DE2716671A1 - Amino:pyrimidine-developed oxidn. hair dyes - contain amino derivs. of indoline, isatin or indole(s) as the coupler to provide brown to violet colouration - Google Patents

Abstract

An oxidn. hair dye compsn. contains a cpd. of formula (I) as the coupler and a conventional developer (II). In (I), R1 and R2 may each be H or 1-4C alkyl and X and Y may each be CR1R2 or CO). Some of (I) are new cpds. (II) is pref. a tetraaminopyrimidine deriv. The (I)-(II) combination produces intense brown to violet hues and (I) has good water solubility, storage stability and is toxicologically and dermatologically innocuous. The dyeings are light-fast.

Description

"Hair dye"

The invention relates to agents for the oxidative coloring of hair based on diaminoindoline, diaminoisatin or diaminooxindole derivatives as a coupler component.

The so-called oxidation colors play a role in the coloring of hair, that by oxidative coupling of a developer component with a coupler component arise because of their intense colors and very good fastness properties preferred role. Nitrogen bases are usually used as developer substances, such as p-phenylenediamine derivatives, diaminopyridines, 4-amino-pyrazolone derivatives, heterocyclic ones Hydrazones used. Phenols, naphthols, Resorcinol derivatives and pyrazolones called.

Good oxidative hair dye components must primarily include the following Meet the prerequisites: You must with the oxidative coupling with the respective Developer or coupler components the desired color nuances in sufficient Develop intensity. They must also have sufficient to very good absorbability on human hair and they are also said to be toxicological and be dermatologically harmless. It is also important that Strong and natural hair color nuances on the hair to be dyed largely obtained corresponding shades will. Further comes the general stability of the dyes formed and their lightfastness, Wash fastness and thermal stability are of particular importance to avoid color shifts from the original color nuance or even color changes to other shades.

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

It has now been found that hair dyes based on oxidation dyes with a content of diaminoindoline, diaminoisatin or diaminooxindole derivatives of the general formula in which R1 and R2, which can be identical or different, denote hydrogen or an alkyl radical having 1-4 carbon atoms and X and Y, which can be identical or different, denote the groups> CR1R2 or> CO, where R1 and R2 are the have the abovementioned meaning, and their inorganic or organic salts as coupler substances and the developer components customary in oxidation hair dyes meet the requirements set to a particularly high degree.

When used as coupler components, those according to the invention provide Compounds with the developer substances generally used for oxidation hair coloring very intense color nuances ranging from brown to purple and thus represent a essential enrichment of the oxidative hair coloring possibilities. In addition the indoline, isatin and oxindole derivatives according to the invention are distinguished by very good fastness properties of the dyeings achieved therewith, through good Solubility in water, good storage stability and toxicological as well as dermatological Harmlessness.

The indoline to be used according to the invention as coupler components, Isatin or oxindole derivatives can either as such or in the form of their salts with inorganic or organic acids, such as. B. as chlorides, sulfates, phosphates, Acetates, propionates, lactates, citrates can be used.

The indoline to be used according to the invention as coupler components, Isatin or oxindole derivatives are partly new compounds. Their production can in a known manner by catalytic hydrogenation of corresponding nitro derivatives take place.

As coupler components to be used according to the invention are 5,7-diaminoindoline, 5,7-diamino-1-methylindoline, 5,7-diamino-2-methylindoline, 5,7-diamino-3-methylindoline, 5,7-diamino-2,2-dimethylindoline, 5,7-diamino-2,3-dimethylindoline, 5,7-diamino-2-methyl-3-ethylindoline, 5,7-diamino-1-ethyl-2-methyl-2-ethylindoline, 5,7-diamino-6-methylindoline, 5,7-diamino-1,6-dimethylindoline, 5-dimethylamino-7-amino-1-butylindoline, 5-diethylamino-7-amino-2,2-dipropylindoline, 5-amino-7-dimethylamino-2-methyl-3-butylindoline, 5-amino-7-dibutylamino-3, 3-diethylaminoindoline, 5,7-bis-dimethylaminoindoline, 5,7-diaminoisatin, 5,7-diamino-6-ethylisatin, 5,7-diamino-2-oxindole, 5,7-diamino-1-methyl-2-oxindole, 5,7-diamino-3-ethyl-2-oxindole r 5,7-diamino-6-butyl-2-oxindole, 5,7-diamino-1,3-dimethyl-2-oxindole, 5,7-diamino-3,3-diethyl-2-oxindole, 5-diethylamino-7-amino-2-oxindole, 5,7-bis-dimethylamino-2-oxindole and 5,7-diamino-3-oxindole to call.

As examples of those to be used in the hair colorants according to the invention Developer components are primary aromatic amines with another in the p-position functional group located such as p-phenylenediamine, p-tolylenediamine, p-dimethylaminoaniline, p-aminophenol, p-diaminoanisole or other compounds of the type mentioned, which continue to one or more functional groups such as OH groups, NH2 groups, NHR groups, NR2 groups, where R is an alkyl or hydroxyalkyl radical with 1 - 4 carbon atoms represents, also diaminopyridine derivatives, heterocyclic hydrazone derivatives, 4-aminopyrazolone derivatives, how to list 4-amino-1-phenyl-3-carbamoylpyrazolon-5.

The indoline, isatin or oxindole derivatives to be used according to the invention as coupler components in combination with tetraaminopyrimidines of the general formula are of particular importance in which R1 - R6 is hydrogen, an alkyl radical with 1 - 4 carbon atoms, the radical - (ClI2) nX, in which n = 1 - 4 and X is a hydroxyl group, a halogen atom, an -NH2 -, -NHR'- and -NR 'R' group, where R 'and R''can be alkyl radicals with 1-4 carbon atoms or with the nitrogen atom to form a heterocyclic ring which can contain a further nitrogen atom or oxygen atom, R1 and R2, or R3 and R4, or R5 and R6 together with the respective nitrogen atom can represent a heterocyclic 5- or 6-membered ring with one or two nitrogen atoms or one nitrogen atom and one oxygen atom and their inorganic or organic salts as developer substances.

The tetraaminopyrimidines to be used as developer components can either as such or in the form of their salts with inorganic or organic Acids, e.g.

as chlorides, sulfates, phosphates, acetates, propionates, lactates, citrates can be used.

As in combination with the indoline, isatin or oxindole derivatives Tetraaminopyrimidines to be used in the hair dyes according to the invention are z. B. 2,4,5,6-tetraamino, 4,5-diamino-2,6-bismethylamino, 2,5-diamino-4,6-bismethylamino, 4, 5-diamino-6-butylamino-2-dimethylamino, 2, 5-diamino-4-diethylamino-6-methylamino, 4,5-diamino-6-diethylamino-2-dimethylamino-> 4,5-diamino-2-diethylamino-6-methylamino, 4, 5-diamino-2-dimethylamino-6-ethylamino, 4, 5-diamino-2-dimethylamino-6-isopropylamino, ii, 5-diamino-2-dimethylamino-6-methylamino-, 4,5-diamino-6-dimethylamino-2-methylamino, 4,5-diamino-2-dimethylamino-6-propylamino-, 2,4,5-triamino-6-dimethylamino-, 4,5,6-triamino-2-dimethylamino, 2,4,5-triamino-6-methylamino, 4,5,6-triamino-2-methylamino, 4,5-diamino-2-dimethylamino-6-piperidino, 4,5-diamino-6-methylamino-2-piperidino-, 2,4,5-triamino-6-piperidino-, 2,4,5-triamino-6-anilino-, 2,4,5-triamino-6-benzylamino, 2,4,5-triamino-6-benzylideneamino, 4,5,6-triamino-2-piperidino, 2,4,6-trismethylamino-5-amino-, 2,4,5-triamino-6-di-n-propylamino-, 2,4,5-triamino-6-morpholino, 2,5,6-triamino-4-dimethylamino-, 4,5,6-triamino-2-morpholino-, 2,4,5-triamino-6-B-hydroxyethylamino-, 4,6-triamino-2-a-amino-ethylamino-, 2,5,6-triamino-4-B-methylamine-ethylamine 2, 5-diamino-4, 6-bis-y-diethylamino-propylamino, 4,5-diamino-2-methylamino-6-ß-hydroxy-sthylamino, 5-amino-2,4,6-triethylamino-, 2,4-bis-ß-hydroxyethylamino-6-anilino-5-aminopyrimidine to call.

The preparation of the tetraaminopyrimidines to be used as developer components is already known from the literature and can be compared to the monograph by D.J. Brown, "The Pyrimidines in the series Heterocyclic Compounds, Interscience Publishers (1962) Volumes I and II can be removed.

For the synthesis of the compounds to be used as developer components one generally starts from 2,4,6-triaminopyrimidines, in which the 5-amido group is introduced by nitrosation and subsequent reduction. But you can too start from appropriately substituted triaminoalkylmercaptopyrimidines and the Substitute alkyl mercapto groups with amines. The latter method is suitable especially for the introduction of amino groups or substituted amino groups in the 2-, 4- or 6-position of the pyrimidine ring.

To achieve the strongest and most natural hair color shades possible A full-fledged blue dye is used as a nuance component of largely corresponding color shades of particular importance. When creating natural color nuances with the help of blue coupler components, however, difficulties arise with the usual blue couplers, even with the use of the otherwise very satisfactory tetraaminopyrimidines as developing agents. This deficiency can be overcome by using the to be used indoline, isatin or oxindole derivatives can be remedied.

These coupler components deliver with the tetraaminopyrimidines as well other shades of dark blue to violet-black particularly intense hair colors, which are characterized by extraordinary lightfastness.

The coupler components are used in the hair dyes according to the invention generally in approximately molar amounts, based on the developer substances used, used. If molar use also proves useful, so it is but not disadvantageous if the coupler component is in a certain excess or a shortfall is used.

It is also not necessary that the developer component and the coupler substance represent uniform products, rather both the Developer component Mixtures of the developer compounds to be used according to the invention as well as the coupler substance mixtures of the indoline to be used according to the invention, Represent isatin or oxindole derivatives.

In addition, the hair colorants according to the invention can optionally Usual substantive dyes contained in the mixture, if this is to achieve certain color nuances is required.

The oxidative coupling, i.e. the development of the color, can in principle As with other oxidation hair dyes, it is done by means of atmospheric oxygen. Appropriately however, chemical oxidizing agents are used. As such come in particular Hydrogen peroxide or its addition products with urea, melamine and sodium borate as well as mixtures of such hydrogen peroxide addition compounds with potassium peroxide disulfate into consideration.

The tetraaminopyrimidines have the developer component The advantage that they are fully satisfactory even with oxidative coupling by atmospheric oxygen Provide coloring results and thus a hair damage by the otherwise for the oxidative Coupling used oxidizing agents can be avoided. However, it will be at the same time In addition to the coloring, if a lightening effect is desired on the hair, it should also be used of oxidizing agents required.

The hair dyes according to the invention are suitable for use in cosmetic preparations such as creams, emulsions, gels or simple solutions incorporated and immediately before application on the hair with one of the mentioned Oxidizing agents added. The concentration of such dyeing preparations of the coupler-developer combination is 0.2 to 5 percent by weight, preferably 1 to 3 percent by weight. Used in the production of creams, emulsions or gels the dye components with the other ingredients customary for such preparations mixed. As such additional ingredients are e.g.

Wetting or emulsifying agents of the anionic or nonionic type such as alkyl benzene sulfonates, fatty alcohol sulfates, alkyl sulfonates, fatty acid alkanolamides, Addition products of ethylene oxide to fatty alcohols, thickeners such as methyl cellulose, Starch, higher fatty alcohols, paraffin oil, fatty acids, also perfume oils and hair care products like pantothenic acid and cholesterol. The additives mentioned are used in the amounts customary for this purpose, such as. B. Wetting and emulsifying agents in concentrations of 0.5 to 30 percent by weight and thickeners in concentrations from 0.1 to 25 percent by weight, in each case based on the total preparation.

The application of the hair colorants according to the invention can, independently whether it is a solution, an emulsion, a cream or a gel, in a weakly acidic, neutral or especially alkaline environment at a pH value from 8 to 10. The application temperatures are in the range from 15 to 400C. After an exposure time of about 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 following examples are intended to explain the subject matter of the invention in greater detail explain without, however, restricting it to this.

Examples First, the preparation of some to be used in accordance with the present invention will be described Indoline, isatin and oxindole derivatives are described in the following examples serve as coupler components.

A) 5,7-Diamino-2-methylindoline trihydrochloride a) 5,7-Dinitro-2-methylindoline.

In a solution, cooled to 100C, of 7.8 g of 2-methylindoline in 90 ml of acetic anhydride were added dropwise to 5 ml of fuming nitric acid. The solution was poured onto ice and the separated bl recrystallized from ethanol. The product was dissolved in 175 ml of acetic anhydride and 14 ml were added to the solution at 150.degree Nitric acid (D = 1.5 added dropwise. The solution was stirred for 3 hours while the temperature rose to 50 ° C. The solution was poured into 600 ml of ice water. The resulting precipitate was filtered off and the crystals concentrated in 180 ml Hydrochloric acid refluxed for 1 hour. The precipitate was filtered off and recrystallized from ethanol.

There were 4.4 g of the nitro compound in the form of yellow crystals Melting point 149-151 ° C. The mass spectrum showed the molecular mass of 222.

b) 4.2 g of the nitro compound obtained were in 100 ml of ethanol in the presence of 0.5 g of catalyst (5% palladium on carbon) at room temperature reduced. After the uptake of hydrogen had ended, the catalyst was filtered off and acidified with dilute hydrochloric acid. There were 3.4 g of 5,7-diamino-2-methylindoline trihydrochloride obtained in the form of black-brown crystals with a melting point of 1820C (decomposition).

B) 5,7-diamino-3-methylindoline trhydrochloride a) 5,7-dinitro-3-methylindoline.

30 g of 3-methylindoline were made as described above nitrided. There were 6 g of the nitro compound in the form of yellow crystals having a melting point 1640C received.

b) 6 g of the nitro compound obtained were corresponding to the above Information catalytically reduced. There were 5 g of 5,7-diamino-3-methylindoline trihydrochloride obtained in the form of gray-brown crystals with a melting point of 233 ° C. (decomposition).

C) 5,7-diaminoindo.nindihydrochloride 0.3 hydrate 5 g 5,7-dinitroindoline, prepared according to the information in J. Org. Chem. 29, page 948, were accordingly catalytically reduced to the above information under A) b). There were 3 g of 5,7-diaminoindoline dihydrochloride 0.3 hydrate obtained in the form of brown crystals with a melting point> 2500C.

D) 5,7-diaminoisatin dihydrohoride monohydrate 3.5 g of 5,7-dinitroisatin, prepared as described in J. Chem. Soc. (1930) page 839, were accordingly catalytically reduced to the above information under A) b).

There was obtained 2.1 g of 5,7-diamitoisatin dihydrochloride monohydrate in the form brown crystals with a melting point of> 2700 ° C. were obtained.

E) 5,7-diamino-2-oxindole dihydrochloride tetrahydrate 5 g 5,7-dinitro-2-oxindole, manufactured according to the specifications of Can. J. Chem. 3747, 48 (1974) have accordingly catalytically reduced to the above information under A) b).

There were 2.9 g of 5,7-diarnino-2-oxindole dihydrochloride tetrahydrate in Obtained in the form of yellow crystals with a melting point of> 270 C. The mass spectrum showed the molecular mass 163.

t t B n, r 1 infrared spectrum (cm): 1695> 1630, 1540, 1485, 1400, 1330, 1300, 1255, 1205, 1115, 890, 860, 815.

As the developer components in the following examples, the following were used compounds mentioned are used: El 2,4,5,6-tetraaminopyrimidine E2 2-dimethylamino-4,5,6-triaminopyrimidine E3 2-morpholino-4,5,6-triaminopyrimidine E4 p-aminophenol E5 p-phenylenediamine E6 N, N-Dimethyl-p-phenylenediamine E7 p-Tolylenediamine E8 2-piperidino-4,5,6-triaminopyrimidine E9 2-methylamino-4,5,6-triaminopyrimidine The following coupler components were used Compounds: K1 5,7-diaminoindoline K2 5,7-diamino-2-methylindoline K3 5,7-diamino-3-methylindoline K4 5,7-diaminoisatin K5 5,7-diamino-2-oxindole The hair colorants according to the invention were used in the form of a cream emulsion. They were made into an emulsion 10 parts by weight of fatty alcohols of chain length C12-C18, 10 parts by weight of fatty alcohol sulfate (Sodium salt) of chain length C12-C18, 75 parts by weight of water 0.01 mol of each in the table below listed developer substances and indoline, isatin respectively.

Oxindole derivatives incorporated. After that, the pH was the Emulsion adjusted to 9.5 with ammonia and the emulsion with water to 100 Parts by weight filled up. The oxidative coupling was carried out with either atmospheric oxygen or carried out with 1% hydrogen peroxide solution as the oxidizing agent, wherein 10 parts by weight of hydrogen peroxide solution were added to 100 parts by weight of the emulsion became.

The respective coloring cream with or without an additional oxidizing agent was applied to 90% gray, not specially treated human hair and leave there for 30 minutes.

After completing the dyeing process, the hair was treated with a usual Shampoo washed out and then dried.

The colorations obtained are shown in Table 1 below.

Table 1 At- a) Ent- b) Kupp- Color obtained Play winder with air with 1% oxidation of H2O2 solution 1 tbsp K1 violet-blue violet-black 2 E2 K1 dark blue dark blue 3 E3 K1 gray blue black blue 4 E4 K1 red brown purple brown 5 E5 K1 dark ruby purple gray 6 E6 K1 purple gray dark purple 7 El K2 dark brown dark brown 8 E7 K2 gray-brown gray-brown 9 E8 K2 olive gray olive gray 10 E9 K2 brown gray brown gray 11 El K3 black-blue black-blue 12 E7 K3 dark purple dark purple 13 E1 K4 violet brown brown 14 E7 K4 red brown dark brown 15 E2 K4 violet brown brown 16 E5 K4 red brown brown gray 17 E8 K4 gray ruby red brown 18 E9 K4 violet brown gray red 19 El K5 gray-red red-brown 20 E7 K5 gray brown dark brown

Claims (9)

"Hair colorant" claims: 1. Hair colorant based on oxidation dyes, characterized by a content of diaminoindoline, diaminoisatin or diaminooxindole derivatives of the general formula in which R1 and R2, which can be identical or different, denote hydrogen or an alkyl radical having 1-4 carbon atoms and X and Y, which can be identical or different, denote the groups) CR1R2 or = CO, where R1 and R2 denote have the aforementioned meaning, as well as their inorganic or organic salts as coupler substances and the developer components customary in oxidation paints. 2. Hair dye according to claim 1, characterized in that the developer component is tetraaminopyrimidines of the general formula in which R1 - R6 is hydrogen, an alkyl radical with 1 - 4 carbon atoms, the radical - (CH2) nX, in which n = 1 - 4 and X is a hydroxyl group, a halogen atom, an -NH2-, -NHR 'and -NR' R "group, where R 'and R" can represent alkyl radicals with 1-4 carbon atoms or with the nitrogen atom to form a heterocyclic ring which can contain a further nitrogen atom or oxygen atom, R1 and R2, or R3 and R4, or R5 and R6 together with the respective nitrogen atom can represent a heterocyclic 5- or 6-membered ring with one or two nitrogen atoms or one nitrogen atom and one oxygen atom, and their inorganic or organic salts can be used. 3. Hair dye according to claim 1 and 2, characterized by a Content of other customary coupler substances and, if appropriate, customary substantive substances Dyes. 4. Hair dye according to claim 1-3, characterized by a Content of developer-coupler combinations of 0.2-5 percent by weight, preferably from 1 to 3 percent by weight. 5. 5,7-diaminoindoline. 6. 5,7-diamino-2-methylindoline. 7. 5,7-diamino-3-methylindoline. 8. 5,7-diaminoisatin. 9. 5,7-diamino-2-oxindole.