NO853431L - HAARFARGEMIDDEL. - Google Patents

Abstract

N-benzyl-p-phenylenediamine and derivatives of the general formula. wherein R represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R 2 represents hydrogen, chlorine or an alkyl group having 1 to 4 carbon atoms, R 1 represents hydrogen or a hydroxyl group and R 2 represents independently hydrogen or chlorine or their salts suitable as oxidation hair dye precursors for hair dyes. The compounds alone or together with known couplers and / or developer compounds give brilliant hair dyes of high authenticity, especially in the area of blue. red and brown shades.

Description

The object of the invention is hair dyes based on oxidation dyes. Such hair dyes contain oxidation dye precursors in a cosmetic carrier.

Developers and coupling agents are used as oxidation dye precursors, which form dyes under the influence of oxidizing agents or atmospheric oxygen. Creams, emulsions, gels, shampoos, foam aerosols or other preparations suitable for application to the hair serve as cosmetic carriers for the oxidation dye precursors.

For coloring hair, they play so-called oxidation dyes,

which occurs by oxidative coupling of one or more developer components with each other or with one or more coupling components due to their intense colors and good authenticity properties a preferred role. Primary aromatic amines with an additional free or substituted hydroxy or amino group in the para or ortho position, further diaminopyridine derivatives, heterocyclic hydrazone derivatives, 4-aminopyrazolone derivatives and tetraaminopyrimidines are usually used as developers. As so-called coupling substances, m-phenylenediamine derivatives, naphthols, resorcin derivatives and pyrazolones are used.

Good oxidation hair dye pre-products must first of all fulfill the following requirements: They must at the oxidation

tive coupling formed the desired color shades in sufficient intensity and authenticity. They must also have a good ability to attract human hair without coloring the scalp too strongly, and they must above all be harmless from a toxicological and dermatological point of view.

It is true that p-phenylenediamine and many derivatives of this compound have long been known as oxidation dye precursors. However, it is also known that many of these compounds are toxicologically and dermatologically questionable,

as they have mutagenic and/or allergenic properties.

There was therefore a high technical interest in oxidation dye precursors, which on the one hand form intense colors with high authenticity properties, but on the other hand are safe in toxicological and dermatological terms.

It has now been found that hair dyes containing oxidation dye precursors in a cosmetic carrier, which as oxidation dye precursors contain N-benzyl-p-phenylenediamine or its derivatives of the general formula

in which R means hydrogen or an alkyl group with 1-4 C atoms, R 2 means hydrogen, chlorine or an alkyl group with 1-4 C atoms,

3 4 5

R means hydrogen or a hydroxyl group, and R and R independently mean hydrogen or chlorine or their salts and the coupling and/or developer substances common in oxidation dyes to a high degree meet the requirements, and above all with regard to the toxicological and dermatological properties are harmless and safe. The hair dyes according to the invention give particularly intense and brilliant hair colors of high light and heat fastness, especially in the area of the blue, red and brown shades.

Particularly intense and stable shades of color are obtained when the N-benzyl-p-phenylenediamines of formula I used according to the invention contain substituents in the combinations E1, E2, E3, E4

or E5.

E 1: R<1>= H R<2>= H R<3>= H R<4>= H R<5>= H

E 2: R1 = CH3 R2 = H R3 = H R4 = H R5 - H

E 3: R1 = H R2 = H R3 = H R4 = H R5 = H

E 4: R<1>= H R<2>= H R<3>= OH R<4>= Cl R<5>= Cl E 5: R<1>= H R<2>= CH3R<3>= OH R<4>= H R<5>= H

According to the invention, N-benzyl-p-phenylenediamine (E1), which can be used as an oxidation hair dye precursor, is a compound known in the literature (compare Annalen der Chemie, 263, 302). The other compounds corresponding to the general formula I are available by synthetic methods known in the literature.

3 4 5

In general, when R , R and R mean halogen or a hydroxyl group, a correspondingly substituted p-nitroaniline can be reacted with a correspondingly substituted benzyl alcohol according to the general reaction scheme

3 4 5 or, if R , R and R are hydrogen or alkyl groups, react a correspondingly substituted p-chloro-nitrobenzene with a correspondingly substituted benzylamine according to the general reaction scheme _ A

to N-benzyl-p-nitroaniline and catalytically hydrogenate this to N-benzyl-p-phenylenediamine. The preparation of the derivatives E 2 - E 5 not known in the literature is discussed in more detail in the examples.

The N-benzyl-p-phenylenediamines of the general formula I that can be used according to the invention are developers, i.e. they are capable of forming dyes under the influence of oxidizing agents. In the presence of coupling substances, however, particularly brilliant and intense colors are formed. As coupling substances, m-phenylenediamines, m-aminophenols, resorcins, naphthol-1, 1,5- and 2,7-dihydroxynaphthalene, hydroxy- and aminopyridines and aminopyrazolones are suitable above all. For modifying the color shades, however, not only the typical coupling compounds known from the literature are suitable, which themselves (without developer) do not manage to form usable dyes, but also typical developers which couple with the N-benzyl-p-phenylenediamines applicable according to the invention to new shades. Such compounds suitable for modifying hair dyes are above all aromatic amines, which in the ortho or para position have another, substituted or free amino group, a hydroxyl group, a phenol ether group or a thiophenol ether group, diaminopyridines, 4-aminopyrazolones and 2,4,5 ,6-tetraaminopyrimidine and their derivatives. Also direct dyes, e.g. nitro-phenylenediamine derivatives, anthraquinone dyes or indophenols, can be combined for the production of natural hair dye shades with the oxidation dye precursors and used in the hair dye agents according to the invention.

In the hair dyes according to the invention, the developer compounds and the coupling compounds are usually used in approximately equimolar amounts. Although the equimolar application also proves to be appropriate, it is not unfortunate when certain oxidation dye precursors are used in excess. It is also not necessary that the N-benzyl-p-phenylenediamines or the otherwise present oxidation dye precursors are uniform compounds.

Mixtures of these compounds can also be used.

The oxidative development of the coloring can in principle

take place with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially when a lightening effect on the hair is desired in addition to the dyeing. As oxidizing agents, hydrogen peroxide or its addition products to urea, mela-

mine or sodium borate as well as mixtures of such hydrogen peroxide clay products with potassium peroxide disulphate.

For the production of the hair dyes according to the invention, the oxidation dye precursors are mixed in a suitable cosmetic carrier. Such carriers are, for example, creams, emulsions, gels or also surfactant-containing, foaming solutions, e.g. shampoos or other preparations, which are suitable for application to the hair. Common components of such cosmetic preparations are, for example, wetting agents and emulsifiers such as anionic, non-ionic or ampholytic surfactants, for example fatty alcohol sulphates, alkane sulphonates, α-olefin sulphonates, fatty alcohol polyglycol ether sulphates, ethylene oxide coating products for fatty alcohols, fatty acids and alkylphenols, sorbitan fatty acid esters and fatty acid partial glycerides, fatty acid alkanolamides as well as thickeners, such as methyl or hydroxyethyl cellulose, starch, fatty alcohols, paraffin oils, fatty acids, further perfume oils and hair care additives, such as e.g. water-soluble cationic polymers, protein derivatives, pantothenic acid and cholesterol. The components of the cosmetic carrier are used for the production of hair dyes according to the invention in quantities customary for this purpose, e.g. emulsifiers are used in concentrations from 0.5-30% by weight and thickeners in concentrations from 0.1-25% by weight of the total colorant. The oxidation dye precursors are mixed in amounts from 0.2-5% by weight, preferably 1-3% by weight, of the total colorant in the carrier. The N-benzyl-p-phenylenediamines usable according to the invention can be used in an amount from 0.05-10 millimoles per 100 g.

The use of the hair dyes according to the invention can, regardless of the type of cosmetic preparation, e.g.

such as cream, gel or shampoo, take place in a slightly acidic, neutral or alkaline environment. Use of the hair dye in a pH range of 8-10 is preferred. The application temperatures can lie in a range between 15 and 40°C. After an impact time of approx. After 30 minutes, the hair dye is removed by rinsing the hair to be dyed. The hair is then washed with a mild shampoo and dried. After-washing with a shampoo is omitted, when a strong surfactant was used

containing carrier, e.g. a color sahmpoo.

The dyes obtainable with the hair dyes according to the invention have a high brilliance as well as superior heat, light, washing and friction fastness properties. The invention will be explained in more detail with the help of some examples.

Examples

1st step: N-benzyl-N-methyl-p-nitroaniline

A mixture of 7.9 g of 1-chloro-4-nitrobenzene (0.05 mol) and 12.1 g of benzylmethylamine (0.1 mol) was heated for 6 hours with stirring at 180°C. After cooling to 20°C, the reaction mixture was taken up in dilute hydrochloric acid and the precipitate filtered off, washed with water. dried and recrystallized from ethanol.

8.2 g of a yellow powder with a melting point were formed

at 66°C.

2nd step: ylbenzYl-methylamino-4-aminobenzene

The product from the 1st step was catalytically hydrogenated for approx. 200 ml of ethanol in the presence of 0.5 g of palladium on activated charcoal (10%). After completion of hydrogen absorption, the catalyst was filtered off by filtration and the filtrate was evaporated to dryness. A light brown oil was formed and identified by infrared spectrum: IR spectrum (film): 1615, 1520, 1470, 1450, 1430, 1415, 1334, 1310, 1260, 1180, 1150, 1125, 1050, 820.

1st step: ii22G5Yi§mil22l?.llSi2Slil2it£22§0S22

A mixture of 9.6 g of 3,4-dichloro-nitrobenzene (0.05 mol) and

16 g of benzylamine (<0>.15 mol) was heated for 30 minutes at 110°C and then for 2 hours at 150°C. After cooling, the reaction mixture was poured into ice water, the precipitate was filtered off, washed with water and recrystallized from ethanol. 10.8 g of a yellow powder with a melting point of 95°C were formed. 2nd step: il22SZYlamino-2-chloro-4-aminobenzene-diY<drocl>oride 2.6 of the product from the 1st step was heated with 11.3 g of SnCl2• 21^0 in 20 ml of ethanol for 40 minutes to boiling during reflux. After cooling, 100 ml of ice water was added and, with stirring, a pH value of approx. 8. The reaction mixture was then extracted twice with 50 ml of ethyl acetate each time. After evaporating the extract to dryness, the residue was mixed with approx. 5 ml of concentrated hydrochloric acid and again evaporated to dryness. 1.6 g of the product with a melting point of 184°C (under cleavage) was formed.

ili2ihHydroksYi3 i52dichlorobenYl]_-amino34-aminobenzenediHydro-_ ?si2£i<L!E_4 1

1st step: IM 2zhY^£2!S§Ylli5l^ilsl2^il22Q5Yi^mi22lll2i£E222!}52D

A mixture of 9.65 g of 2-hydroxy-3,5-dichlorobenzyl alcohol

(0.05 mol) and 6.9 g of p-nitroaniline (0.05 mol) were heated for 1 hour with stirring at 160°C. After cooling, the reaction mixture was taken up in diluted caustic soda (45 ml of 10% caustic soda in 300 ml of water). Upon introduction of CC₂ gas, the product was precipitated, then filtered off, dried and recrystallized from ethanol. 8 g of a yellow powder with a melting point of 129-132°C were formed. 2nd step: illi-hydroxYi^^S-dichlorobenzYll-a k§2z§ndihYdr<oklor>id 10 g of the product from the 1st step was dissolved in 400 ml of ethanol and catalytically hydrogenated after the addition of 0.5 g of Raney nickel . After completion of hydrogen absorption, the catalyst was separated by filtration and the filtrate acidified with concentrated hydrochloric acid. After evaporation, 5 g of 1-(2-hydroxy-3,5-dichloro)-benzylamino-4-aminobenzene dihydrochloride were formed with a melting point of 190°C (with cleavage).

ili2-HydroxYbenzYli-amino-2-m

1st step: lli2;hydroxybenzYll3amino-2-methyll^

A mixture of 12.4 g of 2-hydroxybenznyl alcohol (0.1 mol) and 15.2 g of 2-methyl-4-nitroaniline (0.1 mol) was heated for 2 hours with stirring at 160°C. After cooling, the reaction mixture was taken up in diluted caustic soda (45 ml of 10% caustic soda in 300 ml of water). Upon introduction of CC₂ gas, the product was precipitated, then filtered off, dried and recrystallized from ethanol. 6 g of an olive yellow powder with a melting point of 125°C (during cleavage) were formed. 2. step: lll2-hydroxybe'nzYl2-§mino-2-m^ diHydrochlorld 5 g of the product from the 1st step was dissolved in 400 ml of ethanol and hydrogenated catalytically after the addition of 0.5 g of Raney nickel. After completion of hydrogen uptake, the catalyst was separated by filtration and the filtrate acidified with concentrated hydrochloric acid. After the evaporation, 4.2 g of 1-(2-hydroxybenzyl)-amino-2-methyl-4-aminobenzene dihydrochloride with a melting point of 210° C. (with cleavage) was formed.

^nY2!2^2l§§§2lSsem£ler

Hair dyes according to the invention were produced in the form of a hair dye cream emulsion of the following composition:

The ingredients were mixed in sequence. After the addition of the oxidation dye precursor and the inhibitor, the pH value of the emulsion was first adjusted to 9.5 with concentrated ammonia solution and then filled with water to 100 g.

The oxidative development of the staining was carried out with a 3% hydrogen peroxide solution as an oxidizing agent. To this end, 100 g of the emulsion was mixed with 50 g of hydrogen peroxide solution (3% strength).

The color cream was applied approx. 5 cm long straws standardized

to 90% greyed, but not specially pretreated human hair and left there for 30 minutes at 27°C. After finishing the coloring process, the hair was rinsed, washed out with a regular hair detergent and then dried.

The following N-benzyl-p-phenylenediamines (component E) were used:

E 1: 1-benzylamino-4-aminobenzene

E 2: 1-benzyl-methyl-amino-4-aminobenzene

E 3: 1-benzylamino-2-chloro-4-aminobenzene dihydrochloride

E 4: 1-(2-hydroxy-3,5-dichlorobenzyl)-amino-4-aminobenzene dihydrochloride

E 5: 1-(2-hydroxybenzyl)-amino-2-methyl-4-aminobenzene dihydrochloride

As other oxidation dye precursor (component M)

to modify the hair coloring the following compounds were used:

M 1: naphthol-1

M 2: 1,5-dihydroxynaphthalene

M 3: 2,7-dihydroxynaphthalene

M 4: resorcinol

M 5: 2-methylresorcinol

M 6: 4-chlororesorcinol

M 7: diresorcyl sulfoxide

M 8: m-aminophenol

M 9: 5-amino-2-methylphenol

M 10: 2,4-dichloro-3-aminophenol

M 11: 2,4-diaminophenol

M 12: 3,4-methylenedioxyphenol

M 13: 3,4-methylenedioxyaniline

M 14: 2,4-diaminophenoxyethanol

M 15: 1,3-bis-(2,4-diaminophenoxy)-propane

M 16: 5-chloro-2,3-pyridinediol

M 17: 2-amino-3-hydroxypyridine

M 18: 3-amine6-2-methylamino-6-methoxypyridine M 19: 1-phenyl-3-methyl-pyrazolone-5

M 20: 1-phenyl-4-amino-pyrazolone-5

M 21: p-phenylenediamine

M 22. 2,5-diaminotoluene

M 23: N-methyl-p-phenylenediamine

M 24: 1-(2-hydroxypropyl)-amino-4-aminobenzene

M 25: 1-ethyl-1-(2-hydroxyethyl)-amino-4-aminobenzene M 26: 1,1-bis-(2-hydroxyethyl)-amino-4-aminobenzene M 27: 2,5-diaminoanisole

M 28: p-aminophenol

M 29: 2,4,5,6-tetraaminopyrimidine

The hair dyes achieved with the aforementioned oxidation dye precursors are listed in table I.

Claims (4)

1. Hårf argemid.de 1 containing oxidation hair dye precursors in a cosmetic carrier, characterized in that the oxidation dye precursors contain N-benzyl-p-phenylenediamine or its derivatives with the general formula I in which R means hydrogen or an alkyl group with 1-4 C atoms, R 2 means hydrogen, chlorine or an alkyl group with 1-4 C atoms, 3 4 5 R means hydrogen or a hydroxyl group, and R and R unav dependent on each other means hydrogen or chlorine, or their salts and the coupling and/or developer substances common in oxidation dyes. 2. Hair dye according to claim 1, characterized in that compounds of the general formula I are contained as oxidation dye precursors, in which the substituents have the following meaning: 1 2 3 4 5 a: R = H, R = H, R = H, R = H, R = H 1 2 3 4 5 b: R = CH,, R = H, R = H, R = H, R = H 1 2 3 4 5 R = H, R = Cl, R = H, R = H, R = H d: R <1> = H, R <2> = H, R <3> = OH, R <4> = Cl, R <5> = Cl e: R <1> = H, R <2> = CH3, R3 = OH, R <4> = H, R <5> = H 3. Hair dye according to claim 1 or 2, characterized in that it also contains direct hair dyes. 4. Hair dye according to claims 1-3, characterized in that it contains N-benzyl-p-phenylenediamine or its derivatives of the general formula I in an amount of 0.05-10 millimol per 100 g.