WO1991013881A1

WO1991013881A1 - Paraphenylenediamine derivatives and their use in oxidative dyes

Info

Publication number: WO1991013881A1
Application number: PCT/EP1991/000409
Authority: WO
Inventors: Günther KONRAD; Edgar Lieske
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1990-03-14
Filing date: 1991-03-05
Publication date: 1991-09-19
Also published as: DE4008049A1

Abstract

New paraphenylenediamine derivatives of general formula (I), where R?1 and R2¿ stand for hydrogen, alkyl groups with 1 to 4 carbon atoms, hydroxyalkyl groups with 2 to 4 C atoms or alkoxyalkyl groups with 1 to 4 C atoms in the alkoxy group and 2 to 4 C atoms in the alkyl group and n is a number from 2 to 4, and their salts, are useful preliminary products for oxidative hair dyes. These products are suitable for use as developer ingredients, together with usual coupler ingredients, for formulating oxidative hair dyes, in particular for producing blue to brown tints.

Description

"Paraphenylenediamine Derivatives and Their Use in Oxidation Dyes"

The invention relates to new paraphenylenediamine derivatives, a process for their preparation and their use as oxidation dye precursors, in particular as developer components in oxidation hair colorants.

The so-called oxidation hair dyeing agents play a preferred role for dyeing hair because of their intense colors and good fastness properties. Such hair colorants contain oxidation dye precursors in a cosmetic carrier. Developer substances and coupler substances are used as oxidation dye precursors. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components.

Good oxidation dye precursors must first of all meet the following requirements: they have to develop the desired color shades with sufficient intensity and authenticity in the oxidative coupling. They must also have a good ability to draw on human hair, with no noticeable differences between damaged and freshly regrown hair. They should be resistant to light, heat and the influence of chemical reducing agents, e.g. B. against permanent wave fluids. After all, they shouldn't stain the scalp too much and above all, they should be safe from a toxicological and dermatological point of view.

Primary aromatic amines with a further free or substituted hydroxyl or amino group located in para or ortho position, furthermore diaminopyridine derivatives, heterocyclic hydrazone derivatives and 4-aminopyrazolone derivatives are usually used as developer substances. M-Phenylenediamine derivatives, naphthols, resorcinol derivatives and pyrazolones are used as so-called coupler substances.

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 because they have utagenic and / or allergic properties. There is therefore a high level of technical interest in oxidation dye precursors which, on the one hand, form intense colors with high fastness properties, but on the other hand are safe from a toxicological and dermatological point of view.

It has now been found that hair colorants containing oxidation dye precursors in a cosmetic carrier, the oxidation dye precursors paraphenylene diamine derivatives of the general formula (I)

in which R ¹ and R ^{2 are} hydrogen, alkyl groups with 1 to 4 carbon atoms, hydroxyalkyl groups with 2 to 4 carbon atoms or alkoxyalkyl groups with 1 to 4 carbon atoms in the alkoxy group and 2 to 4 carbon atoms in the alkyl - are group and n = 2 - 4, or their salts and the coupler compounds present in oxidation dyeing agents, which meet the requirements to a high degree and are, above all, safe and safe with regard to the toxicological and dermatological properties. Heat stability, cold wave fastness and fastness to rubbing of the oxidation dyeings which can be produced therewith are also very high. In addition, the dyeings show a very even lift on the damaged hair tips and the hairline.

The compounds of the formula (I) in which R ^{1 is} hydrogen show particularly favorable behavior.

The compounds of the general formula (I) are new and are therefore themselves the subject of the present invention. They can be prepared by synthetic methods known per se from the literature by adding one mole of 4-nitro-N-aminoalkylaniline of the formula (II)

with one mole of a compound of the formula

in which X is chlorine or a group NR * R ² , in the presence of a base, the reaction product, in the case where X = chlorine, is reacted with an amine of the formula HNR ^ R ² , and then in the reaction product Nitro group converted into the amino group by catalytic reduction.

The new compounds of formula (I) or their salts are suitable for use as oxidation dye precursors of the developer type, in particular as developers in oxidation hair colorants. They are able to form dyes under the influence of oxidizing agents. However, particularly intense and brilliant dyes are formed by oxidative coupling in the presence of coupler substances.

The paraphenylenediamine derivatives of the formula (I) according to the invention can be used either as such or in the form of their water-soluble salts with inorganic or organic acids, for. B. isolated as hydrochloride, sulfates, phosphates, acetates, propionates, lactates or citrates and used in hair dyes.

Another object of the invention are hair dyes containing oxidation dye precursors in a cosmetic carrier, which as oxidation dye precursors 2- (4-amino-anilinoalkyl) -amino-4,6-diamino-l _f 3,5-triazines. general formula (I) according to claim 1 or 2 or their water-soluble salts as developer component in addition to conventional developer and Kup ler- koπφonent and optionally direct hair dyes. Among the numerous known coupler substances for the new developers of the formula (I) are especially those with phenolic hydroxyl groups, preferably phenols and resorcinols, or those of the 1,3-bis (2,4-diaminophenoxy) propane type are suitable. Such hair dyes produce particularly brilliant colors in the range from blue to brown shades.

In the hair colorants according to the invention, the developer substances and the coupler substances are generally used in equi-polar amounts, but a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer substances and coupler substances in a molar ratio of 1: 0.5 to 1 : 2 can be used. The paraphenylene diamine derivatives according to the invention of the formula (I) or their salts can be used in an amount of 0.05 to 10 millimoles per 100 g of the hair dye. It is not necessary for the compounds of the formula (I) to be uniform compounds. Mixtures of such compounds can also be used.

In order to modify the hair coloring, the hair dye compositions according to the invention can also be known direct hair dyes, for. B. nitrophenylenediamine derivatives, anthraquinone dyes or indophenols can be added.

To produce the hair colorants according to the invention, the oxidation dye precursors and any substantive dyes are incorporated into a suitable cosmetic carrier. Such carriers are e.g. B. creams, emulsions, gels or surfactant-containing, foaming solutions, eg. B. shampoos or other preparations that are suitable for use on the hair. Common components of such cosmetic preparations are e.g. B. wetting and emulsifying agents such as anionic, nonionic or ampholytic surfactants, for example fatty alcohol sulfates, alkane sulfonates, alpha-olefin sulfonates, fatty alcohol polyglycol ether sulfates, ethylene oxide adducts with fatty alcohols, fatty acids and alkyl phthalates nols, sorbitan fatty acid esters and fatty acid partial glycerides, fatty acid alkanolamides and thickeners, such as. As methyl or hydroxyethyl cellulose, starch, fatty alcohols, paraffin oils, Fettäu¬ ren, also perfume oils and hair care additives, such as. B. water-soluble cationic polymers, protein derivatives, pantothenic acid and cholesterol.

The constituents of the cosmetic carriers are used for the production of the hair colorants according to the invention in amounts customary for these purposes, for. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant. The oxidation dye precursors are mixed in the carrier in amounts of 0.2 to 5% by weight, preferably 1 to 3% by weight, of the total colorant.

A preferred application form for the 2- (4-

Aminoanilinoalkyl) -amino-4,6-diamo, l, 3,5-triazines of the formula (I) are cream hair dye in the form of an oil-in-water emulsion with a content of

1 to 10 millimoles per 100 g of developer components,

1 to 10 millimoles per 100 g of coupler components,

1 to 10 wt .-% of an alkyl (-Cιo-Cιβ) sulfate or

Alkyl (Cιo-Cl6) - ^etnersu ^ ^a-ttensι'ds f 5 to 20 wt .-% of a fatty alcohol ^mixture with 12 to 18 carbon atoms, 0.1 to 2 wt .-% of an oxidation inhibitor, preferably from the

Group alkali sulfite, alkali ascorbate or

Alkali dithionite and ammonia in an amount to adjust the pH of the emulsion to a value between 8 and 10. The alkyl sulfate or alkyl ether sulfate surfactant mentioned can be present as an alkali, ammonium or alkanolammonium salt with 2 or 3 carbon atoms in the alkanol group, e.g. B. as sodium, triethanol a monium or isopropanol moniu salt. As the alkyl (Cι-Cιs) ether sulfate surfactant, a sulfuric acid monoester salt of an adduct of 1 to 10 moles of ethylene oxide with a Cifj-Ciδ fatty alcohol can be used.

The oxidative development of the color can in principle be carried out with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially when a lightening effect on the hair is desired in addition to the coloring. Particularly suitable oxidizing agents are hydrogen peroxide or its adducts with urea, melamine or sodium borate and mixtures of such hydrogen peroxide adducts with potassium peroxide disulfate.

The use of the hair dye according to the invention can, regardless of the type of cosmetic preparation, for. B. as a cream, gel or shampoo, in a weakly acidic, neutral or alkaline environment. Preferably, the hair colorant in a pH range of 8 to 10. The application temperatures is kön¬ nen in a range between 15 ° C and 40 lie ^β C.

After an exposure time of about 30 minutes, the hair dye is removed from the hair to be colored by rinsing. The hair is then washed with a mild shampoo and dried. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. B. a coloring shampoo was used.

The following examples are intended to explain the subject of the invention in more detail, but without restricting it thereto. Examples

1. Manufacturing examples

1.12 - ([3- (4-Aminoaniliπo) propyl] amino) -4-6-diamino-l, 3,5-triazine-pentahydrochloride (formula (I), π = 3, R ¹ = H, R ² = H)

Step 1:

27.5 g (0.14 mol) of N- (p-nitrophenyl) -1, 3-diamino-propane (according to J. Heterocyl, Chem. .10 (1973), 915, 920) were mixed with 20.5 g ( 0.14 mol) of 2-chloro-4,6-dia wo-l, 3,5-triazine and 20.5 g of calcium carbonate in 500 ml of water and heated to boiling under reflux for 8 hours. The precipitated substance was treated three times with hot water. After drying it showed a melting range of 193 ° - 199 ° C.

Level 2:

29.9 g (0.098 mol) of the substance obtained in stage 1 were hydrogenated in water, in the presence of platinum (on activated carbon) (hydrogen absorption 6.93 l at 20 ° C.). After acidifying the solution with concentrated hydrochloric acid, the solution was evaporated to dryness and dried at 20 ° C. under reduced pressure. 34.6 g of the product with a melting point of 242 ° C. were obtained.

Analysis: C ^ HiβNβ + 5 HC1 (MW: 456.6)

% By weight C H N

calculated 31.56 5.08 24.5 determined 31.70 5.15 23.7

iH-NMR spectrum in D2O:

7.7 ppm: 2d, 4H 3.6 ppm:, 4H 2.2 ppm: m, 2H

1.22 - ([3- (4-Aminoanilino) propyl] amino) -4,6-bis (2-methoxyethylamino) -l, 3,5-triazine-pentahydrochloride (formula I, n = 3, Rl = H, R ² = -CH2CH2-OCH3)

Step 1:

Analogously to the synthesis of 2-amino-4,6-dichloro-5-triazines by JT Thurston et al., JACS 73 (1951), 2981, 2983, cyanuric chloride with N- (p-nitrophenyl) -l, 3- diaminopropane to 2 - ([3- (4-nitroanilino) propyl] amino) -4,6-dichloro-1,3,5-triazine. This had a melting point of 158 ° C.

Level 2:

3.4 g (10 mmol) of the product from stage I were refluxed with 3.0 g (40 mmol) of 2-methoxyethylamine in 100 ml of water / ethanol (1: 1) for 4 hours. After cooling, it was decanted from a greasy mass. The solution was evaporated. The residue was treated twice with cold and with hot water. The product was obtained as an amorphous, poorly crystallizing mass. iH-NMR spectrum in de-DMSO + D2O

8.1 ppm: d, 2H

6.7 ppm: d, 2H

3.2 - 3.6 ppm: m, 18H

1.8 ppm: m, 2H (C-CH2-C)

Level 3:

1.8 g of the substance obtained in stage 3 were hydrogenated in water in the presence of platinum (on activated carbon). (Hydrogen uptake 300 ml at 20 ° C). The work-up was carried out analogously to 1.1, stage 2. 1.8 g of a very hygroscopic product were obtained.

iH NMR spectrum in D2O

7.7 ppm: 2d, 4H 3.6 ppm: m, 12H

3.4 ppm: 2s, 6H (2 CH3) 2.1 ppm:, 2H

1.32 - ([3- (4-Aminoanilino) propyl] amino) -4,6-bis (2-hydroxyethylamino) -l, 3,5-triazine, (formula (I), n = 3, R ¹ = H, R ² = CH2-CH ₂ -0H)

Step 1:

5.8 g (18 mmol) 2-chloro-4,6-bis- (2-hydroxyethyl) amino-l, 3,5-triazine (according to JT Thurston et al., JACS 73_, (1951), 2981-2983) and 3.5 g (18 mmol) of N- (p-nitrophenyl) -l, 3-diaminopropane were reacted in toluene at 110 ° C for 8 hours. The precipitated reaction product was recrystallized from ethanol. 3.7 g of a product melting at 158 ° -163 ° C. were obtained.

H-MNR spectrum in d6-DMS0 + D2O

8.0 ppm: d, 2H

6, 7 ppm: d, 2H

3, 5 - 3.6 ppm: m, 16H

3, 2 - 3.4 ppm: 2t, 4H

1.8.8 ppm: m, 2H

Level 2:

3.6 g of the substance obtained in stage 1 were hydrogenated in water / ethanol (1: 1) in the presence of platinum (on activated carbon). The hydrogen uptake was 0.6 1 (20 ^β C). After the catalyst had been filtered off, the solution was evaporated. 3.4 g of a very hygroscopic substance were obtained as the residue.

iH-MNR spectrum in de-DMSO + D2O

7.0 ppm: d, 2H

6.8 ppm: d, 2H

3.5 - 3.6 ppm: m, 16H (CH2CH2 group)

3.2 - 3.4 ppm:, 4H (N * -CH2 and N ² -CH2 group)

1.8 ppm: m, 2H

1.42 - ([3- (4-Aminoanilino) propyl] amino) -4,6-bis (dimethylamino) - 1,3,5-triazine (Formula I, n = 3, R ¹ = CH3, R ² = CH3)

Step 1:

8.0 g (40 mmol) of N- (4-nitrophenyl) -l, 3-diaminopropane were added to 100 ml of a mixture of ethanol and water (1: 1) with 4.0 g (20 mmol) of 2-chloro-4,6-bis- (dimethylamine) -l, 3,5-triazine under reflux for six hours Boiling heated. Decantation was carried out from a low, highly viscous sediment. After cooling, 1.7 g of the reaction product with a melting point of 121 ° -123 ° C. precipitated.

Level 2:

1.7 g (4.7 mol) of the product from stage I were hydrogenated in 100 ml of ethanol in the presence of palladium (5% by weight on activated carbon) as a catalyst. After filtering off the catalyst and evaporating the ethanol, 1.2 g of the product were obtained with an empirical formula C16H26N8 'C2H5OH ^• 0.5H20 (MW: 386.0).

Analysis C H N

calculated 56.01 8.62 29.16 found 56.10 8.70 29.10

2. Examples of use

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

Fatty alcohol C12-14 10.0 g fatty alcohol C12-14 + 2 EO sulfate,

Na salt, 28% 25.0 g

Water 60.0 g

Developer according to Example 1.1-1.4 7.5 mmol

Coupler component 7.5 mmol

Na2S03 (inhibitor) 1.0 g concentrated ammonia solution up to pH = 9.5

Water ad 100 g

The ingredients were mixed together in order. After the oxidation dye precursors and the inhibitor had been added, the pH of the emulsion was first adjusted to 9.5 with concentrated ammonia solution, and the mixture was then made up to 100 g with water.

The oxidative development of the color was carried out using 3% hydrogen peroxide solution as the oxidizing agent. For this purpose, 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (3%) and mixed.

The coloring cream was applied to approx. 5 cm long strands of standardized, 90% gray, but not particularly pretreated human hair and left there at 27 ° C. for 30 minutes. After the dyeing process had ended, the hair was rinsed, washed out with a customary shampoo and then dried. The following compounds were used as couplers:

Kl aminophenol

K2 2,4-dichloro-3-aminophenol

K3 5-amino-2-methylphenol

K4 5-amino-4-chloro-2-methylphenol

K5 5-amino-6-chloro-2-methylphenol

K6 1-naphthol

K7 1,5-dihydroxynaphthalene

K8 2,6-diaminopyridine

K9 l, 3-bis (2,4-diaminophenoxy) propane

K10 resorcinol

Kll 4-chlororesorcinol

K12 1-phenyl-3-aminopyrazolone-5

K13 2,4-dihydroxybenzylidene anthranilic acid

K14 2,7-dihydroxynaphthalene

The results of the dyeing tests are shown in Table I:

Table I

Example No. Developer Coupler Nuance of the colored hair

2.1 1.1 Kl black-brown violet

2.2 1.1 K2 blue-black

2.3 1.1 K3 dark purple

2.4 1.1 K4 dark purple

2.5 1.1 K5 dark purple

2.6 1.1 K6 dark blue

2.7 1.1 K7 blue

2.8 1.1 K8 dark blue

2.9 1.1 K9 blue-black

2.10 1.1 K10 dark brown

2.11 1.1 Kll dark brown

2.12 1.1 K12 purple brown

2.13 1.1 K13 olive

2.14 1.1 K14 green

2.15 1.2 K6 purple

2.16 1.2 K10 brown.

2.17 1.3 K3 purple

2.18 1.3 K10 brown

2.19 1.3 K9 blue

2.20 1.4 K9 blue

2.21 1.4 K10 brown

Claims

1. Paraphenylenedia-in derivatives of the general formula (I)

in which R ¹ and R ^{2 are} hydrogen, alkyl groups with 1 to 4 carbon atoms, hydroxyalkyl groups with 2 to 4 carbon atoms or alkoxyalkyl groups with 1 to 4 carbon atoms in the alkoxy group and 2 to 4 carbon atoms in the alkyl group and n = 2-4, and their salts.

2. Paraphenylenediamine derivatives according to claim 1, characterized gekenn¬ characterized in that Rl is hydrogen.

3. Process for the preparation of paraphenylenediamine derivatives of the general formula (I)

in which R * and R ^{2 are} hydrogen, alkyl groups with 1 to 4 carbon atoms, hydroxyalkyl groups with 2 to 4 carbon atoms or alkoxyalkyl groups with 1-4 carbon atoms in the alkoxy group and 2-4 carbon atoms in the alkyl group and n = 2-4, characterized in that one mole of 4-nitro-N-aminoalkyl-aniline of the formula ( II)

0 ₂ N-τ j — NH- (C _n H2n) -NH ₂ (II)

with one mole of a compound of formula (III)

in which X is chlorine or a group -NRIR, in the presence of a base, the reaction product in the event that X = chlorine is reacted with two moles of an amine of the formula HNR ^ ² and then in the reaction product the nitro group by catalytic Reduction transferred to the amino group.

4. Use of paraphenylenediamine derivatives of the general formula (I) according to Claim 1 or 2 or their water-soluble salts as oxidation dye precursors of the developer type in oxidation hair dyeing agents.

5. Hair dye containing oxidative dye precursors in a cosmetic carrier, characterized in that the oxidation dye precursors include paraphenylenediamine derivatives of the formula (I) according to Claim 1 or 2 or their water-soluble salts as developer component in addition to customary developer and coupler components and possibly direct hair dyes.

6. Hair dye according to claim 5, characterized in that phenolic, resorcinol or 1,3-bis- (2,4-diaminophenoxy) propane are contained as coupler components.

7. Hair dye according to claim 5 or 6, characterized gekennzeich¬ net that developer substances and coupler substances are contained in the molar ratio 1: 0.5 to 1: 2, that the content of oxidation dye precursors 0.2 to 5.0 wt .-% of the hair dye and the content of paraphenylenediamine derivatives of the formula (I), according to claim 1, or their water-soluble salts are 0.05 to 10 mllimol per 100 g of the hair dye.