JPH0684337B2 - 2-Alkyl-4-methoxy-5-aminophenol or salt thereof and keratin fiber dyeing composition using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel 2-alkyl-4-methoxy-5-aminophenol or a salt thereof, and a keratin fiber dyeing composition containing the same.

[Conventional technology]

For dyeing keratinous fibers such as hair, so-called oxidative dyes, which are used in combination with a color-developing substance and a coupling substance, have been widely used. This oxidative dyeing agent utilizes what is called an oxidative dye, which is generated by oxidative coupling of a color-developing substance and a coupling substance, strongly dyes hair and the like.

Conventionally, as the developer, generally, a p-phenylenediamine derivative, a p-aminophenol derivative, a diaminopyridine derivative, a 4-aminopyrazolone derivative, a heterocyclic hydrazone, etc., and a coupling substance, α
-Naphthol, o-cresol, m-cresol, 2,6
-Dimethylphenol, 2,5-dimethylphenol, 3,4
-Dimethylphenol, 3,5-dimethylphenol, benzcatechin, pyrogallol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 5-amino-
2-methylphenol, hydroquinone, 2,4-diaminoanisole, m-toluylenediamine, 4-aminophenol, resorcin, resorcin monomethyl ether,
m-phenylenediamine, 1-phenyl-3-methyl-
5-pyrazolone, 1-phenyl-3-amino-5-pyrazolone, 1-phenyl-3,5-diketo-pyrazolidine,
1-methyl-7-dimethyl-amino-4-hydroxyquinolone-2, 1-amino-3-acetyl-acetamino-4-nitrobenzol, 1-amino-3-cyanacetyl-amino-4-nitro-benzol, m -Aminophenol, 4-chlororesorcin, 2-methylresorcin, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 3,5-diamino-trifluoromethylbenzene, 2,4-diamino-fluorobenzene, 3, 5-diamino-
Fluorobenzene, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-triaminopyrimidine, 2-amino-
4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4,6-diamino-2-hydroxypyrimidine, p-nitro-o-phenylenediamine, 2
-Amino-5-nitrophenol, p-nitro-m-phenylenediamine, o-nitro-p-phenylenediamine, 2-amino-4-nitrophenol and the like are used.

[Problems to be Solved by the Invention]

However, the conventional oxidative dyes have not been sufficiently satisfactory in terms of saturation, dyeing power and fastness.
Since these properties are greatly influenced by the properties of the coupling substance, it is extremely important to find a substance having excellent properties as a coupling substance in order to obtain an excellent oxidative dyeing agent.

[Means for Solving the Problems]

Under such circumstances, the present inventors have synthesized many compounds and examined their properties as a coupling substance, and as a result, a novel 2-alkyl-4-methoxy represented by the following general formula (I) was obtained. The present invention has been completed by finding that -5-aminophenol and its salts have the above-mentioned excellent properties.

That is, the present invention provides the following general formula (I): (In the formula, R represents a lower alkyl group) 2-alkyl-4-methoxy-5-aminophenol represented by the formula: and a salt thereof and an intermediate thereof, 2-nitro- represented by the following general formula (II). 4-mesyloxy-
The present invention provides 5-alkylphenol or 2-nitro-4-hydroxy-5-alkylphenol.

(In the formula, R ₁ represents lower alkyl, R ₂ represents a hydrogen atom or a mesyl group.) Furthermore, the present invention provides a keratin fiber dyeing composition containing the compound (I) as a coupling substance. is there.

The 2-alkyl-4-methoxy-5-aminophenol (I) of the present invention can be prepared, for example, from 2-nitro-4-mesyloxy-5-alkylphenol (II
It is prepared by methylating I) to compound (IV), demesylating it to compound (V), and then reducing it.

(In the formula, R represents the same as above.) The starting compound (III) can be easily produced, for example, by the method described in JP-A-62-240960.

Methylation of compound (III) can be carried out by a usual phenol methylation method, and among them, the dimethyl sulfate method is simple and efficient. The demesylation reaction of compound (IV) is preferably carried out in alkali. The reduction of the compound (V) can be carried out by an ordinary method for reducing a nitro group, but a catalytic hydrogenation method or an acetic acid aqueous solution-iron reduction method is simple and efficient. In catalytic hydrogenation, palladium, platinum, copper, nickel or the like is used as a catalyst. As the solvent, methanol, ethanol, ethyl acetate, dimethylformamide and the like are preferable. The reaction temperature may be room temperature to the boiling point of the solvent used, and the hydrogen pressure may be 1 to 250 kg / cm ² . After completion of the reduction, the catalyst can be filtered off, and the filtrate can be purified very easily by concentration or distillation or recrystallization.
The reduction method with an iron-acetic acid aqueous solution is a solvent miscible with an acetic acid aqueous solution, for example, methanol, ethanol, acetone, N, N-dimethylformamide, dimethylsulfoxide, etc. are added as necessary and heated under reflux in the presence of excess iron. It is carried out by. After the reaction is completed, the solid is filtered,
The filtrate can be easily purified by extraction with a suitable organic solvent, concentration and distillation or recrystallization.

The compound (I) of the present invention thus obtained is a salt of an inorganic or organic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid, citric acid or the like by a conventional method in order to improve the handleability of formulation. Can be

When the compound (I) of the present invention is used as a coupling substance together with an ordinary color-developing substance, a keratin fiber dyeing composition exhibiting a wide color tone of yellow to red to blue is obtained.

In the present invention, as the color-developing substance, those which are generally used for oxidative hair dyes can be used. For example, p-phenylenediamine, toluene-2,5-diamine, N-phenyl-p- P-phenylenediamine derivative such as phenylenediamine; p-aminophenol, 5-aminosalicylic acid, p-aminophenol derivative such as 2,4-diaminophenol; 2,5-diaminopyridine, 2,3-
Pyridine derivatives such as diaminopyridine; and pyrimidine derivatives such as tetraaminopyrimidine. Among these color-developing substances, the following general formula (VI) (In the formula, X represents a hydrogen atom, a halogen atom, a carboxyl group or an acetylamino group).
It is possible to obtain a reddish color tone having extremely high saturation and high fastness. Examples of the compound of the formula (VI) include p-aminophenol, 5-aminosalicylic acid, 3-carboxy-4-aminophenol, 2-acetylamino-4-aminophenol, 2-chloro-4-aminophenol and the like. To be

Other coupling substances may be incorporated into the dyeing composition of the present invention, and in some cases, direct dyes may be incorporated to additionally change the shade. Examples of such direct dyes include 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, and nitro-hydrochloric acid described in the dye raw material standard issued by Japan Hair Color Industry Association.
p-phenylenediamine, nitro-p-phenylenediamine, p-aminophenylsulfamic acid, p-nitro-o-phenylenediamine, picramic acid, sodium picramate, picric acid, chrome brown RH, hematein, nitro-p-phenylene sulfate Diamine, sulfuric acid p-
Nitro-o-phenylenediamine, sulfuric acid p-nitro-m
-Phenylenediamine, 1-amino-4-methylaminoanthraquinone, 1,4-diaminoanthraquinone; Acid dyes Red No. 2, Red No. 3, Red No. 102, Red 104
No., Red No. 105, Red No. 106, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1, Blue No. 2, Red No. 201, Red No. 227, Red No. 230, Red No. 231, Red No. 232, Orange 205, Orange 207,
Yellow 202, Yellow 203, Green 201, Green 204, Green 20
No. 5, Blue No. 202, Blue No. 203, Blue No. 205, Brown 201
No., Red No. 401, Red No. 502, Red No. 503, Red No. 504, Red No. 506, Orange No. 402, Yellow No. 402, Yellow No. 403, Yellow No. 406
No. 407, Yellow 407, Green 401, Green 402, Purple 401, Black
401; oil-soluble dyes Red 215, Red 218, Red 2
No. 25, Orange 201, Orange 206, Yellow 201, Yellow 204, Green
No. 202, purple 201, red 501, red 505, orange 403,
Yellow 404, Yellow 405, Blue 403; basic dyes Red 213, Red 214; and Arianor basic dyes Sienna brown, Mahogany, Madder Red, Steel Blue,
Examples thereof include Straw Yellow, but nitrophenylenediamine, nitro-aminophenol and anthraquinone dyes are particularly preferable.

The dyeing composition of the present invention causes oxidative coupling even by oxygen in the air to dye hair and the like, but it is more preferred to cause oxidative coupling by adding a chemical oxidizing agent. Particularly preferred oxidizing agents include hydrogen peroxide; products of hydrogen peroxide added to urea, melamine or sodium borate; mixtures of such hydrogen peroxide adducts and potassium peroxide-disulfate.

The dyeing composition of the present invention is usually a cream, emulsion,
It is preferably provided in the form of gel, solution or the like. In order to obtain such a dosage form, a moisturizer (emulsifier), a solubilizer, a thickener, a stabilizer, a touch improver, and a hair styling base which are usually used in the field of cosmetics are added to the color-developing substance and coupling substance. It may be produced according to a conventional method by adding agents, flavors and the like. Examples of the wetting agent (emulsifier) used here include alkylbenzene sulfonate, fatty alcohol sulfate, alkyl sulfonate, fatty acid alkanolamide, addition product of ethylene oxide and fatty alcohol, and the like. Examples of thickeners include methyl cellulose, starch, higher fatty alcohols, paraffin oil, and fatty acids, and examples of stabilizers include reducing agents such as sulfites, hydroquinone derivatives, chelating agents, and the like. Examples of the improver and hair styling base include silicones, higher alcohols, oils such as various nonionic surfactants, and various cationic polymers.

The total amount of the color-developing substance and the coupling substance in these dosage forms is 0.2 to 10% by weight (hereinafter simply referred to as%),
Particularly, 1 to 5% is preferable. Wetting agent (emulsifier) is usually 0.5
-30%, and the thickener is preferably 0.1-25%.

Further, in these dosage forms, the pH of the entire composition is preferably adjusted to about 8-10.

To carry out dyeing of keratinous fibers using the dyeing composition of the present invention, for example, an oxidizing agent is added to the dyeing composition of the present invention to carry out oxidative coupling to prepare a dyeing solution, and this dyeing solution is applied to keratinous fibers. It is applied by washing the keratinous fibers after application for a working time of about 10 to 50 minutes, preferably about 25 to 35 minutes, and then drying. The application of the dyeing solution here takes place at 15-40 ° C.

〔The invention's effect〕

As described above, in a keratin fiber dyeing composition comprising a color-developing substance and a coupling substance, when the 2-alkyl-4-methoxy-5-aminophenol or the salt thereof of the present invention is used as the coupling substance, saturation, A wide range of dyeing excellent in dyeing power and fastness is possible, and in particular, by combining a p-aminophenol derivative as a color-developing substance, it is possible to obtain a reddish color tone having extremely high saturation and high fastness. Moreover, the obtained color tone has good light resistance, washing resistance and abrasion resistance.

〔Example〕

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1 (i) To 200 ml of acetone, 19.1 g (77.3 mmol) of 2-nitro-4-mesyloxy-5-methylphenol, 31.2 g of sodium carbonate and 19.2 g of dimethyl sulfate were added, and the mixture was heated under reflux for 3 hours. The reaction solution was cooled, poured into 700 ml of water, extracted with 700 ml of chloroform, washed with water, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was recrystallized from a mixed solvent of hexane-acetone (2: 1) to obtain 15.4 g (59.1 mmol) of 3-mesyloxy-4-methyl-6-methoxynitrobenzene. Melting point 110.0
~ 113.0 ° C. Yield 77%.

(Ii) 3-Mesyloxy-4-methyl-6-methoxynitrobenzene (15.5 g, 59.4 mmol) was dissolved in methanol (110 ml), and sodium hydroxide (6.5 g) dissolved in water (20 ml) was added thereto, followed by heating under reflux for 1 hour. After cooling, concentrated hydrochloric acid was added to make the mixture acidic, and 400 ml of water was added to precipitate crystals. This is collected by filtration, washed with water and treated with 3-nitro-4-methoxy-
10.9 g (59.4 mmol) of 6-methylphenol was obtained. Melting point 7
9.5-80.5 ° C. Yield 100%.

(Iii) Add 10% palladium on carbon to 300 ml autoclave.
320 mg, 3-nitro-4-methoxy-6-methylphenol 2.90 g (15.8 mmol), and ethanol 75 ml were added, and 50
Hydrogenation was carried out at 50 ° C. and 50 kg / cm ² for 5 hours. After cooling, the catalyst was filtered off and the solvent was distilled off under reduced pressure to give 1.90 g (12.4 m) of brown crystals of 3-amino-4-methoxy-6-methylphenol.
mol) got. The ¹ H-NMR spectrum of this product showed no impurities, and the yield was 78%.

Further, this 3-amino-4-methoxy-6-methylphenol was subjected to silica gel column chromatography [Merck silica gel 60, 230-400 mesh, 200 g, elution solvent:
It was purified with acetone-chloroform (1: 1)], dissolved in ether and blown with hydrogen chloride gas to give the hydrochloride of 3-amino-4-methoxy-6-methylphenol. Decomposition point 197-203 ℃.

Example 2 Base composition: (%) Oleic acid 10 Oleic acid diethanolamide 8 Oleyl alcohol 2 Polyoxyethylene octyldodecyl ether (average EO
20 mol addition) 10 Ethanol 15 Propylene glycol 10 Ammonium chloride 3 25% Ammonia 7 Water 35 In 100 g of the base having the above composition, the color developing substances shown in Table 1
01 mol and 0.01 mol of coupling substance were mixed in. Next, the dyeing composition of the present invention was produced by adjusting the pH of the composition to 9.5 with ammonia.

A dyeing solution was prepared by adding an equal weight of a 6% aqueous hydrogen peroxide solution to 100 g of the dyeing composition of the present invention. This dyeing solution was applied to human hair containing white hair and left at 30 ° C. for 30 minutes. The hair was then washed with normal shampoo and dried. The result of observing the color tone of the obtained dyeing is shown in Table 1, and the result of observing the color tone, saturation, dyeability and discoloration resistance is shown in Table 2.

The resistance to discoloration and fading was determined by comparing the change after storage for 100 hours at 40 ° C. and 70% RH with that of the stored product at −5 ° C. All of the judgments were made visually.

Developer substance P _1: p-phenylenediamine P _2: Toluene-2,5-diamine P _3: p-aminophenol P _4: 5-aminosalicylic acid P _5: 2-chloro-4-aminophenol P _6: 2- Trifluoromethyl-4-aminophenol coupling substance C ₁ : 2-methyl-4-methoxy-5-aminophenol C ₂ : 2-methyl-5-aminophenol C ₃ : 2-methyl-4-methoxy-5- Aminophenol hydrochloride Criteria ◎: Very good ○: Normal ×: Poor

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hidetoshi Tagami 2-1-3 Fumika, Sumida-ku, Tokyo 2-1-3 Inside Kao Corporation, Tokyo Research Institute (72) Toru Yoshihara 2-1-3 Fumika, Sumida-ku, Tokyo Kao Corporation, Tokyo Research Institute (72) Inventor Jiro Kawase, 2-1-3, Fumika, Sumida-ku, Tokyo Kao Corporation, Tokyo Research Institute (56) Reference West German Patent Publication 4017516 (DE, A)

Claims (4)

[Claims] 1. The following general formula (I): (In the formula, R represents a lower alkyl group) or a 2-alkyl-4-methoxy-5-aminophenol or a salt thereof. 2. General formula (II) (In the formula, R ₁ represents a lower alkyl group and R ₂ represents a hydrogen atom or a mesyl group.) A 2-alkyl-4-methoxy-5-nitrophenol derivative. 3. A keratin fiber dyeing composition comprising the 2-alkyl-4-methoxy-5-aminophenol or the salt thereof according to claim 1 as a color-developing substance and a coupling substance. 4. The color-developing substance has the following general formula: The keratin fiber dyeing composition according to claim 3, which is a p-aminophenol derivative represented by the formula (wherein X represents a hydrogen atom, a halogen atom, a carboxyl group or an acetylamino group).