6-(2'-methoxyethylamino)-2,3-dihydro-5,8-dihydroxynaphthalene-1,4 - Confirmed that it is a dione.

Mass spectrum M = 265 Elemental analysis value C = 58.85 (calculated value 58.86) H = 5.58 (calculated value 5.70) N = 5.21 (calculated value 5.28) Nuclear magnetic resonance spectrum (CDCl ₃ , δ, ppm) ¹ H-NMR 13.01 ( 1H, OH, S), 12.54 (1H,
OH, S), 6.58 (1H, NH, broad), 6.31 (1H,
arom., s), 3.01 (3H, OMe, s), 2.95 (4H, −
(CH ₂ ) ₂ −, t), 3.14−3.66 (4H for ethyl
group) ¹³ C-NMR carbonyl group 203.8, 197.5 In the general formula (), n=2, R=H; n=
2. Synthesis examples of R=CH ₃ are shown in Synthesis Examples 1 to 4, but n=2, R=C ₂ H ₅ ; n=3, R=H; n=
3. Even in cases where R=CH ₃ ; n=3, R=C ₂ H ₅ , etc., almost the same results were obtained, although there were some differences in yield, and mass spectra, nuclear magnetic resonance spectra, and elemental analysis were obtained. The compound was identified by

Next, examples of dyeing using the naphthalene derivative of the present invention will be shown.

Example 1 6-(2'-hydroxyethylamino)2,3 represented by n=2 and R=H in the general formula ()
-dihydro-5,8-dihydroxynaphthalene-
1,4 _- dione and 6-(2'-ethoxypropylamino)-2,3 with n=3 and R= _C2H5
-dihydro-5,8-dihydroxynaphthalene-
20 mg of each 1,4-dione was dissolved in 20 g of water, and a wool muslin test fiber made by Shikisensha Co., Ltd. was immersed in the solution at a bath ratio of 1/40, and the solution was heated to 45°C at a temperature of 30°C or 40°C. The wool muslin was dyed by shaking for a minute, and although there were some differences due to differences in substituents, a bright reddish brown wool muslin was obtained in each case.

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 In general formula (), n=2, R=H; n=
3, 6-(2'-hydroxyalkylamino)-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione represented by R=H, and n
6-(2'-alkoxyethylamino)-2,3-dihydroxy-5,8 _- dihydroxynaphthalene- represented by =2, R= _CH3 ; n=2, R= _C2H5
20 mg of each of the 1,4-diones 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. After that, soak the dyed hair in 200ml of water at 30℃5.
After washing for several minutes, hair with no gray hair was obtained.

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 reddish-brown dyed fiber was obtained.

Claims (1)

[Claims] 1. A naphthalene derivative represented by the following general formula () [In formula (), R represents hydrogen, methyl or ethyl group, and n represents a number from 1 to 3. ]