DE2441599A1 - HAIR DYE PRODUCTS - Google Patents

Description

The invention relates to agents for oxidative coloring of hair based on 5,7,8-triaminoquinolines as a developer component.

The so-called oxidation colors, which are produced by the oxidative coupling of a developer component with a coupler component, play a preferred role for dyeing hair because of their intense colors and very good fastness properties. Nitrogen bases, such as p-phenylenediamine derivatives, diaminopyridines, 4-amino-pyrazolone derivatives, and heterocyclic hydrazones are usually used as developer substances. As so-called coupler components, m-phenylene-diamine derivatives, phenols, naphthols , resorcinol derivatives and pyrazolones are mentioned.

Good oxidation hair dye components must primarily meet the following requirements:

In the oxidative coupling with the respective developer or coupler components, you must have the desired Develop color nuances with sufficient intensity. They must also have sufficient to very good absorbability on human hair and they are also said to be toxicological and dermatological Respect to be harmless.

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Sheet Ji for patent application D H 9 8 3

Henkel & Cie GmbH

Patent department

The class of substituted or unsubstituted compounds commonly used as developer substances p-Phenylenediamines have the disadvantage that they cause sensitization in a number of people and in their wake causes severe allergies. The ones proposed recently to avoid these dermatological disadvantages Developer substances cannot always be fully satisfactory in terms of their application properties.

There was therefore a search for useful oxidation hair dyes the task of finding suitable components, the aforementioned requirements in an optimal way fulfill.

It has now been found that hair dyes based on oxidation dyes with a content of 5,7,8-triamino quinolines of the general formula

are X and Y are independently hydrogen, a hydroxyl group or an alkyl group having 1-4 carbon atoms, R and R ₂ are independently hydrogen, an alkyl group having 1 - ¹ J carbon atoms which may be substituted one or more times by halogen or hydroxyl, , represent, or R. and R_ together with the nitrogen atom form a five- or six-membered heterocyclic ring which can contain oxygen or nitrogen as further hetero ring members, as well as their

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Henkel & Cie GmbH

Sheet ij for patent application D 4 98 3 patent department

inorganic or organic salts as developer substances and the coupler substances common in oxidation hair colors meet the requirements set to a particularly high degree.

When used as developer components, the. Compounds according to the invention with the in general Coupler substances used for oxidation hair coloring the most varied of very intense shades of brown, as they were and are not achievable with these couplers and the previously known developers thus represent a significant enrichment of the oxidative hair coloring options. In addition, the 5,7,8-triaminoquinolines according to the invention due to the very good fastness properties of the dyeings obtained therewith good solubility in water, good storage stability and toxicological and dermatological harmlessness the end.

The 5,7,8-triaminoquinolines to be used as developer components according to the invention can either be used as such or in the form of their salts with inorganic or organic acids, e.g. as chlorides, sulfates, phosphates, acetates, Propionate, lactate, citrate can be used.

The production of the developer components according to the invention 5,7,8-triaminoquinoline to be used can according to general known processes are carried out by catalytic hydrogenation of the corresponding 5 »7-dinitro-8-aminoquinolines. The latter can be achieved by reacting 8-chloro-5,7-dinitroquinolines obtained with the corresponding amines, as described by H. Hennig, J. Tauchnitz and KV Schöne in Z. Chem. 11 (1971) pp. 267/68. The preparation of the unsubstituted 5,7,8-triaminoquinoline can according to the information provided by Ad. Claus and E. Dewitz in J. Prakt. Chem.

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53 (1896) pp. 54-7 by reducing 5,7-dinitr0-8-aminoquinoline can be carried out using nascent hydrogen.

Developer components to be used in accordance with the invention are, for example, 5i7j8-triaminoquinoline, 5i7-diamino-8-methylaminoquinoline, S ^ -diamino-e-dimethylaminoquinoline, S ^ -diamino-S-ethylaminoquinoline, 5i7-dia.mino-8-propyl-aminoquinoline, SiO-aminoquinoline -Diamino-S-butylaminoquinoline, 5 * 7-diamino-8-diethylaminoquinoline, 5. »7-diamino-8-di-isopropylaminoquinoline, 5i7-diamino-8-dibutylaminoquinoline _J 5,7i8-triamino-2-methylquinoline, 5j7i8- Triamino-2-ethylquinoline, 5i7i8-triamino-2-butylquinoline _J 5i7j8-triamino-2-hydroxyquinoline, 5i7i8-triamino-6-methylquinoline, S ^ iß-triamino-o-propylquinoline, 5>7> 8-triamino-6- butylquinoline, 5i7i8-T ^ ia-mino-2,6-dimethylquinoline _i 5>Ί>& - triamino-2,6-diethylquinoline, 5> 7i8-triamino-2-methyl-6-ethyl-quinoline, S ^ jS- Triamino - ^ - methylquinoline, 5 _J 7,8-triamino-4 "6-dimethylquinoline, 5.7 _J 8-triamino-4-hydroxyquinoline, 5i7i8-triamino-3-methylquinoline, 5-7-diamino-8-methylamino-2- methylquinoline, 5> 7-diamino-S-dimethylamino-δ-methylquinoline, 5i7-diamino-8-ethylamino-2-butylch inoline, 5j7-diamino-8-propylamino-2,6-dimethylquinoline, S ^ -diamino-S-butylamino - ^^ o 5 _i 7-diamino-8-dibutylamino-4-hydroxyquinoline, 8-morpholinoquinoline, 5JT-diamino-8 -piperidinoquinoline, 5,7-diamino -8 -py rr olidinochino lin, 5, ¹ J -diamino -8 - /? - hydr oxy ■ ethylaminoquinoline, 5,7-diamino-8 - /? - chloroethylaminoquinoline, 5ί7-diamino -8-morpholino-2,6-dimethylquinoline _ί 5i7-Di ^a mino-8-piperidino-4-hydroxyquinoline should be mentioned.

Examples of coupler components to be used in the hair colorants according to the invention are

üC-naphthol, o.cresol, m-cresol, 2,6-dimethylphenol,

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2,5-dimethylphenol, ^, ^ - dimethylphehol, 3,5-dimethylphenol, pyrocatechol, pyrogallol, 1,5- or 1,7-dihydroxy-naphthalene, S-amino ^ -methylphenol, hydroquinone, 2 , 4-diamino-anisole, m-toluenediamine, 4-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, l-phenyl-j5-methyl-pyrazolone-5> 1-phenyl- I> -amino pyrazolone-5, l-phenyl - ^ iS-diketo-pyrazolidine, 1-methyl-7-dimethy 1 -amino- ¹ I - hydroxy-quinolone-2, 1-amino-3-acety1-acetamino-4-nitro-benzene or l-amino-3 -cyanacetylamino-4-nitro-benzene.

In the hair colorants according to the invention, the developer components are generally used in approximately molar amounts, based on the coupler substances used. When molar use turns out to be advisable, however, it is not disadvantageous if the developer component in a certain ^excess: or deficiency passes used. ■■■ "-.- '

Furthermore, it is not necessary that the decomposer components and the coupler substance represent uniform products, rather both the developer component Mixtures of the 5,7,8-triaminoquinolines to be used according to the invention as well as the coupler substance mixtures represent the aforementioned coupler components.

In addition, the hair colorants according to the invention other known and customary developer components and also, if appropriate, customary substantive dyes included in the mixture if this is necessary to achieve certain parbo nuances.

The oxidative coupling, i.e. the development of the color, can basically be carried out as with other oxidized hair dyes also, done by atmospheric oxygen. Expedient- '

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However, chemical oxidizing agents are wisely used. As such, in particular hydrogen peroxide or its addition products onto urea, melamine, and sodium borate, and mixtures of such hydrogen peroxide addition compounds with Kaliumperoxid- ■ disulfate come into consideration.

As a developer component have the invention .. according to 5,7j8-triaminoquinolines the advantage that they even with oxidative coupling by atmospheric oxygen fully satisfactory dyeing results "deliver and thus damage to the hair by the otherwise, for the oxidative Coupling used oxidizing agents can be avoided., Can. However, if at the same time a ■ next to the coloring If you want a lightening effect on your hair, you should use it. of oxidizing agents required.

Surprisingly, they are suitable according to the invention. ■; 5> 7> 8-triaminoquinolines to be added as the only ones Dye component in oxidation hair colors without special Needing coupler components. In doing so, they result in self-condensation with at least one other Mol 5i7jö-triaminoquinoline, which in this case as Coupler component acts under the oxidative action from air or oxidizing agents to hair colors with interesting Brown-red nuances.

The hair colorants according to the invention are for use in corresponding cosmetic preparations, such as Creams, emulsions, gels or even simple solutions incorporated and immediately before application on the Hair mixed with one of the oxidizing agents mentioned. The concentration of such dyeing preparations of the coupler-developer combination is 0.2 to 5 percent by weight, preferably 1-3 percent by weight. To the In the manufacture of creams, emulsions or gels, the coloring components are mixed with the

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the usual additional ingredients. Such additional components are e.g. network or Emulsifiers of the anionic or nonionic type, viie alkylbenzene sulfonates, fatty alcohol sulfates, Alkyl sulfonates, fatty acid alkanolamides, addition products of ethylene oxide with fatty alcohols, thickeners, like methyl cellulose, starch, higher fatty alcohols, Paraffin oil, fatty acids, also perfume oils and hair care products, such as pantothenic acid and cholesterol. The additives mentioned are used in the amounts customary for these purposes, such as ne tz- and emulsifiers in concentrations of 0.5-30 Weight percent and thickener in concentrations of 0.1-25 percent by weight, each based on the entire preparation.

The application of the hair dye according to the invention can, regardless of whether it is a solution, a Emulsion, a cream or a gel acts, in a weakly acidic, neutral or especially alkaline medium at a pH fourth of 8-10. The application temperatures are in the range from 15 to 40 C. After an exposure time of approx. 30 minutes the hair dye is removed from the hair to be colored by rinsing. Afterwards the hair is treated with a mild one Shampoo washed and dried.

The advantages attainable with the inventive hair dye shades show using different developer and coupler components, a wide variation possibility that from light brown to dark brown enough and leads to particularly intense natural brown tones. The dyeings achieved have good 'light, wash and rub fastness properties and can easily be reduced with

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Henkel & Cie GmbH

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remove the agents again.

The following examples are intended to explain the subject matter of the invention in more detail, but without referring to it restrict.

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Henkel & Cie GmbH

Sheet ri to patent application D 49ö3 · Patent Department

Examples

First, preparation inventive hair dyes to be used 5 / 7j8 ~ T ^r iämihochinoline is einiger.in the e £ described, which are not known from the literature. '

A) 5 y 7-diamino-8-methylaminoquinoline trihydrochloride monohydrate - -

8.7 g of 5,7-dinitro-8-methylaminoquinoline were hydrogenated in 200 ml of methanol containing 15 ml of concentrated hydrochloric acid in the presence of 1 g of catalyst (10 % platinum on carbon) at room temperature. After the uptake of hydrogen had ended, the catalyst was filtered off and the filtrate was concentrated. 10.1 g, that is 87 % of theory, of 5j7-diamino-8-methyla-minoquinoline trihydrochloride monohydrate were obtained. The analysis resulted in the following values:

fo C% H Jß. N -

calculated 38.5 5 * 44 17.9 found 38.3 5.2 l8, l

Infrared data in cm " ¹ : 1648, I630, 1590, 1570, 1558,

1500, 1460, 1455 * 1420, 1390,. 1320, 1290, I250, 1220,

1180, 1145, 1120, 1060, 990, 900, 820, 8o4, 760, 647.

The 5> 7-dinitro-8-methylaminoquinoline required as starting material was according to the information from H. Hennig, J. Tauchnitz, K. Schöne in Z.Chem. (1971) Page 267 obtained, whereby the production of 8-chloro-5,7-dinitroehinolins was carried out at 60 ° C. According to this information were also used for the production the 5,7,8-triaminoquinolines described below required dinitro compounds obtained. -

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B) 5j7-DiaraIno-8-dimethyl-aminoquinoline-trihydrochloride-

dihydrate ,,, - ,, -

The production was carried out analogously to product A) with 64% strength Yield from hydrogenation of 5,7-Mnitro-8-dimethylaminoquinoline. The analysis resulted in the following values:

calculated 16.3
found 16.4

Infrared data in cm " ¹ : 1710, I630, I6o4, 1580, 1484, - \

1468, 1430, I4o8, 1340, 1315, 1265, 1235, ■ ll80 -, - 1158, 1135, 1062, 1050, 1020, 975, 888, 875, 815, 785, 640. "- ■■■ - ■■

5,7-di ^on: i ^no "eight-rnorpholinochinolin trihydrochloride tri h ydrat

The production took place analogously to product A) with 87 $ i Yield, by hydrogenation of 5,7-Dirä tr ο-8-morpholi.no quinoline ... The analysis showed the following values:

% N calculated 13.9 found 13.6

Infrared data in cm " ¹ : 1630, 1560, 1450, 1432, 1350, 1305, 1224, 1190, 1100, 1044, 890, 875, 868, 820.

D) 5,7-diamino-8 - /? - hydroxyethylaminoquinoline trihydrochloride monohydrate ''

The preparation was carried out analogously to product A) by hydrogenation of 5> 7-dinitro-8- hydroxyethylaminoquinoline. The analysis resulted in the following values:

% N

calculated 16.2

found 16.3

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Infrared data in cm " ¹ : 1655, 16IO, 1595, 1555, 1484, 1452, 1440, 1410, 1520, 1294, .1230, II80, 1090, IO58, 980, 895, 855, 800, 780, 755, 645 .

The unsubstituted 5j7,8-triaminoquinoline also used in the examples below is known from the literature and its preparation was carried out according to the instructions of Ad. Claus and E. Dewitz in J. Prakt. Chem. 55 (I896) Page 547 -

The hair dyes according to the invention were in the form of a Cream emulsion used. They were made into an emulsion

10 parts by weight of fatty alcohols with a chain length of Cip-C-g 10 parts by weight of fatty alcohol sulfate (sodium salt)

Chain length C ₁₂ ^- C ₁ Q 75 parts by weight V / ater

0.01 mol each of the 5,7> 8-triaminoquinolines and coupler substances listed in the table below are incorporated. The pH of the emulsion was then adjusted to 9.5 by means of ammonia and the emulsion was made up to 100 parts by weight with water. The oxidative coupling was carried out either with atmospheric oxygen or with 1 strength hydrogen peroxide solution as the oxidizing agent, 10 parts by weight of hydrogen peroxide solution being added to 100 parts by weight of the emulsion. The respective coloring cream with or without an additional oxidizing agent was applied to 90 % gray, not specially pretreated human hair and left there for 30 minutes. After the dyeing process was complete, the hair was washed out with a conventional shampoo and then dried. The colorations obtained are shown in Table 1 below.

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Table 1 example

developer

Coupler

1) 2) 5) Oi if) σ co
OO 5) 6) CD 7)

8th) 9)

10)

η)

Preserved color after air oxidation with 1 %

H ₂ O ₂ Ig

5i7j8-triaminoquinoline m-aminophenol "cC-naphthol

"Resorcinol mono-

methyl ether

5,7-diamino-8-methylaminoquinoline

quinoline m-aminophenol

"or naphthol

"Resorcinol mono-

methyl ether

" 5, 7-diamino-8-

methy1-aminoquinoline

5i7-Dlamino-8-dimethyl-m-aminophenol amino quinoline

"Resorcinol mono-

methyl ether

"5,7-diamino-8-

dimethyl-aminoquinoline Brown

dark brown

brown brown brown

brown red-brown

red-brown

brown brown light brown

Brown

red-brown

Brown

light brown brown

brown brown

Brown

yellow-brown yellow-brown light brown

CD

CD

T a b e 1 1 developer . ν π e 1 Preserved shade H ₂ O ₂ Ig SS.
N
C. example Coupler b.air oxidation with 1 % "D
Q
I.
ω light brown f to
O 5,7-diamino-8- yellow-brown olive brown 4 = " 12) morpholinequinoline m-aminophenol dark brown VD
OO It olive brown Previous year 13) 5.7 -Diamino -8 - /? - hydroxy- cC-naphthol dark brown red-brown 14) äthy! aminochinolin m-aminophenol Brown Il Brown 15) ti dt-naphthol Brown dark brown 16) Resorcinol mono- methyl ether Brown 17} 5.7 -Diamino -8-ß-

hydroxyethylamino quinoline

ι- »■ 4 = -.

(P
3 (P ST ßo ;, ο O - * hurry S ' ; 3
(Q Q CD CD -

O"

Claims (1)

Claims 1) Hair dye based on oxidation dyes> characterized by a content of 5.> 7j8-triaminoquinolines of the: general formula '' ^: H ^ N in which X and Y are independently hydrogen, a hydroxyl group or an alkyl radical having 1-4 carbon atoms, R and FU are independently hydrogen, an alkyl radical having 1-4 carbon atoms which can be monosubstituted or polysubstituted by halogen or hydroxyl or R, and R ₂ together with the Stiekstoffa'tom form a five- or six-membered heterocyclic ring, which can contain oxygen or nitrogen as further hetero ring members, and their inorganic or organic salts as developer substances and coupler substances. 2) Hair dye according to claim 1, characterized in that the coupler substances in oxidation colors usual coupler substances are used. J5) hair dye according to claim 1, characterized in that that as coupler substances 5; 7> 8-triaminoquinolines to serve. - 15 - 60981 1/0940 Hang! & Cie GmbH Sheet yfy for patent application D 49Ö3 '. Patent department 4) Hair dye according to claim 1 ->, characterized by a content of a mixture of 5> 7 > -8-triaminoquinolines as developer substances. 5) Hair colorants according to claims 1-4, characterized by a content of other customary developer substances and optionally customary direct-drawing dyes. ^! 6) Hair dye according to claim 1 - % characterized by a content of developer-coupler combinations of 0.2 to 5 percent by weight, preferably 1 to 1 percent by weight, based on the total hair dye. 7) 5 > 7-diamino-8-methylaminoquinoline. -. · < 8) 5 > 7-diamino-δ-dime thy laminoquinoline. :. ". 9) i ^ -Diamino-S-morpholinoquinoline. · ';"■-'" ■ - '·· 10) 5i7-Diamino-8-y9-hydroxyethylaminoquinoline * _:. r 6098 11/09 40