JPH0653652B2 - Keratin fiber dye composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel benzoxazine derivative or a salt thereof, an intermediate useful for the production thereof, and a keratin fiber dyeing composition containing the benzoxazine derivative or a salt thereof as a coupling substance. .

[0002]

2. Description of the Related Art For dyeing keratinous fibers such as hair, so-called oxidative dyes, which use a combination of 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, a p-phenylenediamine derivative, a p-aminophenol derivative, a diaminopyridine derivative, a 4-aminopyrazolone derivative, a heterocyclic hydrazone, etc. are generally used, and as 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, o-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-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-diaminotrifluoromethylbenzene, 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.

[0003]

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, a coupling substance excellent in saturation, dyeing power and fastness has been desired.

[0004]

Under such circumstances, the present inventors have synthesized many compounds and examined their properties as coupling substances.
The inventors have found that the benzoxazine derivative represented by (1) and its salt have the above-mentioned excellent properties, and completed the present invention.

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

[Chemical 3] [Wherein R ¹ represents a lower alkyl group, ═X represents ═O or two hydrogen atoms], or a salt thereof, and the compound as a coupling substance and a color developing substance. The present invention provides a keratin fiber dyeing agent composition containing: In the formula, the lower alkyl group represented by R ¹ is a methyl group, an ethyl group,
Examples include propyl group and the like.

The benzoxazine derivative of the present invention is produced, for example, according to the following reaction formula.

[Chemical 4] [In the formula, R ¹ represents a lower alkyl group, and R ² represents an alkylsulfonyl group or an arylsulfonyl group]

That is, first, compound (3) is reduced to form compound (4), and then this compound (4) is reacted with α-halogenoacetic acid or a reactive derivative thereof in the presence of a base to give N-halogeno. After converting to an acetyl derivative, the compound is reacted with a base to ring-close to obtain a compound (2a). Further, by hydrolyzing the compound (2a), the compound (1a) of the present invention can be obtained.

On the other hand, the compound (2a) obtained above is reduced to give the compound (2b), which is then hydrolyzed to obtain the compound (1b) of the present invention.

In the above reaction formula, R ² is an alkylsulfonyl group or an arylsulfonyl group, and specific examples thereof include a methylsulfonyl group, an ethylsulfonyl group and a p-toluenesulfonyl group.

The compound (3) as a raw material is disclosed, for example, in JP-A-62-62.
-240960 publication and other known methods.

The reduction reaction for obtaining the compound (4) from the compound (3) is carried out according to a reduction reaction known per se, for example, catalytic reduction using a catalyst such as palladium-carbon.
In addition, examples of the base used in the reaction of compound (4) to compound (2a) include sodium hydrogencarbonate and the like, and the halogen of α-halogenoacetic acid includes chlorine, bromine, iodine and the like.

The reduction reaction for obtaining the compound (2b) from the compound (2a) is also carried out according to a reduction reaction known per se, and sodium borohydride or the like can be used as the reducing agent. Then, the compound (2a) or the compound (2b) is hydrolyzed using sodium hydroxide or the like according to a conventional method to produce the compound (1a) of the present invention or the compound (1b) of the present invention.

Benzoxazine derivative thus obtained
(1) is used as a coupling substance, and can be used in the form of a salt in order to improve the handling property in formulation. As such a salt, for example, a salt with an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid, citric acid or an organic acid is preferable.

In the present invention, as the color-developing substance, those which are generally used for oxidation dyes can be used. For example, p-phenylenediamine, toluene-
2,5-diamine, N-phenyl-p-phenylenediamine, p-aminophenol, methoxy-p-phenylenediamine, 2,5-diaminopyridine, p-methylaminophenol, tetraaminopyrimidine, 2,4-diaminophenol , Orthoaminophenol, orthochloro-p-phenylenediamine, 4,4′-diaminodiphenylamine and the like. Among them, p-phenylenediamine, toluene-2,5-diamine, N-phenyl-p-phenylenediamine, methoxy-p-phenylenediamine, orthochlor-p-phenylenediamine and the like are particularly preferable.

The mixing ratio of the color-developing substance to the benzoxazine derivative or its salt (1) in the dye composition of the present invention may be one in excess of the other, but the molar ratio is 1: It is preferably about 0.5 to 1: 5. Further, the color-developing substance and the coupling substance may 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 and the like, if necessary, in order to obtain a desired color tone. Examples of such a direct dye include 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, nitro-p-phenylenediamine hydrochloride, which are described in the dye raw material standard issued by the Japan Hair Color Industry Association. Nitro-p-phenylenediamine, p-aminophenylsulfamic acid, p-nitro-o-phenylenediamine, picramic acid, sodium picramate, picric acid, chrome brown RH, hematein, nitro-p-phenylenediamine sulfate, p-sulfate Nitro-o-phenylenediamine, p-nitro-m-phenylenediamine sulfate, 1-amino-4-methylaminoanthraquinone, 1,4-diaminoanthraquinone; acid dyes Red No. 2, Red No. 3, Red No. 102,
Red 104, Red 105, Red 106, Yellow 4, Yellow 5, Green 3, Blue 1, Blue 2, Red 201, Red 227, Red 230, Red 231, Red 232 No., orange 20
No. 5, Orange 207, Yellow 202, Yellow 203, Green 201
No. 204, Green No. 204, Green No. 205, Blue No. 202, Blue No. 203
No. 205, Blue No. 205, Brown 201, Red 401, Red 502
No., red 503, red 504, red 506, orange 402,
Yellow No. 402, Yellow No. 403, Yellow No. 406, Yellow No. 407, Green No. 401, Green No. 402, Purple No. 401, Black No. 401; Oil-soluble dyes Red No. 215, Red No. 218, Red No. 225, Orange 20
No. 1, orange 206, yellow 201, yellow 204, green 202
No. 201, 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 Blu.
e, Straw Yellow and the like, but nitrophenylenediamine, nitro-aminophenol and anthraquinone dyes are particularly preferable.

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 preferred to cause oxidative coupling by adding a chemical oxidant. . 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, 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 preferably 0.001 to 10% by weight (hereinafter simply referred to as%), particularly 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%.

To carry out dyeing of 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 carry out oxidative coupling to prepare a dyeing solution,
Apply this dyeing solution to keratinous fibers for 5 to 50 minutes, preferably
It is carried out by washing the keratinous fibers after a working time of about 25 to 35 minutes and then drying. The application of the dyeing solution here takes place at 15-40 ° C.

[0021]

INDUSTRIAL APPLICABILITY As described above, in the keratin fiber dyeing composition comprising a color-developing substance and a coupling substance, the benzoxazine derivative of the present invention or a salt thereof is used as the coupling substance.
By using (1), good dyeability, light resistance, resistance to discoloration,
It is possible to obtain a color tone of high saturation having washing resistance and abrasion resistance.

[0022]

EXAMPLES Next, more detailed description will be given with reference to Examples.
The present invention is not limited to these.

Example 1 (1) 5'-Amino-4'-hydroxy-2'-methylphenyl methanesulfonate (4-1, (4) wherein R ^{1 is} :
Methyl, R ^2: Synthesis of methanesulfonyl group): 200 ml
In the autoclave, 10% palladium on carbon 1.66g, 5 '
- nitro-4'-hydroxy-2'-methylphenyl methanesulfonate (3-1 (3) wherein, R ^1: a methyl group, R ^2: methanesulfonyl group) 20.26 g (82.0 mmol),
Add 120 ml of ethanol, press-fit 50 kg / cm ² of hydrogen, and
The mixture was stirred at ℃ for 4.5 hours. After cooling, palladium carbon was filtered and the solvent was distilled off under reduced pressure to obtain brown crystals. This was washed with hexane-ethyl acetate (1: 1) to obtain 15.21 g (70.1 mmol) of pale yellow crystals of the title compound. Yield 86%. mp. 151.0-153.0 ℃ ¹ H-NMR (200MHz, DMSO-d ₆ ) δppm; 2.05 (3H, s), 3.35 (3H, s), 4.62 (2H, brs), 6.89
(1H, s), 6.93 (1H, s), 9.18 (1H, s) IR (KBr) νcm ^-1 ; 3392, 3300, 3030, 1346, 1170 Elemental analysis (as C ₈ H ₁₁ NO ₄ S) Calculated value C; 44.23%, H; 5.10%, N; 6.45%, S;
14.76% Found C; 44.48%, H; 5.11%, N; 6.24%, S;
14.62%

(2) 3,4-dihydro-6- (methanesulfonyl) oxy-7-methyl-2H-1,4-benzoxazin-3-one (2a-1, (2) where R ^{1 is} : methyl, R ^2: methanesulfonyl group, = X: = O) synthesis of:
5.00 g (23.0 mmol) of compound (4-1) in 50 ml of dioxane,
Sodium hydrogen carbonate (4.97 g) was added, and chloroacetic acid chloride (3.12 g, 27.6 mmol, 1.2 eq.) Was added dropwise to this solution over 5 minutes, and the mixture was further stirred at room temperature for 30 minutes. This was poured into 150 ml of water and extracted with 200 ml of ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 6.38 g of N-chloroacetyl derivative. Water this
In addition to 300 ml, sodium hydrogen carbonate 5.48 g (65.2 mmol, 3.
0 eq.) Was added and the mixture was stirred at 60 ° C. for 220 minutes. After cooling, this solution was poured into 300 ml of water and extracted with 400 ml of ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain yellowish brown crystals. This was recrystallized from ethanol to obtain 4.55 g (17.7 mmol) of light brown crystals of the title compound. Yield 77%. mp. 172.0-173.0 ℃ ¹ H-NMR (200MHz, DMSO-d ₆ ) δppm; 2.19 (3H, s), 3.40 (3H, s), 4.57 (2H, s), 6.88 (1
H, s), 6.95 (1H, s) IR (KBr) νcm ^-1 ; 3210, 3052, 1690, 1348, 1192, 1164 Elemental analysis (as C ₁₀ H ₁₁ NO ₅ S) Calculated value C; 46.69%, H 4.31%, N; 5.44%, S;
12.46% Actual value C; 46.70%, H; 4.33%, N; 5.26%, S;
12.64%

Example 2 3,4-Dihydro-6- (methanesulfonyl) oxy-
7-methyl-2H-1,4-benzoxazine (2b-1,
(2) In the formula, synthesis of R ¹ : methyl group, R ² : methanesulfonyl group, = X: = H ₂ ): dioxane 50 ml, compound (2a-1) 4.48 g (17.4 mmol), acetic acid 2.0 ml In addition, sodium borohydride 3.29 g (124 mmol,
7.2 eq.) Was gradually added, and the mixture was further heated under reflux for 4 hours. After cooling, this solution was poured into 300 ml of water and left standing overnight. This was extracted with 300 ml of ethyl acetate, the organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain a brown oily substance. Silica gel column chromatography (Merck Si60, 70-230 mesh, 200
g, chloroform) and brown crystals (3.36 g) were obtained from the 700-1900 ml fraction. This was recrystallized from hexane-ethyl acetate (1: 1) to give pale yellow crystals of the title compound as 2.
40 g (9.88 mmol) was obtained. Yield 57%. mp. 86.5-87.5 ℃ ¹ H-NMR (200MHz, CDCl ₃ ) δppm; 2.20 (3H, s), 3.13 (3H, s), 3.39 (2H, t, J = 4.0H
z), 4.22 (2H, t, J = 4.0Hz), 6.58 (1H, s), 6.63 (1H, s) IR (KBr) νcm ^-1 ; 3404, 1338, 1180, 1158 Elemental analysis (C ₁₀ H ₁₃ NO ₄ as S) calculated C; 49.37%, H; 5.39 %, N; 5.76%, S;
13.18% Found C; 49.27%, H; 5.31%, N; 5.71%, S;
13.30%

Example 3 3,4-Dihydro-6-hydroxy-7-methyl-2H
Synthesis of -1,4-benzoxazin-3-one (1a-1, (1) in the formula, R ¹ : methyl group, = X: = O): methanol
To 35 ml, 4.00 g (15.6 mmol) of compound (2a-1) and 1.64 g of sodium hydroxide were added, and the mixture was heated under reflux for 3.5 hours. After cooling
It was poured into 200 ml of water, neutralized with acetic acid, further poured into 200 ml of water and extracted with 400 ml of chloroform. The organic layer is washed with water,
It was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure,
Brown crystals were obtained. Silica gel column chromatography (Merck Si60, 230-400 mesh, 200g, ethyl acetate)
Purified by 940 mg of light brown crystals of the title compound (5.25 mmo
l) Got it. Yield 34%. The title compound was purified by recrystallization from hexane-ethyl acetate. mp. 235-240 ℃ (decomp.) ¹ H-NMR (200MHz, DMSO-d ₆ ) δppm ； 2.01 (3H, s), 4.39 (2H, s), 6.40 (1H, s), 6.65 (1
H, s), 9.06 (1H, s) IR (KBr) νcm ⁻¹ ; 3476, 3070, 1688 Elemental analysis (as C ₉ H ₉ NO ₃ ) Calculated value C; 60.33%, H; 5.06%, N; 7.82 % Measured value C; 59.22%, H; 5.04%, N; 7.45%

Example 4 3,4-Dihydro-6-hydroxy-7-methyl-2H
-1,4-benzoxazine (1b-1, (1) in the formula,
R ¹ : Methyl group, = X: = H ₂ ) Synthesis: In 45 ml of methanol, 2.40 g of compound (2b-1).
(9.88 mmol) was added, and the atmosphere was replaced with nitrogen at room temperature.
20 ml of 3.3N aqueous sodium hydroxide solution was added, and the mixture was heated under reflux for 4 hours while bubbling nitrogen through. After cooling, add acetic acid to neutralize, pour into 200 ml of water, and add 250 ml of ethyl acetate.
Extracted with ml. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain brown crystals. This was recrystallized from ethanol to obtain 700 mg (4.24 mmol) of yellow crystals of the title compound. Yield 43%. mp. 134.7-136.2 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm; 2.28 (3 H, s), 3.37 (2 H,
t, J = 4.0 Hz), 4.19 (2H, t, J = 4.
0 Hz), 6.12 (1H, s), 6.55 (1H,
s) IR (KBr) νcm ⁻¹ ; 3320 Elemental analysis (as C ₉ H ₁₁ NO ₂ ) Calculated value C; 65.44%, H; 6.71%, N; 8.48% Measured value C; 65. 44%, H; 6.71%, N; 8.45%

Example 5 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 Total 100 In 100 g of the base having the above composition, the color-developing substances shown in Table 1
0.01 mol and 0.01 mol of coupling substance were mixed in. Next, the dye 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. Table 1 shows the results obtained by observing the color tone, dyeability, saturation, and fading resistance of the obtained dyed hair. The resistance to fading is 40
After storing at 60 ° C. and 75% RH for 60 hours and then drying at room temperature, it was visually compared with hair dye tress stored at −5 ° C. and judged according to the following criteria.

(Evaluation Criteria for Dyeing Property, Saturation and Fading Resistance) ◎: Very Good ○: Good Δ: Slightly Poor ×: Poor (Developer Substance) P ₁ ; Paraphenylenediamine P ₂ ; Toluene 2,5-diamine P _3; para-aminophenol (coupling agent) C _1; 3,4-dihydro-6-hydroxy-7-methyl-2H-1,4-benzoxazine C _2; 3,4-dihydro - 6-hydroxy-7-methyl-2H-1,4-benzoxazin-3-one C _3; m-phenylenediamine C _4; para-ortho-cresol C _5; 2-methyl-5-(beta-hydroxyethyl) aminophenol

[0031]

[Table 1]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michio Tanaka 2606 Akabane, Kaiga-cho, Haga-gun, Tochigi Prefecture Kao Institute of Bioscience (72) Inventor Hidetoshi Tagami 2-1-3 Sumika-ku, Tokyo Kao Tokyo Lab In-house (72) Inventor Toru Yoshihara 2-1-3 Bunka, Sumida-ku, Tokyo 2-1-3 Kao Tokyo Lab In-house (72) Inventor Masahiko Ogawa 2-1-3 Bunka, Sumida-ku, Tokyo Kao-Tokyo Lab (72) ) Inventor Tsutomu Muraoka 2-1-3 Bunka, Sumida-ku, Tokyo Inside Kao Tokyo Laboratory (72) Inventor Jiro Kawase 2-1-3 Bunka, Sumida-ku, Tokyo Inside Kao Tokyo Laboratory

Claims (3)

[Claims] 1. The following general formula (1): [Wherein, R ¹ represents a lower alkyl group, ═X represents ═O or two hydrogen atoms], or a benzoxazine derivative or a salt thereof. 2. The following general formula (2): [In the formula, R ¹ represents a lower alkyl group, ═X represents ═O or two hydrogen atoms, and R ² represents an alkylsulfonyl group or an arylsulfonyl group] or a salt thereof. 3. A keratinous fiber dyeing composition comprising a benzoxazine derivative or a salt thereof according to claim 1 and a color developing substance as a coupling substance.