NO151086B - ALKYLIDENAMINOPHENOLS AND THE USE OF THE ALKYLIDENAMINOPHENOLS AND THEIR SALTS WITH INORGANIC OR ORGANIC ACIDS AS COUPLING COMPONENTS IN OXIDATION HAIR COLORING AGENTS - Google Patents

Description

The object of the invention is new 2,4-dichloro-3-alkylidene aminophenols of the general formula

where k-j means hydrogen or an alkyl residue with 1-6 carbon atoms and R2 means an alkyl or phenyl residue with the precaution that R2 can only be a phenyl residue when Rj means hydrogen. Preferably, R ± and R 2 , which may be the same or different, mean an alkyl radical with 1-4 carbon atoms. The production of the new 2,4-dichloro-3-alkylidene-aminophenols takes place by prolonged heating of 2,4-dichloro-3-aminophenol with a compound of the general formula

wherein and R2 have the above meaning. Compounds with the formula Rj-CO-R2 are preferably used in excess, as these also serve as a solvent. The method can also be carried out in the presence of other solvents such as alcohols or chlorinated hydrocarbons. Boil for a short time under reflux and let it react for a few hours at 0 - 50°C.

The turnover is suitably carried out in the presence of catalysts favoring water splitting. These are preferably mineral acids such as HC1, H2SO4, as well as toluenesulfonic acid and the like. Preferably, HC1 is used.

A further object of the invention is the use of the new 2,4-dichloro-3-alkylideneaminophenols as such or in the form of their salts with inorganic or organic acids as coupling components in oxidation hair dyes.

For coloring hair, the so-called oxidation dyes that occur by oxidative coupling of a developer component with a coupling component play a preferred role because their intense colors and very good authenticity properties. Nitrogen bases such as p-phenylenediamine derivatives, diaminopyridines, 4-aminopyrazolone derivatives, heterocyclic hydrazones are usually used as developers. As so-called coupler components, m-phenylenediamine derivatives, phenols, naphthols, resorcin derivatives and pyrazolones are mentioned.

Good oxidation hair dye components must primarily fulfill the following requirements: They must form the desired color shades in sufficient intensity through the oxidative coupling with any developing or coupling components. They must also have a sufficient to very good pulling ability for human hair and they must also be harmless from a toxicological and dermatological point of view.

Therefore, when searching for usable oxidation hair dyes, the task was to find suitable components that fulfill the above-mentioned prerequisites in an optimal way.

It has now been found that oxidation hair colors that meet these requirements to a particularly high degree are achieved when 2,4-dichloro-3-alkylideneaminophenols with the general formula are used as coupling components

in which R.j means hydrogen or an alkyl residue with 1-6 carbon atoms and R2 means an alkyl or phenyl residue with the precaution that R2 can only be an eri phenyl residue when R^ means hydrogen,

as well as their salts with inorganic or organic acids in combination with usual developer substances.

The hair coloring agent based on oxidation dyes with a content of 2,4-dichloro-3-alkylideneaminophenols with the general formula

in which R 1 and R 2 have the above-mentioned meaning as well as their salts with inorganic or organic acids as coupling components and the developing agents common in oxidation hair dyes are consequently valuable compositions in the field of oxidation hair dyes.

According to the invention, their use as coupler components gives, in developing substances usually used for oxidative hair dyeing, very intense shades ranging from brown to dark blue to dark violet and is thus a significant enrichment of oxidative hair dyeing possibilities. Moreover, the 2,4-dichloro-3-alkylidene-aminophenol according to the invention is distinguished by very good authenticity properties of the dyes thus obtained, with a good solubility in water, good storage stability and toxicological and dermatological harmlessness.

2,4-dichloro-3-alkylideneaminophenols can either be used

as such or in the form of their salts with inorganic or organic acids such as chlorides, sulphate, phosphate, acetate, propionate, lactate, citrates.

Examples of usable coupler components include 2,4-dichloro-3-(methyl-3'-butylidene-2)-aminophenol, 2,4-dichloro-3-(isopropylidene)-iminophenol, 2,4-dichloro-3 -benzylideneaminophenol.

For example in hair dyes

usable developer components are to list primary aromatic amines with an additional p-position functional group such as p-phenylenediamine, p-toluylenediamine, p-aminophenol, N-methyl-p-phenylenediamine, N,W-dimethyl-p-phenylenediamine, N -ethyl-N-hydroxyethyl-p-phenylenediamine, chloro-p-phenylenediamine, N,N-bis-hydroxyethylamino-p-phenylenediamine, methoxy-p-phenylenediamine, 2-chloro-, 2,6-dichloro-p-phenylenediamine, 2-chloro-6-bromo-p-phenylenediamine, 2-chloro-6-methyl-p-phenylenediamine, 6-methoxy-3-methyl-p-phenylenediamine, other compounds of the aforementioned types which further form one or more functional groups which OH groups, Nl^ groups, NHR groups, NR2_groups, where R means an alkyl or hydroxyalkyl residue with 1-4 carbon atoms, further diaminopyridine derivatives, heterocyclic hydrazone derivatives such as 1-methyl-pyrrolidone-(2)-hydrazone, 4-aminopyrazolone derivatives " such as 4-amino-l-phenyl-3-carbamoyl-pyrazolone-5, N-butyl-N-sulfobutyl-p-phenylenediamine, tetraamino-pyrimidines such as 2,4,5,6-tetraaminopyrimidine, 4,5-diamino- 2, 6-bismethylaminopyrimidine, 2,5-diamino-4-diethylamino-6-methylaminopyrimidine, 2,4,5-triamino-6-dimethylaminopyrimidine, 2,4,5-triamino-6-piperidinopyrimidine, 2,4,5- triamino-6-anilino-pyrimidine, 2,4,5-triamino-6-morpholini-pyrimidine, 2,4,5-triamino-6-g-hydroxy-ethylamino-pyrimidine.

The coupler components provide, alongside other color shades with corresponding developer substances, dark blue, particularly intense hair dyes that are distinguished by extraordinary lightfastness. They are therefore also of particular importance as tinting components for achieving the most powerful and natural hair color shades and the most possible corresponding hue, as difficulties often arise when exhibiting natural color shades using blue coupler components.

In the hair dyes, the coupler components are usually used in approximately molar amounts with reference to the developers used. However, when molar application also proves appropriate, it is not unfortunate when the coupler components come into use.

otherwise in a certain surplus or deficit.

Furthermore, it is not necessary that the developer component and the coupler component are uniform products, while both the developer components can form mixtures of the developer components that can be used according to the invention, and the coupling substance can also form mixtures of the 2,4-dichloro-3-alkylideneaminophenols that can be used according to the invention, optionally in admixture with further common coupling agents.

In addition, the hair dye can optionally

contain normal direct dyes in the mixture, if this is necessary to achieve certain color shades.

The oxidative coupling, i.e. development of the colouring, can in principle take place as with other oxidation hair dyes also with the help of atmospheric oxygen. However, chemical oxidizing agents are used appropriately. As such, it particularly mentions hydrogen peroxide and its formation products for urea, melamine and sodium borate, as well as mixtures of such hydrogen peroxide formation compounds with potassium peroxide disulphate.

The hair dye is incorporated before use

in the corresponding cosmetic preparations such as creams, emulsions, gels or also simple solutions, and mixed immediately before application to the hair with one of the aforementioned oxidizing agents. The concentration of such color preparations of the coupler-developer combination amounts to 0.2 to 5% by weight, preferably 1 to 3% by weight. For the production of creams, emulsions or gels, the dye components are mixed with the additional components usual for such preparations. Examples of such additional ingredients include wetting or emulsifying agents of anionic or non-ionic type such as alkylbenzene sulphonates, fatty alcohol sulphates, alkyl sulphonates, fatty acid alkanol amides, formation products of ethylene oxide to fatty alcohols, thickeners such as methyl cellulose, starch, higher fatty alcohols, paraffin oil , fatty acids, further perfume oil and hair care products such as pantothenic acid and cholesterol. They mentioned

additives are thereby used in the usual amounts for these purposes, such as wetting and emulsifying agents in concentrations from 0.5 to 30% by weight and thickeners in concentrations from 0.1 to 25% by weight, each time referring to the overall preparation.

The application of the hair dye can be independent

of whether it is a solution, emulsion,

cream or a gel, take place in a slightly acidic, neutral or particularly alkaline environment at a pH value of 8-10. The application temperatures thereby move in a range from 15 to 40°C. After an impact duration of approx. After 30 minutes, the hair dye is removed from the hair to be dyed by rinsing. The hair is then washed with a mild shampoo and dried.

The colorings that can be achieved with the hair dye, especially the blue tones, show particularly intense color nuances when different developers and coupling components are used. The obtained colorings have

good light, washing and friction fastness properties and can be easily removed again with reducing agents.

The invention will be explained in more detail with the help of some examples;

Example 1

2, 4- dichloro- 3-( methyl- 3'- butylidene- 2)- aminophenol- hydrochloride

5 g of 2,4-dichloro-3-aminophenol hydrochloride (prepared according to the specification in the German offenlegungs-schrift 2 509 096) are boiled in 50 ml of methyl isobutyl ketone for half an hour under reflux. After cooling, the product was sucked off and dried. The formed 2,4-dichloro-3-(methyl-3'-butylidene-2)r-aminophenol hydrochloride has the following IR absorption spectrum: IR spectrum (KBr) cm-1: 1650, 1620, 1520, 1475 , 1435, 1370, 1315, 1260, 1215, 1180 , 1090 ,- 1045, 1010, 980, 970, 825, 815, 790, 785, 760, 690.

Example 2

2/ 4- dichloro- 3-( isopropylidene)- aminophenol hydrochloride

Corresponding to the indication in example 1, 2,4-dichloro-3-aminophenol hydrochloride was reacted with acetone. The formed reaction product according to the invention has the following characteristic data;

IR spectrum (KBr) cm"<1>: 1652, 1598, 1570, 1480, 1438, 1370, 1315, 1260, 1238, 1225, 1218, 1176, 1112, 1085, 1010, 980, 930, 870, 835, 805, 762, 730, 710, 675, 655.

Example 3

2, 4- dichloro- 3- benzylidene- aminophenol- hydrochloride

Analogous to the indication in example 1, 2,4-dichloro-3-aminophenol hydrochloride was reacted with benzaldehyde. The reaction product according to the invention has the following characteristic data: IR spectrum (KBr) cm"<1>: 1692, 1620, 1598, 1582, 1515, 1480, 1450, 1430, 1310, 1205, 1160, 1075, 1030, 930, 905, 890, 872, 830, 805, 745, 700, 685, 650.

The above in their representation in the examples

The 2,4-dichloro-3-alkylideneaminophenols mentioned in 1, 2 and 3 were used as coupler components according to experiments.

The following substances served as developing substances:

E 1: p-toluylenediamine

E 2: 2,4,5,6-tetraaminopyrimidine

E 3: 2-piperidino-4,5,6-triaminopyrimidine

E 4: 2-methylamino-4,5,6-triaminopyrimidine

E 5: 2-morpholino-4,5,6-triaminopyrimidine

E 6: p-phenylenediamine

E 7: 2-chloro-p-phenylenediamine

E 8: p-aminophenol

E 9: N-methyl-p-phenylenediamine

E 10: N-ethyl-N-g-hydroxyethyl-p-phenylenediamine

E 11: N,N-bis-(3-hydroxymethyl)-amino-p-phenylenediamine.

The hair dye according to the invention was used in the form of a cream emulsion. This resulted in an emulsion of 10 parts by weight of chain-length fatty alcohols

<C>12 <C>18'

10 parts by weight fatty alcohol sulphate (sodium salt)

of the chain lengths C^2~ c^g °9

, 75 parts by weight of water

each time incorporated 0.01 mol of the developing substances and coupling substances listed in the following table. The emulsion's pH value was then adjusted to 9.5 using ammonia and the emulsion filled with water to k00 parts by weight. This oxidative coupling was carried out with a 1% hydrogen peroxide solution as oxidizing agent, 10 parts by weight of hydrogen peroxide solution being added to 100 parts by weight of the emulsion. Any color creams with the addition of oxidizing agents were applied to up to 90% greyed, not specially pre-treated human hair and left there for 30 minutes. After the end of the coloring process, the hair was washed out with

a regular hair detergent and then dried. The resulting colorings are shown in the following table 1.

Claims (3)

1. Alkylideneaminophenols, characterized in that they correspond to the general formula wherein R means hydrogen or an alkyl residue of 1-6 carbon atoms, and R 2 means an alkyl or phenyl residue, with the 2 "1 precaution that R can only be a phenyl residue, when R means hydrogen. 2. Alkylideneaminophenols according to claims 1, 12, characterized in that R and R are the same or different and mean an alkyl residue with 1-4 carbon atoms. 3. Use of alkylidene aminophenols according to claim 1 or 2 as well as their salts with inorganic or organic acids as coupling components in oxidation hair dyes with the developer components common in oxidation dyes.