JPH06116215A - 2-alkyl-4-alkoxy-5-aminophenol derivative or its salt and cuticle fiber dyeing agent composition produced by using the compound - Google Patents

Abstract

PURPOSE:To provide a new 2-alkyl-4-alkoxy-5-aminophenol derivative or its salt useful as a coupling substance having excellent saturation, degree of dyeing power and fastness. CONSTITUTION:The 2-alkyl-4-alkoxy-5-aminophenol derivative of formula 1 [R<1> is lower alkyl; R<2> and R<3> are H, (OH-substituted) alkyl, (halogen-substituted) lower alkanoyl, arylcarbonyl or lower alkylsulfonyl; R<4> is >=2C lower alkyl; R<2> and R<3> are not H at the same time] or its salt. The compound of formula 1 can be produced e.g. by using a compound of formula 3 (R<8> is alkyl) as a starting substance, converting the substance to a compound of formula 8 via the compounds of formula 6 and formula 7 and converting this compound 8 via a compound of formula 10 to a compound of formula 1a, or via a compound of formula 14 (R<10> is arylcarbonyl, etc.) to a compound of formula 1c or directly to a compound of formula 1b (R<9> is alkyl).

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel 2-alkyl-4
The present invention relates to an alkoxy-5-aminophenol derivative or a salt thereof, and a keratin fiber dyeing agent composition containing the same, which is excellent in saturation, dyeing power and fastness and has good storage stability.

[0002]

2. Description of the Related Art 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 between a color-developing substance and a coupling substance, strongly dyes hair and the like.

Conventionally, as the color developing substance, p-
A phenylenediamine derivative, a p-aminophenol derivative, a diaminopyridine derivative, a 4-aminopyrazolone derivative, a heterocyclic hydrazone, etc., and a coupling substance include α-naphthol, o-cresol, m-cresol, 2,6-dimethyl. Phenol, 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, o-aminophenol, resorcin, resorcin monomethyl ether, m -Phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 1-
Phenyl-3-amino-5-pyrazolone, 1-phenyl-3,5-diketopyrazolidine, 1-methyl-7-dimethylamino-4-hydroxyquinolone-2,1-amino-3-acetylacetamino-4 -Nitrobenzol,
1-amino-3-cyanacetylamino-4-nitrobenzol, m-aminophenol, 4-chlororesorcin, 2-methylresorcin, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 3,5-diaminotri Fluoromethylbenzene, 2,4-diaminofluorobenzene, 3,5-diaminofluorobenzene, 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.

[0004]

However, the conventional oxidative dyes have not been sufficiently satisfactory in terms of saturation, dyeing strength 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 oxidation dye. Therefore, the present applicant has studied to find a coupling substance excellent in saturation, dyeing power and fastness, and the following general formula (2)

[0005]

[Chemical 2]

(In the formula, R ⁵ represents a lower alkyl group, and R ^5
6 and R ⁷ represent a hydrogen atom, an alkyl group which may be substituted with a hydroxy group, a lower alkanoyl group which may be substituted with a halogen atom, an arylcarbonyl group or a lower alkylsulfonyl group) −
A 4-methoxy-5-aminophenol derivative or a salt thereof was found to have satisfactory performance as a coupling substance, and a patent application was previously filed (JP-A-3-58915).
Japanese Patent Application Laid-Open No. 3-135912, Japanese Patent Application Laid-Open No. 3-17385
No. 2).

However, although the 2-alkyl-4-methoxy-5-aminophenol derivative or its salt (2) has excellent characteristics in saturation, dyeing power and fastness,
Depending on the method of storage after production, decomposition may occur and the residual rate may decrease, which may cause problems such as deterioration in saturation and dyeing power. Therefore, there has been a demand for a coupling substance which is excellent in saturation, dyeing power and fastness and has good storage stability.

[0008]

Under the circumstances, as a result of intensive studies by the present inventors, a novel 2-alkyl-4-alkoxy-5-type represented by the following general formula (1) was obtained.
The present inventors have completed the present invention by discovering that aminophenol derivatives and salts thereof have excellent properties as a coupling substance and have good storage stability.

That is, the present invention provides the following general formula (1):

[0010]

[Chemical 3]

(In the formula, R ¹ represents a lower alkyl group, and R ^1
2 and R ³ are the same or different and represent a hydrogen atom, an alkyl group which may be substituted by a hydroxy group, a lower alkanoyl group which may be substituted by a halogen atom, an arylcarbonyl group or a lower alkylsulfonyl group, and R ⁴ represents a lower alkyl group having 2 or more carbon atoms. However, a 2-alkyl-4-alkoxy-5-aminophenol derivative represented by the formula (2) or a salt thereof is provided, except that R ² and R ³ are simultaneously hydrogen atoms.

The present invention also provides a keratinous fiber dyeing composition containing the compound (1) as a coupling substance.

In the present invention, in the general formula (1), R
^The lower alkyl group represented by 1 has, for example, 1 carbon atom.
To 5 straight-chain or branched-chain alkyl groups, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Further, among R ² and R ^3, Examples of the alkyl group which may hydroxy group substituted, one or more hydroxy groups in a lower alkyl group and a the lower alkyl group represented by R ¹ has a substituent Is mentioned. Examples of the lower alkanoyl group include linear or branched alkanoyl groups having 1 to 5 carbon atoms, and specifically, formyl group, acetyl group, propionyl group, butyryl group, valeryl group,
Examples thereof include isovaleryl group. These lower alkanoyl groups may be substituted with one or more halogen atoms, and examples of such a halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Moreover, examples of the arylcarbonyl group include a benzoyl group and naphthoyl group, and examples of the lower alkylsulfonyl group include a methanesulfonyl group and an ethanesulfonyl group. Further, the lower alkyl group having 2 or more carbon atoms represented by R ⁴ includes, for example, a linear or branched alkyl group having 2 to 5 carbon atoms, and specific examples thereof include ethyl group, n-propyl group and isopropyl group. Group, n-butyl group, t-butyl group and the like. Of these, an ethyl group is particularly preferable in consideration of both dyeing performance such as high saturation and storage stability.

2-Alkyl-4-alkoxy-of the present invention
The 5-aminophenol derivative (1) is produced, for example, according to the following reaction formula.

[0015]

[Chemical 4]

(Wherein R ¹ and R ⁴ have the same meanings as described above, R ⁸ and R ⁹ represent a lower alkyl group, R ¹⁰ represents an arylcarbonyl group or a lower alkylsulfonyl group, and X represents a halogen. Represents an atom, and n represents an integer of 2 to 4)

That is, compound (3) is reacted with dialkyl sulfuric acid (4) or alkyl halide (5) to give compound (6), which is hydrolyzed to give compound (7), which is then reduced. By doing so, the compound (8) can be obtained. This compound (8) was acylated with ω-chloroalkyl chloroformate (9) to give compound (1
The compound (1a) can be obtained by cyclization and hydrolysis. On the other hand, the compound (1b) can be obtained by reacting the compound (8) with a compound such as an acid anhydride (11) and an acid halide (12).
In addition, compound (1c) can be obtained by reacting compound (8) with a compound such as acid halide (13) to obtain compound (14) and further hydrolyzing this.

The starting material 3-alkyl-4-alkylsulfonyloxy-6-nitrophenol (3) can be produced, for example, by the method described in JP-A-62-240960. The reaction of the compound (3) with the compound (4) or (5) is carried out by elevating the temperature in the presence of a base such as sodium carbonate, and the hydrolysis of the compound (6) is carried out according to a conventional method, for example, It is preferably carried out in the presence of an alkali.

The compound (7) can be reduced by a conventional 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 using an iron-acetic acid aqueous solution is to add a catalyst that can be mixed with an acetic acid aqueous solution, such as methanol, ethanol, acetone, N, N-dimethylformamide, dimethylsulfoxide, etc., if necessary, and heat and reflux in the presence of excess iron. It is carried out by.

Compounds (9), (11) of compound (8),
The acylation or alkylsulfonylation by (12) or (13) is carried out under the same conditions as in the usual acylation or alkylsulfonylation reaction, for example, by raising the temperature in the presence of a base. The cyclization reaction and hydrolysis of the compound (10) and the hydrolysis of the compound (14) are carried out according to a conventional method.

After the reaction, the compound (1) of the present invention can be isolated from the reaction mixture by a conventional method such as recrystallization or column chromatography.

The 2-alkyl-of the invention thus obtained
4-Alkoxy-5-aminophenol derivative (1)
In order to improve the handleability of the preparation, it can be converted into a salt of an inorganic or organic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid by a conventional method.

The keratinous fiber dyeing composition of the present invention comprises the compound (1) of the present invention as a coupling substance and contains this and an ordinary color developing substance. In the present invention, as the color-developing substance, those generally used for oxidative dyeing agents can be used. For example, p-phenylenediamine, toluene-2,5-diamine, N-phenyl-p.
-Phenylenediamine, p-aminophenol, 5-aminosalicylic acid, 4-amino-2-chlorophenol,
Methoxy-p-phenylenediamine, 2,5-diaminopyridine, p-methylaminophenol, tetraaminopyrimidine, 2,4-diaminophenol, o-aminophenol, o-chloro-p-phenylenediamine, 4,
4'-diaminodiphenylamine, N, N-bis (2-
Hydroxyethyl) -p-phenylenediamine and the like. Of these, p-aminophenol, 5-
Aminophenol derivatives such as aminosalicylic acid and 4-amino-2-chlorophenol are preferred.

[0024] A developer and a developer for the dye composition of the present invention
The compounding ratio with the alkyl-4-alkoxy-5-aminophenol derivative or its salt (1) may be in excess if one is more than the other, but the molar ratio is 1: 0.5 to.
It is preferably about 1: 2. The color-developing substance and the coupling substance can be used alone or in combination of two or more kinds. Further, the dyeing composition of the present invention may contain known coupling substances, direct dyes, etc., if necessary in order to obtain a desired color tone.

The dye composition of the present invention causes oxidative coupling even by oxygen in the air to dye hair and the like, but it is more preferable to cause oxidative coupling by adding a chemical oxidant. preferable. 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 dye composition of the present invention is usually a cream,
It is preferably provided in the form of emulsion, gel, solution and 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 group which are usually used in the field of cosmetics are added to the color-developing substance and the 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, and addition product of ethylene oxide and fatty alcohol. As a thickener,
Examples include methyl cellulose, starch, higher fatty alcohols, paraffin oil, fatty acids, etc., and examples of stabilizers include reducing agents such as sulfites, hydroquinone derivatives, chelating agents, etc. Examples thereof include silicones, higher alcohols, oil agents 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 0.001 to 10% by weight.
(Hereinafter, simply indicated by%), particularly preferably 0.01 to 5%. It is preferable that the wetting agent (emulsifier) is usually added in an amount of 0.5 to 30% and the thickening agent is added in an amount of 0.1 to 25%. Further, in these dosage forms, the pH of the entire composition is preferably adjusted to about 6-11.

To dye keratinous fibers using the dye composition of the present invention, for example, an oxidizing agent is added to the dye composition of the present invention to perform oxidative coupling to prepare a dye solution, and the dye solution is prepared. Applied to keratinous fibers for 5 to 50 minutes, preferably 2
The keratinous fibers may be washed after a working time of about 5 to 30 minutes and then dried. Here, the application of the staining solution is 15 to 4
It is carried out at 0 ° C.

[0029]

INDUSTRIAL APPLICABILITY As described above, in a keratin fiber dyeing agent composition comprising a color-developing substance and a coupling substance, a 2-alkyl-4-alkoxy-5-aminophenol derivative or its salt (1) is used as the coupling substance. Is a keratin fiber dyeing composition that can be obtained with a high color tone having good dyeing properties, resistance to fading, washing resistance and abrasion resistance, and is also compounded after long-term storage of the coupling substance. The color saturation and dyeing power of the object are not reduced.

[0030]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) To 500 ml of acetone, 200 g of 4-mesyloxy-5-methyl-2-nitrophenol and 7% of diethylsulfate were added.
20 g and 510 g of sodium carbonate were added, and the mixture was heated under reflux for 24 hours. After cooling, pour into 2 liters of water and add 2 liters of chloroform.
It was extracted with. The extract was washed with saturated brine and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give brown crystals. This was recrystallized from a mixed solvent of hexane-acetone (2: 1),
192 g of 4-ethoxy-2-methyl-5-nitrophenyl mesylate was obtained. Yield 86%. (2) To 1200 ml of methanol, 141.6 g of 4-ethoxy-2-methyl-5-nitrophenyl mesylate (5
(15 mmol), 200 ml of 3N aqueous sodium hydroxide solution was added, and the mixture was heated under reflux for 2 hours. After cooling, it was neutralized with hydrochloric acid and poured into 3000 ml of water to precipitate crystals. This was filtered and washed with water to obtain 114.1 g of 4-ethoxy-2-methyl-5-nitrophenol (containing water). This was used for the next reaction without drying. (3) In a 1200 ml autoclave, 4 obtained above
-Ethoxy-2-methyl-5-nitrophenol (containing water) (30 g), 5% palladium carbon (3.0 g) and ethanol (500 ml) were added, and the mixture was stirred at 50 kg / cm ^-1 and 50 ° C. for 6 hours. After cooling, the catalyst was filtered off and the filtrate was evaporated under reduced pressure to give reddish brown crystals. This is subjected to silica gel column chromatography (Merck Si60, 230 to 400 mesh, 200 g, elution solvent ethyl acetate), and 50
The 0-200 ml eluate was concentrated under reduced pressure to 100 ml.
400 ml of hexane was added to this, and the precipitated crystals were filtered,
After drying, 10.5 g (62.9 mmol) of pale red crystals of 5-amino-4-ethoxy-2-methylphenol were obtained. Yield 47% from 4-ethoxy-2-methyl-5-nitrophenyl mesylate.

(4) 5-amino-in 50 ml of dioxane
4-ethoxy-2-methylphenol 10.0 g (5
9.9 mmol) and 3.37 g of calcium carbonate are added, and 90
The temperature was raised to ° C. To this, 9.9 g of β-chloroethyl chloroformate was added dropwise over 30 minutes, and the mixture was further added for 90 minutes for 1 hour.
Stir at ℃. This was cooled to 50 ° C. and the inorganic salt was filtered off. The inorganic salt was washed with 50 ml of dioxane. The filtrate and washings were combined and concentrated to 40 ml. This is water 150
The precipitated crystals were filtered and washed with water, and N- (2-
Ethoxy-4-methyl-5-hydroxyphenyl) -2
17.21 g of -chloroethyl carbamate (containing water) was obtained. This was used for the next reaction without drying. (5) 16.69 g of N- (2-ethoxy-4-methyl-5-hydroxyphenyl) -2-chloroethylcarbamate (containing water) obtained above was added to 100 ml of 6N sodium hydroxide aqueous solution, and nitrogen was added. The mixture was heated under reflux for 4 hours with aeration. After cooling, it was neutralized with acetic acid, and the precipitated crystals were filtered and washed with water to give red crystals. This was subjected to silica gel column chromatography (Merck Si60, 230 to 400 mesh, 100 g, elution solvent ethyl acetate), and 0
The .about.1000 ml eluate was concentrated under reduced pressure to 100 ml.
400 ml of hexane was added to this, and the precipitated crystals were filtered,
Dry to give pale ethoxy crystals of 4-ethoxy-5- (2-hydroxyethyl) amino-2-methylphenol.
Obtained 50 g (33.6 mmol). Yield 58% from 5-amino-4-ethoxy-2-methylphenol.

Melting point: 115-116 ° C. ¹ H-NMR (200 MHz, DMSO-d ₆ ) δ ppm: 1.27 (3 H, t, J = 7.0 Hz),
1.97 (3H, s), 2.99 (2H, td, J = 5.8,5.5Hz), 3.57 (2H, dt, J =
5.5,5.1Hz), 3.86 (2H, q, J = 7.0Hz), 4.49 (1H, t, J = 5.8Hz),
4.72 (1H, t, J = 5.1Hz), 6.07 (1H, s), 6.49 (1H, s), 8.37 (1
H, s) .IR (KBr) νcm ^-1 : 3492, 3328, 2956, 1624, 1426, 1266,
1198, 1116, 1034, 840.

Example 2 1.50 g of 5-amino-4-ethoxy-2-methylphenol obtained in Example 1 (3) was added to 10 ml of ethanol.
(9.0 mmol), acetic anhydride 1.02 g (10.0 mmol)
Was added and the mixture was stirred at room temperature for 1 hour. 10 ml of water was added to this, and the crystals were filtered and washed with water to obtain crude crystals. This was recrystallized from acetonitrile to give N- (2-ethoxy-5-
1.23 g (5.9 mmol) of pale red crystals of hydroxy-4-methylphenyl) acetamide were obtained. Yield 66%.

Melting point: 218 to 220 ° C. ¹ H-NMR (200 MHz, DMSO-d ₆ ) δ ppm: 1.30 (3 H, t, J = 7.0 Hz),
2.05 (3H, s), 2.05 (3H, s), 3.94 (2H, q, J = 7.0Hz), 6.71 (1
H, s), 7.53 (1H, s), 8.73 (1H, s), 8.79 (1H, s) .IR (KBr) νcm ^-1 : 3424, 3184, 1654, 1536, 1418, 1262,
1202, 1110, 1032, 880, 756.

Example 3 (1) 3 g (20 mmol) of 5-amino-4-ethoxy-2-methylphenol obtained in Example 1 (3) was added to pyridine 3
Dissolve it in 0 ml, and cool with ice, 4.6 ml of benzoyl chloride (4 ml
0 mmol) was added dropwise over 5 minutes. Stir for 1 hour,
Then, after standing overnight at room temperature, the reaction mixture was diluted with water and the precipitated solid was collected by filtration. This was washed with water, dried azeotropically with ethanol, and recrystallized from toluene to obtain 5.2 g (14 mmol) of colorless needle crystals of 5-benzamido-4-ethoxy-2-methylphenylbenzoate. Yield 73% from 5-amino-4-ethoxy-2-methylphenol.

(2) 5-benzamide-obtained above
4-ethoxy-2-methylphenyl benzoate 3
g (8.3 mmol) 0.4 N sodium hydroxide aqueous solution 5
A mixed solvent of 4 ml (21 mmol) and 10 ml of ethanol was added, and the mixture was heated and stirred in an oil bath at 100 ° C. for 3 hours. After cooling
15 ml of 2N hydrochloric acid was added, and the mixture was extracted with ethyl acetate. After drying and concentration with anhydrous sodium sulfate, the obtained solid was recrystallized from ethanol-water to give 5-benzamide-
1.8 g (6.6 mmol) of yellow needle crystals of 4-ethoxy-2-methylphenol were obtained. 5-benzamide-4-
Yield 80% from ethoxy-2-methylphenyl benzoate.

Melting point: 177.0 to 178.2 ° C. ¹ H-NMR (200 MHz, DMSO-d ₆ ) δ ppm: 1.31 (3 H, t, J = 6.9 Hz),
2.11 (3H, s), 3.99 (2H, q, J = 6.9Hz), 6.81 (1H, s), 7.4-7.7
(2H + 1H + 1H, m), 7.92 (2H, d, J = 6.2Hz), 8.94 (1H, s), 9.14
(1H, s) IR (KBr) νcm ^-1 : 3424, 3324, 3164, 1642, 1488, 1434,
1376, 1270, 1192, 1110, 1028, 870, 684, 614

Example 4 (1) 3 g (20 mmol) of 5-amino-4-ethoxy-2-methylphenol obtained in Example 1 (3) was added to pyridine 3
Dissolve in 0 ml, and under ice cooling, methanesulfonyl chloride 3.1
ml (40 mmol) was added dropwise over 5 minutes. The mixture was stirred as it was for 1 hour and then left overnight at room temperature, the reaction mixture was diluted with water, and the precipitated solid was collected by filtration. This was washed with water and recrystallized from acetonitrile to obtain 5.1 g (16 mmol) of colorless plate crystals of 4-ethoxy-5-methanesulfonamido-2-methylphenyl mesylate. 5-amino-4
80% yield from ethoxy-2-methylphenol.

(2) 4-ethoxy-5-obtained above
3 g (9.3 mmol) of methanesulfonamido-2-methylphenyl mesylate was added to 100 ml (0.16 mol) of 1.6N sodium hydroxide aqueous solution, and the mixture was heated under reflux for 1 hour (oil bath temperature 140 ° C.). Under ice cooling, 16 cc of concentrated hydrochloric acid was added dropwise for neutralization, followed by extraction with ethyl acetate and drying with anhydrous sodium sulfate. After concentration under reduced pressure, the obtained solid was washed with ethyl acetate-
Recrystallization from hexane gave 1.8 g of colorless plate crystals of 4-ethoxy-5-methanesulfonamide-2-methylphenol.
g (4.4 mmol) was obtained. Yield 48% from 4-ethoxy-5-methanesulfonamido-2-methylphenyl mesylate.

Melting point: 146.5-149.0 ° C. ¹ H-NMR (200 MHz, DMSO-d ₆ ) δ ppm: 1.32 (3 H, t, J = 6.9 Hz),
2.09 (3H, s), 2.89 (3H, s), 3.96 (2H, q, J = 6.9Hz), 6.77 (1H,
s), 6.78 (1H, s), 8.57 (1H, s), 8.94 (1H, s) IR (KBr) νcm ^-1 : 3472, 3264, 2984, 2924, 2880, 1500,
1482, 1442, 1382, 1338, 1292, 1204, 1124, 1104, 97
2, 898, 854, 756, 564, 504

Test Example 1 In a 10 ml transparent sample bottle, 1.0 g of the coupling substance shown below was placed and stored at 60 ° C. for 5 days. Liquid chromatography was performed on each sample before and after storage under the conditions shown below, and the residual ratio of each coupling substance was calculated from the area of the obtained peak. The results are shown in Table 1.
Shown in. (Coupling agent) C _1: 4-ethoxy-5- (2-hydroxyethyl) amino-2-methylphenol (present invention product) C _2: 5-(2-hydroxyethyl) amino-4-methoxy-2- Methylphenol (Comparative product) (Analysis conditions of liquid chromatography) Sample 50.0 mg
Ethanol was added to the solution and dissolved to make 50 ml. 20 μl of this sample solution was taken and analyzed under the following conditions. Detector: Ultraviolet absorptiometer (measurement wavelength: 254 nm) Column: Mercury Supersphere with an average particle diameter of 4 μm in a stainless steel tube with an inner diameter of 4.0 mm and a length of 125 mm
It was filled with PR-18 (e). Column temperature; room temperature Mobile phase: 1% (w / w) sodium perchlorate aqueous solution-acetonitrile (3: 1, v / v) Flow rate: 0.5 ml / min

[0043]

[Table 1]

As is clear from Table 1, the coupling substance of the present invention showed excellent storage stability as compared with the comparative product.

[0045]

Table 2 Example 5 Base composition: (%) Oleic acid 10 Oleic acid diethanolamide 8 Oleyl alcohol 2 Polyoxyethylene octyldodecyl ether (average EO 20 moles added) 10 Ethanol 15 Propylene glycol 10 Ammonium chloride 3 25% Ammonia 7 Water 35 total 100

In 100 g of the base having the above composition, 0.01 mol of p-aminophenol as a color developing substance and 0.01 of 4-ethoxy-5- (2-hydroxyethyl) amino-2-methylphenol as a coupling substance. Mixed with moles. The pH of the composition is then adjusted to 9 with ammonia.
By adjusting to 5, the dyeing composition of the present invention was produced.

A dyeing solution was prepared by adding an equal weight of a 6% aqueous hydrogen peroxide solution to 100 g of the obtained dyeing composition of the present invention. Apply this dyeing solution to human hair with white hair,
It was left at 30 ° C. for 30 minutes. The hair was then washed with normal shampoo and dried. As a result, a highly saturated reddish color tone having good dyeability, resistance to discoloration, washing resistance and abrasion resistance could be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hidetoshi Tagami 2-1-3 Bunhana Sumida-ku, Tokyo 2-1-3 Kao Co., Ltd. Tokyo Research Laboratory (72) Inventor Toru Yoshihara 2-1-3 Fumika Sumida-ku, Tokyo Tokyo Research Institute, Kao Corporation (72) Kenichi Matsunaga, 2-1-3 Fumika, Sumida-ku, Tokyo 2-1-3 Tokyo Research Institute, Kao Corporation (72) Masahiko Ogawa, 2-1-3, Fumika, Sumida-ku, Tokyo Kao Corporation, Tokyo Research Laboratory

Claims (2)

[Claims] 1. The following general formula (1): (In the formula, R ¹ represents a lower alkyl group, R ² and R ³ are the same or different, and a hydrogen atom, an alkyl group optionally substituted by a hydroxy group, a lower alkanoyl optionally substituted by a halogen atom. Group, an arylcarbonyl group or a lower alkylsulfonyl group, and R ⁴ represents a lower alkyl group having 2 or more carbon atoms, provided that R ² and R ³ are not simultaneously hydrogen atoms). -4-Alkoxy-5-aminophenol derivative or a salt thereof. 2. A keratin fiber dyeing composition comprising a 2-alkyl-4-alkoxy-5-aminophenol derivative or a salt thereof according to claim 1 as a coupling substance and a color developing substance.