WO2008025240A1 - Composition comprising amino heterocyclic compound for hair dyeing and dyeing method - Google Patents

Abstract

A dye composition comprising amino heterocyclic compound and preparing process thereof. The amino heterocyclic compound is selected from tetrahydroquinoline of general formula (I), and the acid addition salts thereof, as well as amino-containing indoline of general formula (II), and the acid addition salts thereof.

Description

 Amino heterocyclic compound-containing composition and dyeing method for hair dyeing, technical field

 The present invention relates to a composition for an amino group-containing heterocyclic compound for dyeing keratin fibers, and a dyeing method using the composition. Background technique

 It has been known that so-called permanent hair dyes are spread into the epidermis of the hair with a sufficiently small substance which is not a dye but forms a dye after entering the hair during the dyeing process.

 A key component of such products is called oxidative dye developers, which are ammonia or phenolic derivatives such as p-phenylenediamine and p-aminophenol. These substances cannot be dyed but can be rapidly oxidized to intermediates. It reacts with other compounds to form a macromolecular dye. Since these macromolecular dyes are formed after entering the hair, they are difficult to wash off with shampoo, and can achieve permanent in a certain sense. Therefore, they are called permanent hair dyes, and the process of forming dyes is actually caused by oxidation reaction. The compound is therefore also known as an oxidative hair dye.

 It is known that the color tone obtained by the oxidation dye developer can be changed by combining with a dye coloring agent or a modifier, and these coloring agents or modifiers are specifically selected from aromatic diamines and meta-aminophenols. , resorcinol and certain heterocyclic compounds.

 We also know that the so-called permanent color obtained from these oxidative dyes should meet certain needs, so it should be no problem on the toxicological diagram, and should be able to obtain different shades at the required strength, and in various External factors such as light, bad weather, washing, permanent perm, sweating, rubbing, etc. all show a good appearance. At the same time, these dyes should also be able to cover white hair, and finally have as little selectivity as possible. This means that the keratin fibers should be able to get as small a color difference as possible, but actually in the hair and hair. The degree of sensitization between the roots is different (ie, dye defects).

Oxidation dyes for permanent dyeing of keratin fibers are usually designed as monocyclic or bicyclic aromatic compounds having substituents such as amino groups and hydroxyl groups. Monocyclic or bicyclic rings are not designed for more rings because often only the molecular diameter of a single or bicyclic aromatic compound is small enough, and only compounds of sufficiently small molecular diameter have the opportunity to diffuse and penetrate keratin fibers. surface layer. In addition to the reactive groups such as substituted amino groups and hydroxyl groups, the aromatic ring should have one or more unsubstituted positions to form a sufficiently large π-conjugated system when oxidative coupling reaction occurs inside the keratin fibers. Colored substance, the colored substance at this time has a larger molecular diameter, and thus it is difficult to extract from the egg The "escape" inside the white fiber can achieve the goal of "permanence." .

 We have found that in some of the previous literatures and patents, there are some polycyclic (more than two rings) compounds reported as oxidative dyes. In actual dyeing operations, it is still possible to use a method of forcibly expanding the surface of keratin fibers, such as A strong alkaline dyeing environment, a penetration-enhancing surfactant, etc., successfully dye the keratin fibers. French patent

Fr2844272—“New tricyclic indole or tetrahydroquinoline derivatives useful as developers in oxidation dye compositions for dyeing keratinic fibers, especially human hair”- proposed a "tricyclic compound" containing hydrazine or tetrahydroquinoline as an oxidative dye composition Report. Its structural formula is -

 ( in ) ( IV )

 The inventors have noted that existing and conventional oxidative dyes, which result in oxidative coupling reactions, often result in dark shades such as red, brown or even near black. This is because in the presence of sufficient oxidant, reactive groups such as amino groups and hydroxyl groups on the aromatic ring undergo complex oxidative coupling reactions with unsubstituted positions on the aromatic ring, forming a "too large" π-co- The yoke system causes dark tones to appear. It is difficult to control the amount of oxidant during the dyeing process, not to mention the presence of oxygen and water in the air, which is often sufficient to cause oxidative coupling reactions in most oxidative dyes. Summary of the invention

 The technical problem to be solved by the present invention is to disclose a composition containing an amino heterocyclic compound for dyeing hair and a dyeing method to overcome the drawbacks of the prior art.

In order to obtain a stable light-colored hue, such as blue and green dyeing results, it is necessary to find some oxidative dyes which can form a "smaller" π-conjugated system by oxidative coupling reaction. The idea of the design of this kind of dye molecule is proposed as follows: Whether it is a benzene ring or a heterocyclic aromatic ring, in addition to the necessary reactive groups such as amino group and hydroxyl group, when the unsubstituted position on the ring is more inactive After the group is substituted by a methyl group, the space on the ring where the oxidative coupling reaction occurs is compressed, which results in the formation of a smaller π-conjugated system, resulting in a stable pale hue. Of course, the inactive groups in adjacent positions can be replaced by saturated rings, which also achieve "closed" Part of the space where the reaction can occur.

 The present inventors have found that the amino group-containing tetrahydroquinoline of the formula (I) as defined below, and the amino group-containing indoline of the formula (II) as defined below are used. It is suitable as an oxidation dye precursor, and it can also obtain a dye composition which is extremely pure in color from blue to green, and is not easy to fade and has good stability. Finally, these compounds have proven to be readily synthesized and these findings form the basis of the present invention.

 The amino heterocyclic compound-containing composition for hair dyeing of the present invention contains at least an amino group-containing heterocyclic compound in a medium suitable for dyeing, and the amino group-containing heterocyclic compound is selected from the formula (I) An aminotetrahydroquinoline, an addition salt of an aminotetrahydroquinoline of the formula (I) with an acid, an amino group-containing indoline of the formula (II), an amino group-containing compound of the formula (II) One or more of the addition salts of hydroquinone and acid;

 Said hair refers to keratin fibers of human or animal;

In the formula (I) and the formula (Π): at a substitutable position of the nitrogen atom, R ₂ is at a position replaceable on the saturated ring, and at a position replaceable at the R ₃ position and the phenyl ring except for the amino group, Simultaneously or independently represent hydrogen, amino, substituted amino, -C^alkyl, decyloxy, halo, ester, carboxy or nitro, and R ₂ and R ₃ may be represented as 1 to 3 identical or different substitutions, respectively. Group.

 In general, the addition salt with an acid is selected in particular from the hydrochloride, hydrobromide, sulfate, tartrate, lactate or acetate;

 Preferred amino-containing tetrahydroquinolines of formula (I) are:

 N-methyl-7-aminotetrahydroquinoline,

 N-benzyl-7-aminotetrahydroquinoline,

 7-Amino-3-hydroxymethyl-1-(2'-methoxyphenyl)tetrahydroquinoline,

 7-Amino-3-hydroxymethyl-1-(3'-methoxyphenyl)tetrahydroquinoline,

 7-Amino-3-light methyl-1-(4,-methoxyphenyl)tetrahydroquinoline,

 N-ethyl-7-aminotetrahydroquinoline,

N-hydroxyethyl-7-aminotetrahydroquinoline, N-isobutyl-7-aminotetrahydroquinoline,

 7-Amino-3-methyl-1-(2,-methoxyphenyl)tetrahydroquinoline,

7-Amino-3-methyl-1-(3'-methoxyphenyl)tetrahydroquinoline,

7-Amino-3-methyl-1-(4,-methoxyphenyl)tetrahydroquinoline,

N-tert-butyl-7-aminotetrahydroquinoline,

 1, 3-dimethyl-7-aminotetrahydroquinoline,

 7-Amino-3-hydroxymethyl-1-isobutyltetrahydroquinoline,

 7-Amino-3-dimethylaminomethyl-1-methyltetrahydroquinoline,

7-Amino-3-dimethylaminomethyl-1-ethyltetrahydroquinoline,

7-Amino-3-dimethylaminomethyl-1-tert-butyltetrahydroquinoline,

7-Amino-3-dimethylaminomethyl-1-isopropyltetrahydroquinoline,

7-Amino-3-methyl-1-hydroxyethyltetrahydroquinoline,

 7-Amino-3-hydroxymethyl-1-tert-butyltetrahydroquinoline,

 7-Amino-3-methyl-1-tert-butyltetrahydroquinoline,

 N-isopropyl-7-aminotetrahydroquinoline,

 7-Amino-3-methyl-1-isopropyltetrahydroquinoline,

 7-Amino-3-hydroxymethyl-1-isopropyltetrahydroquinoline,

 7-Amino-3-tert-butyl-1-methyltetrahydroquinoline,

 7-Amino-3-tert-butyl-1-isopropyltetrahydroquinoline,

 7-Amino-3-ethyl-1-isopropyltetrahydroquinoline,

 7-Amino-3-ethyl-1-methyltetrahydroquinoline,

 7-Amino-3-ethylaminomethyl-1-methyltetrahydroquinoline,

7-Amino-3-ethylaminomethyl-1-ethyltetrahydroquinoline,

7-Amino-3-ethylaminomethyl-1-tert-butyltetrahydroquinoline,

7-Amino-3-ethylaminomethyl-1-isopropyltetrahydroquinoline,

7-Amino-3-isopropyl-1-hydroxyethyltetrahydroquinoline,

 7-Amino 3-tert-butyl-1-ethyltetrahydroquinoline,

 7-Amino-3-methylaminomethyl-1-methyltetrahydroquinoline,

7-Amino-3-methylaminomethyl-1-ethyltetrahydroquinoline, 7-Amino-3-methylaminomethyl-1-tert-butyltetrahydroquinoline, 7-amino-3-methylaminomethyl-1-isopropyltetrahydroquinoline, 7-amino-3-methyl Oxyl small methyl tetrahydroquinoline,

 7-Amino-3-ethoxy-1-ethyltetrahydroquinoline and an addition salt of the above compound with an acid;

 Among the above aminotetrahydroquinolines, more particularly preferred is -N-methyl-7-aminotetrahydroquinoline,

 N-benzyl-7-aminotetrahydroquinoline,

 N-ethyl-7-aminotetrahydroquinoline,

 N-hydroxyethyl-7-aminotetrahydroquinoline, N-isobutyl-7-aminotetrahydroquinoline,

 N-tert-butyl-7-aminotetrahydroquinoline, 1, 3-dimethyl-7-aminotetrahydroquinoline,

 7-Amino-3-hydroxymethyl-1-isobutyltetrahydroquinoline, 7-amino-3-methylsuccinylethyltetrahydroquinoline,

 7-Amino-3-hydroxymethyl-1-tert-butyltetrahydroquinoline, 7-amino-3-methyl-1-tert-butyltetrahydroquinoline,

 N-isopropyl-7-aminotetrahydroquinoline, 7-amino-3-methyl-1-isopropyltetrahydroquinoline,

 7-Amino-3-hydroxymethyl-1-isopropyltetrahydroquinoline, 7-amino-3-tert-butyl-1-methyltetrahydroquinoline,

 7-Amino-3-tert-butyl-1-isopropyltetrahydroquinoline, 7-amino-3-ethyl-1-isopropyltetrahydroquinoline,

 7-Amino-3-ethyl-1-methyltetrahydroquinoline,

 7-Amino-3-isopropyl-1-hydroxyethyltetrahydroquinoline, 7-amino 3-tert-butyl-1-ethyltetrahydroquinoline,

 7-Amino-3-methoxy-1-methyltetrahydroquinoline,

 7-Amino-3-ethoxy-1-ethyltetrahydroquinoline,

And their addition salts with acids; A preferred amino group-containing indoline of formula (II) is -N-methyl-6-aminoindoline,

 N-benzyl-6-aminoindoline,

 N-ethyl-6-aminoindoline,

 6-Amino-3-hydroxymethyl-1-isobutylindoline,

6-Amino-3-methyl-1-hydroxyethylindoline,

6-Amino-3-hydroxymethyl-1-(2,-methoxyphenyl)indoline,

6-Amino-3-hydroxymethyl-1-(3,-methoxyphenyl)indoline,

6-Amino-3-hydroxymethyl-1-(4,-methoxyphenyl)indoline,

6-amino-3-hydroxymethyl-1-tert-butyldihydroanthracene,

N-hydroxyethyl-6-aminoindoline,

 N-isobutyl-6-aminodihydroanthracene,

 N-tert-butyl-6-aminoindoline,

 1, 3-dimethyl-6-aminoindoline,

 6-Amino-3-dimethylaminomethyl-1-methylindoline,

6-Amino-3-dimethylaminomethyl-1-ethylindoline,

6-Amino-3-dimethylaminomethyl-1-tert-butylindoline,

6-Amino-3-dimethylaminomethyl-1-isopropyldihydroindole,

6-amino-3-tert-butyl-1-isopropyldihydroanthracene,

6-Amino-3-ethyl-1-isopropyldihydroindrene,

6-Amino 3-ethylamino-1-methylindoline,

6-Amino 3-ethylamino-1-ethylindoline,

6-amino 3-ethylamino-1-tert-butyl dihydroanthracene,

6-Amino 3-ethylamino-1-isopropyldihydroindole,

6-Amino-3-ethyl-1-methylindoline,

 6-Amino 3-tert-butyl-1-ethyldihydroindrene,

6-Amino-3-methoxy-1-methylindoline,

6-Amino-3-methyl-1-tert-butylindoline,

N-isopropyl-6-aminoindoline, 6-Amino-3-methylamino-1-methylindoline, 6-amino-3-methylamino-1-ethylindoline, 6-amino-3-methylamino-1- Propyl indoline, 6-amino-3-methylamino-1-tert-butylindoline, 6-amino-3-methylamino-1-isopropylindoline, 6-amino 3-methyl-1-isopropylindoline, 6-amino-3-hydroxymethyl-1-isopropylindan, 6-amino-3-tert-butyl-1-methyl Indoline, 6-amino-3-isopropyl-1-hydroxyethylindoline, 6-amino-3-ethoxy-1-ethylindoline, and their addition to acid Salt formation in these aminoindoles, more particularly preferably -N-methyl-6-aminoindoline,

 N-benzyl-6-aminoindoline,

 N-ethyl-6-aminoindoline,

 6-Amino-3-hydroxymethyl-1-isobutylindoline, 6-amino-3-methyl-1-hydroxyethylindoline, 6-amino-3-hydroxymethyl-1 -tert-butylindoline, N-hydroxyethyl-6-aminoindoline,

N-isobutyl-6-aminoindoline, N-tert-butyl-6-aminoindoline, 1, 3-dimethyl-6-aminoindoline,

6-Amino-3-tert-butyl-1-isopropylindan, 6-amino-3-ethyl-1-isopropylindan, 6-amino-3-ethyl-1- Methyl indoline, 6-amino 3-tert-butyl-1-ethylindoline, 6-amino-3-methoxy-1-methylindoline, 6-amino-3- Methyl-1-tert-butylindoline, N-isopropyl-6-aminoindoline, 6-Amino-3-methyl-1-isopropylindoline,

 6-amino-3-hydroxymethyl small isopropyl dihydroanthracene,

 6-amino-3-tert-butyl-1-methylindoline,

 6-Amino-3-isopropyl-1-hydroxyethyldihydroanthracene,

 6-Amino-3-ethoxy-1-ethyldihydroindole,

 And their acid addition salts

 One or a plurality of amino group-containing tetrahydroquinolines or one of the formulas (I) or a plurality of amino group-containing indolines such as the above-mentioned composition (I) The weight is from 0.0005% to 12%, more preferably from about 0.005% to 6% by weight.

Suitable media for dyeing (i.e., carriers) generally include water or a mixture of water and at least one organic solvent which is used to dissolve compounds which are not sufficiently soluble in water. As the organic solvent, there may be mentioned lower alcohols of ₄ such as ethanol and isopropanol, glycerol, diols and ethers of glycols, such as propylene glycol, 2-butoxyethanol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and Ethers, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar compounds and mixtures thereof.

 The solvent is used in an amount of from 1% to 95% by weight based on the total amount of the composition, more preferably from 5% to 30% by weight.

 The pH of the composition is generally between about 3 and 12, preferably between 5 and 11. It can be adjusted to the desired value by an acidifying agent or an alkalizing agent which is often used in keratin fiber dyeing.

 The acidifying agent may, for example, be an inorganic acid or an organic acid such as hydrochloric acid, orthophosphoric acid, sulfuric acid, or a carboxylic acid such as acetic acid, tartaric acid, citric acid, lactic acid or sulfonic acid.

 Examples of the alkalizing agent include ammonia, an alkali metal carbonate, an alkanolamine such as monoethanolamine, diethanolamine, triethanolamine, and derivatives thereof, and an alkaline substance such as sodium hydroxide or potassium hydroxide. .

 In addition to the dyes defined above, the compositions may also contain at least one additional oxidative dye developer, a color former or at least one direct dye or various materials used in hair dyeing compositions. One or more mixtures of auxiliaries;

 The oxidative dye developer is selected from the conventional oxidative dye developers used in the oxidative dyeing process, and among them, p-phenylenediamine, p-toluenediamine, p-aminophenol, o-aminophenol, and the present invention are particularly exemplified. a heterocyclic compound different from the amino group-containing tetrahydroquinoline and the amino group-containing indoline;

In the class of p-phenylenediamine, p-phenylenediamine, p-toluenediamine, 2,6-dimethyl-p-phenylenediamine, 2-β-hydroxyethyl-p-phenylenediamine, 2- n-Propyl-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, Ν-(β-hydroxypropyl)- P-phenylenediamine, anthracene, fluorene-bis(β-hydroxyethyl)-p-phenylenediamine, 4-amino-indole-(β-methoxyethyl)-aniline, patent in France

The p-phenylenediamines and their addition salts with acids are described in the application of FR 2,630,438.

 Examples of the p-aminophenol class include p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, and 4-amino group. 2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino 2-methoxymethylphenol and their addition salts with acids.

 Among the o-aminophenols, as an example, 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetyl-2-aminophenol, and They are added to the acid.

 In the heterocyclic group, pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and addition salts thereof with an acid are particularly exemplified.

 When these additional oxidative dye developers are used, their content is preferably from 0.0005% to 12% by weight based on the total weight of the composition, particularly preferably from 0.005% to 6% by weight based on the total weight.

 The coloring agent or the direct coloring agent is for changing the color tone and enriching the gloss, and the coloring agent may be selected from the coloring agent conventionally used in the oxidation dyeing method, and particularly, m-phenylenediamine and m-amino group are mentioned. Phenol, m-diphenol and heterocyclic color formers, such as anthracene derivatives, pyridine derivatives and pyrazolone, and their addition salts with acids, these colorants may especially be selected from 2-methyl-5 -aminophenol, 5-indole-(β-hydroxyethyl)-amino-2-methylphenol, 2-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyl)-benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxy Benzobenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)-propionamidine, sesame phenol, 1-naphthol, 6-hydroxyindole, 4-hydroxyindole , 4-hydroxy-indole-methylhydrazine, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyridyl An oxazol-5-one and an addition salt thereof with an acid; the amount of said color former or direct dyeing agent is preferably the total weight of said composition 0.0001% to 10%, more preferably 0.005% to 5% of the total weight;

 Said various auxiliaries, such as anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants or mixtures thereof, anionic polymers, cationic polymers, nonionic polymers, amphoteric polymers , anionic or cationic polymers or mixtures thereof, inorganic or organic thickeners, antioxidants, penetrants, sequestrants, perfumes, buffers, dispersants, conditioning agents such as polymethylsiloxanes, film formers The amount of the preservative, the opacifier, and the auxiliary agent is preferably 0.0001% to 20% by weight based on the total weight of the dyeing composition;

 Of course, those skilled in the art must select these additional compounds that can be arbitrarily added in such a way that the superior properties inherent to the compositions of the present invention are not or substantially not altered by these contemplated additives.

The composition of the present invention may be in various shapes such as solid, liquid, paste, gel, or various suitable Entering keratin fibers, especially other shapes suitable for human hair dyeing.

 Another object of the present invention is a method for dyeing keratin fibers, particularly a method for dyeing human keratin fibers such as hair, as defined above.

 According to this method, the composition is applied to the fiber, either in the air or by means of an oxidizing agent or a metal salt for catalytic oxidation, in the air or by means of an oxidizing agent, sufficient to produce The time required for color.

 According to the first form of the practice of the present invention, the coloration of the fibers can be carried out without the addition of an oxidizing agent and only by contact with oxygen in the air. In this case, an oxidation catalyst may be optionally added to the composition to accelerate the progress of the oxidation.

 Said metal salts, for example, salts of manganese, cobalt, copper, iron, silver and zinc.

 Such compounds may be, for example, manganese diacetate tetrahydrate, manganese dichloride and its hydrates, manganese dicarbonate, manganese acetylacetonate, manganese triacetate and its hydrates, manganese trichloride, zinc dichloride, Zinc diacetate dihydrate, zinc carbonate, zinc dinitrate, zinc sulfate, iron dichloride, iron sulfate, iron diacetate, cobalt diacetate tetrahydrate, cobalt carbonate, cobalt dichloride, cobalt dinitrate, cobalt sulfate A heptahydrate, a chlorinated ketone, a silver nitrate aqueous ammonia complex or the like, a manganese salt is particularly preferred.

 When these metal salts are used, they are usually used in an amount of 0.001-4% by weight based on the total weight of the composition, preferably 0.005% to 2% by weight based on the total weight of the composition.

 According to a second form of the invention, at least one composition as defined above is applied to the fibers, aided by the simultaneous addition of an oxidizing agent during the use of the composition, at acidic, neutral or alkaline pH. A color is exhibited under the value, and such an oxidizing agent may be present in the coated oxidizing composition or may be added later.

 According to this second form of the dyeing process of the present invention, it is preferred to mix the composition as described above with a composition comprising at least one oxidizing agent in a suitable dyeing medium at a level sufficient to produce The color, preferably the oxidizing agent, comprises from 0.1% to 15% by weight based on the total weight of the composition.

 The resulting mixture is then applied to the keratin fibers for about 3 to 50 minutes, preferably for about 5 to 30 minutes, followed by rinsing, washing with shampoo, re-rinsing and drying.

 The oxidizing agent present in the oxidizing composition is selected from oxidizing agents conventionally used in the method of dyeing keratin fibers, and examples thereof include hydrogen peroxide, urea peroxide, alkali metal bromate, and persalt such as perborate. And persulfate, hydrogen peroxide is particularly preferred.

The oxidizing composition containing the oxidizing agent as defined above, after the pH is mixed with the dyeing composition, the pH of the composition coated on the keratin fibers is preferably between about 7 and 12, more Selected in 5-11 The adjustment of the pH to the desired value is based on the acidulant or basifying agent conventionally used in the keratin fiber dyeing process as defined above.

 The oxidizing agent composition as defined above may also have various auxiliaries which are often used in hair dyeing compositions as defined above.

 The preparation method of the composition of the present invention is a conventional physical mixing method in which the respective components are mixed and obtained.

 A further object of the invention is a dyeing device with a plurality of chambers or boxes or a completely different hair care system with a plurality of chambers, wherein the first chamber contains the defined composition, the second chamber An oxidant composition as defined above is contained therein. These devices can be equipped with a device that can apply the desired mixture to the hair.

 The preparation method of the aminotetrahydroquinoline of the formula (I) and the amino group-containing indoline of the formula (I), in the literature:

 Feer; Koenigs; Chem. Ber.; 18; 1885; 2391.

V; Braun; Grabowski; Rawicz; Chem. Ber.; 46; 1913; 3182.

 Preobrashenskaja; Dokl. Akad. Naulc SSS; 118; 1958; 302, 304; Dokl. Chem. (Engl. Transl.); ll 8- 123 <1958> 49, 51.

 Preobrashenskaja;Zh.Obshch, him.;29;1959;317,322;engl.Ausg.S.322,326

 It has been publicly disclosed, and relevant personnel can prepare it according to the literature if necessary. The method uses metal, hydrogen or other reducing medium as the reducing agent, and the nitro group corresponding to the compound (I) and (Π). The compound is reduced to an amino group by a reduction reaction, which will not be described in detail in the present invention.

 Tests have shown that the composition of the present invention is not only suitable as an oxidation dye precursor, but also provides a dye composition having a very pure color of blue to green color tone, and is not easily faded and has good stability. detailed description

 The following examples are intended to illustrate the invention without any limitation.

Preparation example

 Example 1 : Synthesis of N-methyl-7-aminotetrahydroquinoline hydrochloride

先将 22.4g(0.4mol)铁粉和 2ml浓盐酸 (36%)加入反应瓶， 搅拌并加入 240ml乙醇和 80ml水， 然后升温至回流， 稍冷后分批加入 19.2g(0.1mol)N-甲基 -7-硝基四氢喹啉。 反 应 2.5hr.后， 停止反应， 趁热抽滤， 并用热乙醇冲洗瓶内的铁泥 2-3次， 浓缩滤液， 浓 缩后的滤液用 CH₂C1₂萃取 3次， 减压旋蒸除去 CH₂C1₂后加入 20ml乙醇， 通入 HC1气 体后有固体析出， 干燥后得到 15.37g浅红色固体， 收率 77.4%。

22.4 g (0.4 mol) of iron powder and 2 ml of concentrated hydrochloric acid (36%) were first added to the reaction flask, stirred and added with 240 ml of ethanol and 80 ml of water, and then the temperature was raised to reflux. After a little cold, 19.2 g (0.1 mol) of N- was added in portions. Methyl-7-nitrotetrahydroquinoline. After the reaction for 2.5 hr., the reaction was stopped, and the mixture was filtered while hot, and the iron sludge in the bottle was rinsed with hot ethanol for 2-3 times. The filtrate was concentrated, and the concentrated filtrate was extracted three times with CH ₂ C1 ₂ and then evaporated to dryness. _{After 2} C1 ₂ , 20 ml of ethanol was added, and a solid was precipitated after passing through HC1 gas, and after drying, 15.37 g of a pale red solid was obtained, yield 77.4%.

_3⁄4 -NMR (CDC1 ₃ ): 51.98 (q, 2H), 2.77 (t, 2H), 2.87 (s, 3H), 3.22 (t, 2H), 6.50 (t, 1H), 6.65 (d, lH), 6.96 (d, 1H).

 Example 2: Synthesis of N-ethyl-7-aminotetrahydroquinoline hydrochloride

22.4 g (0.4 mol) of reduced iron powder and 2 ml of concentrated hydrochloric acid (36%) were first added to the reaction flask, stirred and 240 ml of ethanol and SOml zK were added, and then the temperature was raised to reflux. After a little cold, 20.6 g (0.1 mol) of N was added in portions. -ethyl-7-nitrotetrahydroquinoline. After the reaction for 2.5 hr., the reaction was stopped, and the mixture was filtered while hot, and the iron sludge in the bottle was rinsed with hot ethanol for 2-3 times. The filtrate was concentrated, and the concentrated filtrate was extracted three times with CH ₂ C1 ₂ and then evaporated to dryness. _{After 2} C1 ₂ , 20 ml of ethanol was added, and a solid was precipitated after passing through HC1 gas. After drying, it was recrystallized from methanol to obtain 17.68 g of a white solid, yield: 83.2%.

 3⁄4- MR (DMSO): 51.06(t, 3H), 1.84(q, 2H), 2.65(t,2H), 3.21(t, 2H), 3.31(q,2H), 6.45(d, 1H), 6.57 (s, lH), 6.93 (d, 1H), 10.31 (s, 2H).

 Example 3: Synthesis of N-isobutyl-7-aminotetrahydroquinoline hydrochloride

22.4 g (0.4 mol) of reduced iron powder and 2 ml of concentrated hydrochloric acid (36%) were first added to the reaction flask, stirred and added with 240 ml of ethanol and 80 ml of water, and then the temperature was raised to reflux. After a little cold, 23.4 g (0.1 mol) of N was added in portions. -Isobutyl-7-nitrotetrahydroquinoline. After the reaction for 2.5 hr., the reaction was stopped, and the mixture was filtered while hot, and the iron sludge in the bottle was rinsed with hot ethanol for 2-3 times. The filtrate was concentrated, and the concentrated filtrate was extracted three times with CH ₂ C1 ₂ and then evaporated to dryness. _{After 2} C1 ₂ , 20 ml of ethanol was added, and a solid was precipitated after passing through HC1 gas, and after drying, it was recrystallized from methanol to obtain 17.5 g of a white solid, yield: 85.8%. 3⁄4-NMR (CDClj): 50.91 (d, 6H), 1.91 (q, 2H), 2.06 (sex, 1H), 2.75 (t, 2H), 2.98 (d, 2H): 3.27 (t, 2H), 6.48 (t, 1H), 6.55 (d, lH), 6.97 (d, 1H).

 Example 4: Synthesis of N-hydroxyethyl-7-aminotetrahydroquinoline hydrochloride

22.4 g (0.4 mol) of reduced iron powder and 2 ml of concentrated hydrochloric acid (36%) were first added to the reaction flask, stirred and added with 240 ml of ethanol and 80 ml of water, and 22.2 _g (0.1 mol) of N-hydroxyethyl-7-nitrotetra was added. Hydroquinoline is then warmed to reflux. After the reaction for 3.5 hr., the reaction was stopped, filtered while hot, and the iron mud in the bottle was rinsed 2-3 times with hot ethanol, and the filtrate was concentrated. The concentrated filtrate was extracted three times with CH ₂ C1 ₂ and then evaporated to remove CH. _{After 2} C1 ₂ , 20 ml of ethanol was added, and a solid was precipitated after passing through HC1 gas, and after drying, 15.5 g of a white solid was obtained in a yield of 80.7%.

3⁄4-employment R(D ₂ 0): 52.19(m, 2Η), 2.98(t, 2H), 3.64(m, 4H), 3.87(t,2H), 7.34(d, 2H), 7.47(t,

1H).

 Example 5: Synthesis of N-methyl-6-aminoindoline hydrochloride

22.4 g (0.4 mol) of reduced iron powder and 2 ml of concentrated hydrochloric acid (36%) were first added to the reaction flask, stirred and added with 240 ml of ethanol and 80 ml of water. After a little cold, 17.8 g (0.1 mol) of N-methyl-6 was added in portions. -Nitroindole, then warmed to reflux. After the reaction for 2.5 hr., the reaction was stopped, filtered while hot, and the iron mud in the bottle was rinsed 2-3 times with hot ethanol. The filtrate was concentrated, and the concentrated filtrate was extracted three times with C C1 ₂ and then evaporated to remove C C1 under reduced pressure. After adding ₂ ml of ethanol, a solid was precipitated after passing through HC1 gas, and after drying, 10.5 g of an off-white solid was obtained in a yield of 70.9%.

 ^- MRCDzO): 53.21(s, 3H), 3.317(t, 2H), 3.95(t, 2H), 7.42(d, 1H), 7.48(s,lH), 7.576(t,

1H).

Example 6: Synthesis of N-ethyl-6-aminoindoline hydrochloride

22.4 g (0.4 mol) of reduced iron powder and 2 ml of concentrated hydrochloric acid (36%) were first added to the reaction flask, stirred and added with 240 ml of ethanol and 80 ml of water, and 19.2 g (0.1 mol) of N-ethyl-6-nitrodihydrogen was added. Hey, then warm to reflux. After the reaction for 2.5 hr., the reaction was stopped, filtered while hot, and the iron mud in the bottle was rinsed 2-3 times with hot ethanol, and the filtrate was concentrated. The concentrated filtrate was extracted three times with CH ₂ C _{1 2} and then evaporated to remove CH. _{After 2} C1 ₂ , 20 ml of ethanol was added, and a solid was precipitated after passing through HC1 gas, and after drying, 9.5 g of an off-white solid was obtained in a yield of 58.6%.

3⁄4-NMR (D ₂ 0): 51.15 (t, 3H), 2.96 (t, 2H), 3.19 (m, 2H), 3.47 (t, 2H), 6.647 (s, lH), 6.71 (d, lH) , 7.17 (t, 1H).

The application column, wherein the concentration is a weight concentration unless otherwise specified.

 Example 7: Preparation of the composition of the invention as follows

 Hair oxidative dye, alkaline hexadecanol/octadecyl alcohol 17.00g

 Sodium decyl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia (25% aqueous solution, weight) 3.00g

 P-phenylenediamine (PPD) 0.10g

 N-methyl-7-aminotetrahydroquinoline hydrochloride 0.005g

 Soften the water to lOOg The pH of the hair dye is 10.5. The above respective components are mixed and obtained.

In use, 10 g of the above dye composition (component A) was first mixed with 10 g of a 6% strength aqueous hydrogen peroxide solution (component B). Then, the resulting composition (pH 10) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, washed with shampoo and dried to give a pure Prussian blue dyed hue. Example 8: Preparation of the oxidative dye for hair styling of the composition of the present invention, alkaline cetearyl alcohol 17.00 g

 Sodium lauryl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 P-phenylenediamine (PPD) 0.10g

 N-methyl-7-aminotetrahydroquinoline hydrochloride 6.0g

 Demineralized water to 100 g The pH of the hair dye is 10.5, and the above components are mixed to obtain.

In use, 10 _{g of the} above dye composition (component A) was first mixed with 10 g of a 6% strength aqueous hydrogen peroxide solution (component B). Then, the resulting composition (pH 9) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, washed with shampoo and dried to give a pure Prussian blue dyed hue.

 Example 9: A composition of the present invention was prepared as follows. Hair oxidative dye, basic hexadecyl octadecyl alcohol 17.00 g

 Sodium lauryl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 P-phenylenediamine (PPD) 0.10g

 N-methyl-7-aminotetrahydroquinoline hydrochloride 0.20g

Soften water to lOOg The hair dye has a pH of 10.5, and the above respective components are mixed and obtained.

 In use, first, 10 g of each of the above dye compositions (component A) was mixed with 10 g of a 6% by weight aqueous hydrogen peroxide solution (component B). Then, the obtained composition (pH 9.5) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, washed with shampoo and dried to give a pure Prussian blue dyed hue.

 Example 10: A composition of the invention was prepared as follows

 Hair oxidative dye, alkaline hexadecanol/octadecyl alcohol 17.00g

 Sodium decyl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 p-Toluenediamine Sulfate (TDS) 0.50g

 N-methyl-7-aminotetrahydroquinoline hydrochloride 0.20g

 Demineralized water to 100 g The pH of the hair dye is 10.5, and the above components are mixed to obtain.

 When used, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 8.5) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, washed with shampoo and dried to give a pure Prussian blue dyed hue. Example 11: A composition of the present invention was prepared as follows. Hair oxidative dye, basic hexadecanol/octanyl alcohol 17.00 g

 Sodium decyl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

Ammonia water (25% aqueous solution) 3.00g P-aminophenol (PAP) 0.50g

N-methyl-7-aminotetrahydroquinoline hydrochloride 0.20g

 The softening water to 100 g of the hair dye has a pH of 10.5, and the above respective components are mixed to obtain.

 In use, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 8.5) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, and the shampoo is washed and dried to obtain a pure purple-red dyed hue.

Example 12: A composition of the present invention was prepared as follows. Hair oxidative dye, basic hexadecyl octadecyl alcohol 17.00 g

 Sodium decyl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 P-phenylenediamine (PPD) 0.10g

 N-ethyl-7-aminotetrahydroquinoline hydrochloride 0.20g

 The softening water to 100 g of the hair dye has a pH of 10.5, and the above respective components are mixed to obtain.

 In use, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 10) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, washed with shampoo and dried to give a pure Prussian blue dyed hue. Example 13: A composition of the present invention was prepared as follows. Hair oxidative dye, basic hexadecyl octadecyl alcohol 17.00 g

Sodium lauryl ether sulfate (28%) 3.50g Ascorbic acid 0.60g sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 p-Toluenediamine Sulfate (TDS) 0.50g

 N-ethyl-7-aminotetrahydroquinoline hydrochloride 0.20g

 The softening water to 100 g of the hair dye has a pH of 10.5, and the above respective components are mixed to obtain.

 In use, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 8) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, washed with shampoo and dried to give a pure Prussian blue dyed hue. Example 14: Preparation of the composition of the invention as follows

 Hair oxidative dye, alkaline hexadecanol/octadecyl alcohol 17.00g

 Sodium lauryl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 P-aminophenol (PAP) 0.50g

 N-ethyl-7-aminotetrahydroquinoline hydrochloride 0.20g

 The softening water to 100 g of the hair dye has a pH of 10.5, and the above respective components are mixed to obtain.

 In use, 10 g of the above dye composition (component A) was first mixed with 10 g of a 6% aqueous hydrogen peroxide solution (component B). Then, the resulting composition (pH 9) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, and the shampoo is washed and dried to obtain a pure purple-red dyed hue.

Example 15: Preparation of the oxidative dye for hair styling of the composition of the invention as follows, alkaline Cetyl/octadecyl alcohol 17.00g sodium decyl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 P-phenylenediamine (PPD) 0.10g

 N-isobutyl-7-aminotetrahydroquinoline hydrochloride 0.20g

 Demineralized water to 100 g The pH of the hair dye is 10.5, and the above components are mixed to obtain.

 When used, 10 g of the above dye composition (component A) and 10 g of 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 9) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, washed with shampoo and dried to give a pure Prussian blue dyed hue. Example 16: A composition of the present invention was prepared as follows. Hair oxidative dye, basic hexadecanol/octanyl alcohol 17.00 g

 Sodium decyl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 p-Toluenediamine Sulfate (TDS) 0.50g

 N-isobutyl-7-aminotetrahydroquinoline hydrochloride 0.20g

 Demineralized water to 100 g The pH of the hair dye is 10.5, and the above components are mixed to obtain.

In use, 10 g of the above dye composition (component A) was first mixed with 10 g of a 6% aqueous hydrogen peroxide solution (component B). The resulting composition (pH 9.5) is then applied to the hair to maintain the composition on the hair 30 minute. The hair is rinsed with running water, washed with shampoo and dried to give a pure Prussian blue dyed hue. Example 17: A oxidative dye for the composition of the present invention was prepared as follows, basic hexadecanol/octadecyl alcohol 17.00 g

 Sodium lauryl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 P-aminophenol (PAP) 0.50g

 N-isobutyl-7-aminotetrahydroquinoline hydrochloride 0.20g

 Demineralized water to 100 g The pH of the hair dye is 10.5, and the above components are mixed to obtain.

 In use, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the obtained composition (pH S. 5) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, and the shampoo is washed and dried to obtain a pure purple-red dyed hue.

Example 18: A composition of the present invention was prepared as follows. Hair oxidative dye, basic hexadecyl octadecyl alcohol 17.00 g

 Sodium decyl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 P-phenylenediamine (PPD) 0.10g

 N-Hydroxyethyl-7-aminotetrahydroquinoline hydrochloride 0.20g

Soften water to lOOg The hair dye has a pH of 10.5, and the above respective components are mixed and obtained.

 In use, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 8.5) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, washed with shampoo and dried to give a pure Prussian blue dyed hue. Example 19: A composition of the present invention was prepared as follows. Hair oxidative dye, basic hexadecyl octadecyl alcohol 17.00 g

 Sodium lauryl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 p-Toluenediamine Sulfate (TDS) 0.50g

 N-Hydroxyethyl-7-aminotetrahydroquinoline hydrochloride 0.20g

 Demineralized water to 100 g The pH of the hair dye is 10.5, and the above components are mixed to obtain.

 In use, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 10) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, washed with shampoo and dried to give a pure Prussian blue dyed hue. Example 20: A composition of the present invention was prepared as follows. Hair oxidative dye, basic hexadecyl octadecyl alcohol 17.00 g

 Twelve yards of sodium ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

P-aminophenol (PAP) 0.50g N-Hydroxyethyl-7-aminotetrahydroquinoline hydrochloride 0.20 g of demineralized water to 100 g The pH of the hair dye is 10.5, and the above respective components are mixed to obtain.

 When used, 10 g of the above dye composition (component A) and 10 g of 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 9) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, and the shampoo is washed and dried to obtain a pure purple-red dyed hue.

Example 21: A composition of the present invention was prepared as follows. Hair oxidative dye, basic hexadecanol/octanyl alcohol 17.00 g

 Sodium lauryl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 P-phenylenediamine (PPD) 0.10g

 N-methyl-6-aminoindoline hydrochloride 0.20g

 Demineralized water to 100 g The pH of the hair dye is 10.5, and the above components are mixed to obtain.

 In use, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 8) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, and the shampoo is washed and dried to give a pure blue dyed hue.

Example 22: A composition of the invention was prepared as follows. Hair oxidative dye, basic hexadecyl octadecyl alcohol 17.00 g

 Sodium lauryl ether sulfate (2S%) 3.50g

Ascorbic acid 0.60g Sodium sulfite 0.80g Ammonia (25% aqueous solution) 3.00g

 p-Toluenediamine Sulfate (TDS) 0.50g

 N-methyl-6-aminoindoline hydrochloride 0.20g

 The softening water to 100 g of the hair dye has a pH of 10.5, and the above respective components are mixed to obtain.

 In use, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 9) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, and the shampoo is washed and dried to give a pure blue dyed hue.

Example 23: A composition of the invention was prepared as follows. Hair oxidative dye, basic hexadecyl octadecyl alcohol 17.00 g

 Sodium lauryl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 P-aminophenol (PAP) 0.50g

 N-methyl-6-aminoindoline hydrochloride 0.20g

 Demineralized water to 100 g The pH of the hair dye is 10.5, and the above components are mixed to obtain.

 In use, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 8) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, and the shampoo is washed and dried to obtain a pure purple-red dyed hue.

Example 24: Preparation of the oxidative dye for hair styling of the composition of the present invention as follows, alkaline T N2007/002505 Hexa/octadecyl alcohol 17.00g

 Sodium lauryl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 P-phenylenediamine (PPD) 0.10g

 N-ethyl-6-aminoindoline hydrochloride 0.20g

 Demineralized water to 100 g The pH of the hair dye is 10.5, and the above components are mixed to obtain.

 In use, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 8.5) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, and the shampoo is washed and dried to give a pure blue dyed hue.

Example 25: Preparation of the composition of the invention as follows

 Hair oxidative dye, alkaline hexadecanol/octadecyl alcohol 17.00g

 Sodium lauryl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 p-Toluenediamine Sulfate (TDS) 0.50g

 N-ethyl-6-aminoindoline hydrochloride 0.20g

The softening water to 100 _{g of} the hair dye has a pH of 10.5, and the above components are mixed to obtain.

In use, 10 g of the above dye composition (component A) was first mixed with 10 g of a 6% aqueous hydrogen peroxide solution (component B). Then, the resulting composition (pH 8) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, and the shampoo is washed and dried to give a pure blue dyed hue. Example 26: Preparation of the oxidative dye for hair styling of the composition of the present invention, alkaline cetearyl alcohol 17.00 g

 Sodium decyl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) · 3.00g

 P-aminophenol (PAP) 0.50g

 N-ethyl-6-aminoindoline hydrochloride 0.20g

 The softening water to 100 g of the hair dye has a pH of 10.5, and the above respective components are mixed to obtain.

 In use, 10 g of the above dye composition (component A) and 10 g of a 6% aqueous hydrogen peroxide solution (component)

B) Mixing. Then, the resulting composition (pH 8) was applied to the hair, and the composition was kept on the hair for 30 minutes. The hair is rinsed with running water, and the shampoo is washed and dried to obtain a pure purple-red dyed hue.

Comparative Example 1~6

The following dyes were prepared according to the following formulation - Comparative Example 1 Hexadecyl alcohol 18.00 g

 Sodium lauryl ether sulfate (28%) 3.50g

 Ascorbic acid 0.60g

 Sodium sulfite 0.80g

 Ammonia water (25% aqueous solution) 3.00g

 P-phenylenediamine (PPD) 0.10g

 2-amino-4-light ethylaminoanisole (AHEAS) 0.20g

Softened water to 100g Comparative Example 2 C16/octadecyl alcohol 17.00 g Sodium lauryl ether sulfate (28%) 3.50 g Ascorbic acid 0.60 g Sodium sulfite 0.80 g Ammonia water (25% aqueous solution) 3.00 g p-Diaminotoluene sulfate (TDS) 0.50 g

2-Amino-4-hydroxyethylaminoanisole (AHEAS) 0.20 g demineralized water to 100 g Comparative Example 3 C16/octadecyl alcohol 17.00 g Sodium lauryl ether sulfate (28%) 3.50 g Ascorbic acid 0.60 g Sodium sulfite 0.80g Ammonia water (25% aqueous solution) 3.00g p-Aminophenol (PAP) 0.50g

2-Amino-4-hydroxyethylaminoanisole (AHEAS) 0.20 g demineralized water to 100 g Comparative Example 4 Hexadecane octadecyl alcohol 17.00 g Sodium decyl ether sulfate (28%) 3.50 g Ascorbic acid 0.60 g Sodium sulfite 0.80g Ammonia (25% aqueous solution) 3.00g P-phenylenediamine (PPD) 0.10g

 2,4-Diaminophenoxyethanol (2,4-DAPE) 0.20g

Softened water to lOOg Comparative Example 5 Hexa/octadecyl alcohol 17.00g

Sodium decyl ether sulfate (28%) 3.50g

Ascorbic acid 0.60g

Sodium sulfite 0.80g

Ammonia water (25% aqueous solution) 3.00g

P-aminotoluene sulfate (TDS) 0.50g

 2,4-Diaminophenoxyethanol (2,4-DAPE) 0.20g

Softened water o !

 Comparative Example 6 e 'ra hexadecanol/octadecyl alcohol 17.00g

Sodium lauryl ether sulfate (28%) 3.50g

Ascorbic acid 0.60g

Sodium sulfite O.SOg

Ammonia water (25% aqueous solution) 3.00g

P-aminophenol (PAP) 0.50g

 2,4-Diaminophenoxyethanol (2,4-DAPE) 0.20g

Soften water to lOOg

The hairs dyed in Examples 9-20 and 21-26 were immersed in a 0.5% sodium lauryl ether sulfate solution (K-12) in C for half an hour with stirring, and rinsed and dried (this process was equivalent For daily shampoo care for 2 months), with no bleaching The washed dyed hair control showed that the keratin fibers (Examples 9-20 and 21-26) dyed using the dye composition containing the present invention (aminotetrahydroquinoline and aminoindoline) were substantially non-fading, The keratin fibers (Comparative Examples 1 to 6) which were dyed without the dye composition of the present invention had good fading and were inferior in stability.

Claims

Rights request An aminoheterocyclic compound-containing composition for hair dyeing, characterized in that it contains at least an amino group-containing heterocyclic compound in a medium suitable for dyeing, and the amino group-containing heterocyclic compound is selected. An aminotetrahydroquinoline of the formula (I), an addition salt of an aminotetrahydroquinoline of the formula (I) with an acid, an amino group-containing indoline of the formula (π), a formula (Π) One or more of the addition salts of an amino group-containing indoline and an acid;

In formula (I) and formula (Π): ^ is at a substitutable position of the nitrogen atom, R ₂ is at a position replaceable on the saturated ring, and at the R ₃ position and at a substitutable position other than the amino group on the benzene ring , or independently, represents hydrogen, amino, substituted amino, -Cw alkyl, alkoxy, halogen, ester, carboxyl or nitro, R ₂ and may be represented as 1 to 3 identical or different substituent groups, respectively .  The amino group-containing heterocyclic compound composition for keratin fiber dyeing according to claim 1, wherein the acid addition salt is selected from the group consisting of hydrochloride, hydrobromide, and sulfuric acid. Salt, tartrate, lactate or acetate.  The amino group-containing heterocyclic compound composition for keratin fiber dyeing according to claim 1, wherein the amino group-containing tetrahydroquinoline of the formula (I) is - N-methyl-7-aminotetrahydroquinoline,  N-nodal -7-aminotetrahydroquinoline,  7-Amino-3-hydroxymethyl-1-(2'-methoxyphenyl)tetrahydroquinoline,  7-Amino-3-hydroxymethyl-1-(3'-methoxyphenyl)tetrahydroquinoline,  7-Amino-3-hydroxymethyl-1-(4'-methoxyphenyl)tetrahydroquinoline,  N-ethyl-7-aminotetrahydroquinoline,  N-hydroxyethyl-7-aminotetrahydroquinoline,  N-isobutyl-7-aminotetrahydroquinoline, 7-Amino-3-methyl-1-(2'-methoxyphenyl)tetrahydroquinoline, 7-Amino-3-methyl-1-(3'-methoxyphenyl)tetrahydroquinoline, 7-Amino-3-methyl-1-(4,-methoxyphenyl)tetrahydroquinoline, N-tert-butyl-7-aminotetrahydroquinoline,  1, 3-dimethyl-7-aminotetrahydroquinoline,  7-Amino-3-hydroxymethyl-1-isobutyltetrahydroquinoline,  7-Amino-3-dimethylaminomethyl-1-methyltetrahydroquinoline, 7-Amino-3-dimethylaminomethyl small ethyltetrahydroquinoline, 7-Amino-3-dimethylaminomethyl-1-tert-butyltetrahydroquinoline, 7-Amino-3-dimethylaminomethyl-1-isopropyltetrahydroquinoline, 7-Amino-3-methyl-1-hydroxyethyltetrahydroquinoline,  7-Amino-3-hydroxymethyl-1-tert-butyltetrahydroquinoline,  7-Amino-3-methyl-1-tert-butyltetrahydroquinoline,  N-isopropyl-7-alkyltetrahydroquinoline,  7-Amino-3-methyl-1-isopropyltetrahydroquinoline,  7-Amino-3-hydroxymethyl-1-isopropyltetrahydroquinoline,  7-Amino-3-tert-butyl small methyltetrahydroquinoline,  7-Amino-3-tert-butyl-1-isopropyltetrahydroquinoline,  7-Amino-3-ethyl-1-isopropyltetrahydroquinoline,  7-Amino-3-ethyl-1-methyltetrahydroquinoline,  7-Amino-3-ethylaminomethyl-1-methyltetrahydroquinoline, 7-Amino-3-ethylaminomethyl-1-ethyltetrahydroquinoline, 7-Amino-3-ethylaminomethylth-tert-butyltetrahydroquinoline, 7-Oxo-3-ethylaminomethyl-1-isopropyltetrahydroquinoline, 7-Amino-3-isopropylsuccinic ethyltetrahydroquinoline,  7-Amino 3-tert-butyl-1-ethyltetrahydroquinoline,  7-Amino-3-methylaminomethyl-1-methyltetrahydroquinoline, 7-Amino-3-methylaminomethyl-1-ethyltetrahydroquinoline, 7-Amino-3-methylaminomethyl-1-tert-butyltetrahydroquinoline, 7-Amino-3-methylaminomethyl-1-isopropyltetrahydroquinoline, 7-Amino-3-methoxy-1-methyltetrahydroquinoline,  7-Amino-3-ethoxy-1-ethyltetrahydroquinoline and An addition salt of the above compound with an acid;  The amino group-containing indoline of formula (II) is - N-methyl-6-aminoindoline,  N-benzyl-6-aminoindoline,  N-ethyl-6-aminoindoline,  6-Amino-3-hydroxymethyl-1-isobutylindoline,  6-Amino-3-methyl-1-light ethyl indoline,  6-Amino-3-hydroxymethyl-1-(2,-methoxyphenyl)indoline, 6-Amino-3-hydroxymethyl-1-(3,-methoxyphenyl)indoline, 6-Amino-3-methyl-1(4'-methoxyphenyl)indoline, 6-Amino-3-hydroxymethyl-1-tert-butyldihydroindole.哚,  N-hydroxyethyl-6-aminoindoline,  N-isobutyl-6-aminodihydroanthracene, N-tert-butyl-6-aminoindoline,  1, 3-dimethyl-6-aminoindoline, 6-Amino-3-dimethylaminomethyl-1-methylindoline, 6-Amino-3-dimethylaminomethyl-1-ethylindoline, 6-Amino-3-dimethylaminomethyl-1-tert-butylindoline, 6-Amino-3-dimethylaminomethyl-1-isopropyldihydroindole, 6-amino-3-tert-butyl-1-isopropyldihydroanthracene,  6-Amino-3-ethyl-1-isopropyldihydroindrene,  6-Amino 3-ethylamino-1-methylindoline,  6-Amino 3-ethylamino-1-ethylindoline,  6-amino 3-ethylamino-1-tert-butyl dihydroanthracene, 6-Amino 3-ethylamino-1-isopropyldihydroindole, 6-Amino-3-ethyl-1-methylindoline, 6-Amino 3-tert-butyl-1-ethylindoline, 6-Amino-3-methoxy-1-methylindoline,  6-Amino-3-methyl-1-tert-butylindoline,  N-isopropyl-6-aminoindoline,  6-Amino-3-methylamino-1-methylindoline,  6-Amino-3-methylamino-1-ethylindoline,  6-Amino-3-methylamino-1-propylindoline,  6-Amino-3-methylamino-1-tert-butylindoline,  6-amino-3-methylamino small isopropyl dihydroanthracene,  6-Amino-3-methyl-1-isopropylindoline,  6-Amino-3-hydroxymethyl-1-isopropylindane,  6-amino-3-tert-butyl-1-methylindoline,  6-Amino-3-isopropyl-1-hydroxyethyldihydroanthracene,  6-Amino-3-ethoxy-1-ethyldihydroindole,  And their addition salts with acids.  The amino group-containing heterocyclic compound composition for keratin fiber dyeing according to claim 1, wherein the amino group-containing heterocyclic compound is used in an amount of 0.0005% to 12% by weight based on the total weight of the composition. .  The amino group-containing heterocyclic compound composition for keratin fiber dyeing according to claim 1, wherein the medium suitable for dyeing comprises water or a mixture of water and at least one organic solvent. The amount of the solvent is from 1% to 95% of the total amount of the composition.  The amino group-containing heterocyclic compound composition for keratin fiber dyeing according to claim 1, wherein the composition has a pH of from 3 to 12.  The amino group-containing heterocyclic compound composition for keratin fiber dyeing according to claim 1, wherein the composition further contains at least one additional oxidative dye developer, one hair a toner or at least one direct coloring agent or a mixture of one or more of the various adjuvants used in the hair coloring composition;  The oxidative dye developer is selected from the conventional oxidative dye developers used in the oxidation dyeing process, and the content is 0.0005% to 12% of the total weight of the composition; The coloring agent or at least one direct coloring agent is selected from the group consisting of a coloring agent or a direct coloring agent conventionally used in an oxidation dyeing method, and is used in an amount of 0.0001% to 10% by weight based on the total weight of the dyeing composition; The amount of the various adjuvants used in the hair dyeing composition is from 0.0001% to 20% by weight based on the total weight of the dyeing composition.  A method for dyeing a keratin fiber using the amino group-containing heterocyclic compound composition for keratin fiber dyeing according to any one of claims 1 to 7, wherein the dyeing composition is applied to The oxidizing agent is selected from the group consisting of a metal salt for catalyzing oxidation in the air, or a metal salt for catalytic oxidation, which is selected from the conventional methods used in the method of dyeing keratin fibers. The oxidizing or oxidizing agent composition, the metal weight is from 0.001-4% by weight based on the total weight of the dyeing composition.  9. A method according to claim 8 wherein the oxidizing agent comprises from 0.1% to 15% by weight based on the total weight of the composition.  10. A device having a plurality of chambers or a "box" having a plurality of chambers, wherein the first chamber contains the dyeing composition as defined in any one of claims 1-7, the second chamber An oxidant composition is contained therein.