Composition and Dyestuffs for use in the Dyeing of Keratinic Fibres

Beginning of the patent period: April 15, 1969.

The inventors mentioned are: Ing. Gregoire Kalopissis in Paris and Ing. Andree Bugaut in Boulogne-sur-Seine (France).

The invention relates to a process for dyeing keratin fibers, in particular hair, which is characterized in that the fibers with a solution containing at least one dye of the general formula

A -NR- (CH 2 -NHR * (I), impregnated and rinsed and dried after an exposure time of 5 to 30 minutes, where in formula I R 'are the same or different and are hydrogen, an alkyl or hydroxyalkyl radical with 1 to 6 carbon atoms and n is an integer from 2 to 6 inclusive.

The symbol A can

a) represent an unsubstituted aniririnone radical, in which case the -NR-fCHg) -NHR * chain is in the 2-position and R and R 'are hydrogen,

b) an aurachinone radical of the formula

O

<img file="AT277463B_D0001.tif" />

O (Π), in which case R is always hydrogen and Z * is hydrogen or the group -NHR., Wherein R ^ is hydrogen or an alkyl radical having 1 to 6 carbon atoms, and Z is water or the group - NRR, in which R has the abovementioned meaning and RW may be an alkyl group having 1 to 6 carbon atoms or the group - (C 1) -NHR * in which

R 'and n have the meaning given above. As far as the substituents Z and Z * of the anthraquinone nucleus are concerned, it should be noted:

1. If the chain contained in formula (I) contains -NR- (CH) -NHR'am anti-nitrosinone nucleus in 1-Stel2 n

No.277463 ment, the symbol Z 'can only be hydrogen and the symbol Z, if it does not mean hydrogen, occupy only the positions 4, 5 and 8.

Second When the chain contained in formula (Γ) is in the 5-position, R 'is hydrogen only, Z' is a group -NHRj in4-position and Z is the group-NHR₂ in 1 position, where

Rg is hydrogen or an alkyl radical of 1 to 6 carbon atoms and Rj and R₂ may be the same or different and the anthraquinone radical of the formula

<img file="AT277463B_D0002.tif" />

(HD equals;

c) an azoradical of the formula

-N-N = N-B - (IV) in which each of the symbols B / indB.j represents an aromatic or heterocyclic radical which is mono- or polysubstituted by halogen, nitro, alkyl, hydroxy or aminoacyl groups may be substituted;

d) a p-nitrophenyl-azo-phenyl radical of the formula °,^N- \? / -^{N = N}~ \? / - (V) in which the chain contained in formula (I) -NR- (CH₂)_n~ NHR 'in the 4-position and the NO ^ -Grup¹pe in 4 'position, can be ».

The symbol A can finally

e) a phenyl group of the formula

OR ' ^{20 R}- | Vi ^(VI) no₂ in which R "'is hydrogen or an alkyl radical having 1 to 6 carbon atoms, where the chain -NR- (CH₂)_n-NHR *, in which R is hydrogen and R 'has the meanings given above, para to the alkoxy group.

The dyes of the formula (I) which are used in the compositions according to the invention mean that A is a radical of the formula (II) which in the 1-position is a chain -NH- (CH₂)_n-NHR 'are prepared in such a way that a diamine of the formula NH₂- (CH₂)_n-NHR * is condensed with an a-mono- or 1,5- or 1,8-dihalogenanthraquinone or with quinizarin.

The process can also be carried out in such a way that, for the preparation of dyes of the formula (I) in which A is a radical of the formula (II) which is in the 2-position, a chain -NH- (CH₂)_nNH₂ 2-aminoanthraquinone first reacted with a Aiylsulfochlorid and the alkali compound of the thus obtained 2-Aminoarylsulfonylanthrachinons is reacted with an α, ω-Dihalogenalkan, whereupon the resulting halogen derivative condensed with potassium phthalimide, and after the condensation, the cleavage of Arylsulfonylrestes takes place and finally the resulting phthalimido derivative is sulfurylated with hydrazine hydrate and hydrazine hydride.

No. 277463

For the preparation of dyes of the formula (I) in which A is a radical of the formula (Π) which in the 5-position is a chain -NH- (CH₂)_n-NH 2, further 1,4-diamino-5-nitroanilhrachlnone with a diamine of the formula NHg- (CH₂)_nNH₂ be condensed.

Furthermore, dyes of the formula (I) in which A is a radical of the formula (IV), by

Coupling of the diazonium salt of an amine of the formula Bj-NH₂ with an amine of the formula

B₂-NR- (CH₂)_n-NHR ', where Bj and B₂ represent aromatic and / or heterocyclic radicals, optionally mono- or polysubstituted by halogens, nitro, alkyl^-, Hydroxy or amino acyl groups may be substituted.

The dyes of the formula (I) in which A is a radical of the formula (VI) are prepared in such a way that in the amino group of amines of the general formula

<img file="AT277463B_D0003.tif" />

NO₂

NH, (VII) the group - (CH₂)_n-NHR * is introduced.

The dyes used in the compositions of the invention corresponding to the formula I have numerous advantages. For example, they have a high affinity for keratin fibers and are very resistant to dyeing the fibers with applied dyeings. In addition, these dyes can be achieved very wide shade ranges, ranging from yellow to blue, and for a long time very light-resistant dyeings.

Furthermore, the dyes also show the advantage of being soluble in water over a wide pjj range.

Not only the duration of exposure of the dyeing solution to the hair, but also the temperature of the application of the dyeing solution may be different, preferably is carried out at ordinary temperature.

The invention also relates to an agent for carrying out the dyeing process, which is characterized in that it consists of a solution of at least one dye of the general formula I, preferably in water, in a concentration of 0.01 to 3%, having a pseudo-colorant. Value of 4 to 10 has.

For the setting of p_HValue, an organic or an inorganic acid, for example lactic acid or hydrochloric acid can be used.

The hair colorants may also contain other dyes customary for hair colorants, as well as otherwise customary additives, for example dispersants, wetting agents, wetting agents, thickeners, cleaners, softeners and fragrances.

The following instructions for the preparation of the dyes contained in the agents according to the invention and the embodiments serve to better understand the subject matter of the invention, without being limiting.

Protocol 1: Preparation of 4-methylamino-l - [(β-aminoethyl) amino] anthraquinone.

The reaction proceeds according to the following scheme:

O Br

O

<img file="AT277463B_D0004.tif" />

O NHCH,

O NH-CHNh₂ch₂NH₂

A solution of 4-methylamino-1-bromoanthraquinone in toluene is presently in excess 4

No. 277,463 of ethylenediamine was refluxed for several hours. After cooling, the toluene-containing solution is treated several times with η-HCl. The hydrochloric acid extracts are combined and made alkaline to liberate the base, which is extracted with ethyl acetate. After adding oxalic acid to the ethyl acetate solution, the desired amine precipitates as an oxalate, which is separated.

The corresponding base is obtained therefrom in the usual way by means of alkali; it melts, after recrystallization from toluene, at 168 ° C.

From this base, the 4-metylamino-l - [(β-acetaminophenyl) -amino] -anthraquinone is prepared by adding to a solution of 4-methylamino-1- [(β-aminoethyl) -amino] -anthraquinone in ethyl acetate-acetic anhydride is added. After recrystallization, the monoacetate melts from n-propyl alcohol at 220 ° C.

<td>Analysis:</td><td>calculated for SAW</td><td>found:</td>

<td>C%</td><td>67.65</td><td>67.50 to 67.44</td>

<td>H%</td><td>5.64</td><td>5.86-5.84</td>

<td>N%</td><td>12.46</td><td>12.20 to 12.22</td>

Rule 2; Preparation of 4-methylamino-l - [(y-aminopropyl) amino] anthraquinone. The reaction proceeds according to the following scheme:

Br O NH- (CH₂) -NH₂

<img file="AT277463B_D0005.tif" />

NHCH_S O NHCH₃

A solution of 4-methylamino-1-bromoanthraquinone in a solvent such as toluene is refluxed in the presence of an excess of 1,3-diaminopropane for several hours. After treatment of the reaction mixture, analogously to Example 1, the 4-metfaylamino -1 - [(γ-aminopropyl) amino] -anthraquinone obtained, which melts after recrystallization from Toluolbeil42 ° C. For this compound, a molecular weight of 309 is calculated; experimentally, the value 303 is determined by potentiometric analysis.

The monoacetate prepared from this base melts at 224 ° C.

Protocol 3: Preparation of 1 - [(γ-aminopropyl) amino] anthraquinone.

The reaction proceeds according to the following scheme:

<img file="AT277463B_D0006.tif" />

H₂N- (CH₂)₃NH₂^&gt;

<img file="AT277463B_D0007.tif" />

oo

A solution of 1-chloroanthraquinone in a solvent such as toluene is refluxed for several hours in the presence of an excess of 1,3-diaminopropane. After cooling, the toluene solution is treated several times with n-HCl solution. The hydrochloric acid extracts are combined and made alkaline to liberate the base. This base crystallizes out and is separated; after recrystallization from toluene, it melts at 152 ° C.

From this base, the l- [(y-acetaminopropyl) amino] anthraquinone is prepared by adding to a

Solution of l - [(y-aminopropyl) amino] anthraquinone in ethyl acetate acetic anhydride is added. This monoacetate melts after recrystallization from ethyl alcohol at 202 ° C.

Nr.277463

<td>Analysis:</td><td>calculated for:^cu^Hii^NA · '</td><td>found:</td>

<td>C%</td><td>70.81.</td><td>70.73 to 70.70</td>

<td>H%</td><td>5.59</td><td>5.61- 5.62</td>

<td>N%</td><td>8.69</td><td>8.54-8.45</td>

Protocol 4: Preparation of 1 - [(0-aminoethyl) amino] -2-nitro-4-methoxybenzene. The reaction proceeds according to the following scheme:

O-CH.

O-CH.

NO.

NH.

Cl-SO-ζ φ \ -CH₃

NO.

NaOH

HNSO₂-ζ φ \ - CH_S

O-CH.

O-CH.

- NO, Br ^ H₂-CH₂-Br so₄H₂

N-Na ¹ / - \ so, - (r ^ -ch,

O-CH.

' ^no2 potassium phthalimide

NH-CH, -CH, -Br

NO,

<td>N-CH-CH, -</td><td>• Br</td>

<td>so- (»/ -</td><td>CH,</td>

<td>O-CH</td><td></td>

<td>|</td><td>O</td>

<td>NO,</td><td>I</td>

<td>1</td><td>/^c\</td>

<td colspan="2">NH-CHCH-N</td>

<td>4 4</td><td>v ·</td>

O

hydrazine hydrate

<img file="AT277463B_D0008.tif" />

nh-ch₂ch₂nh₂

The individual phases of this synthesis are described in more detail below.

1. Phase: Preparation of 1N - [(p-toluenesulfonyl) amino] -2-nitro-4-methoxybenzene.

Zit a solution of 0.1 mol (16.8 g) of 1-amino-2-nitro-4-methoxybenzene in 60 cm³ 0.12 mole (22.86 g) of p-toluenesulphonyl chloride are gradually added to pyridine at 30 ° C. with stirring. After the addition has ended, the reaction mixture is kept at room temperature for 6 hours and then at 300 g

Nr.277463

Ice, which is mixed with 30 cm of hydrochloric acid, poured. The separated crude product is redissolved in n / 2-NaOH solution and the alkaline solution filtered, recovering 4 g of the NaOH-insoluble starting product. After neutralization of the filtrate with hydrochloric acid, 25 g of 1-N - [(p-toluenesulfonyl) amino] -2-nitro-4-methoxybenzene obtained, which after recrystallization from AI5 schholzhol at 102 ° C.

<td>Analysis:</td><td>calculated for</td><td>found:</td>

<td>C%</td><td>52.17</td><td>52.09 to 52.28</td>

<td>H%</td><td>4.34</td><td>4,43-4,44</td>

<td>N%</td><td>8.69</td><td>8.74-8.92</td>

Second Phase: Preparation of the sodium compound of 1N - [(p-toluenesulfonyl) amino] -2-nitro-4-methoxybenzene.

A solution of 0.155 mol of LN- (p-toluenesulfonylamino) -2-nitro-4-methoxybenzene in 600 cm³10 n / 2 NaOH with stirring 250 cm³ ΙΟη-NaOH added to give 48 g of the sodium compound, which are washed with a little alcohol and then with a little acetone.

Third Phase: Preparation of 1- [N- (p-toluenesulfonyl) -N- (β-bromoethyl) amino] -2-nitro-4-methoxybenzene.

0.0103 mol (3.56 g) of the sodium compound of 1- (p-toluenesulfonylamino) -2-nitro-4-methoxy-15-benzene are dissolved in 5 cm³ Dissolved dimethylformamide. This solution is 0.023 mol (2 cm³) 1,2-dibromoethane. The mixture is refluxed for 1/4 h and then in 50 cm³Poured water. It is then extracted with ethyl acetate and the extract is washed with n / 2 NaOH to remove small amounts of 1N- (p-toluenesulfonylamino) -2-nitro-4-methoxybenzene; then it is washed with water, the liquid to about 10 cm³ concentrated and mixed with a little hexane. Obtained therefrom 2.7 g of l- [N- (p-toluenesulfonyl) -N- (ß-bromoethyl) amino] -2-nitro-4-methoxybenzene, which after recrystallization from abs. Alcohol melts at 117 ° C.

<td>Analysis:</td><td>calculated for^Cie^Hn^N2 °₅^SBR:</td><td>found:</td>

<td>C%</td><td>44.75</td><td>44.79 to 44.94</td>

<td>H%</td><td>3.96</td><td>4,17-4,14</td>

<td>N%</td><td>6.52</td><td>6.73-6.61</td>

4th Phase: Preparation of 1- [N- (β-bromoethyl) amino] -2-nitro-4-methoxybenzene.

0.093 mole (40 g) of 1- [N- (p-toluenesulfonyl) -N- (β-bromoethyl) amino] -2-nitro-4-methoxybenzene are dissolved in 160 cm³ dissolved sulfuric acid, the temperature is maintained at 0 to 5 ° C. The reaction mixture is allowed to stand for 3 hours at 0 ° C and then poured onto 1.2 kg of crushed ice. There are obtained 25.1 g of l- [N- (ß-bromoethyl) amino] -2-nitro-4-melhoxybenzol, which melts after recrystallization from a benzene-hexane mixture at 57 ° C.

<td>Analysis:</td><td>calculated for^CS^Hn^N2 ° 3 ^Br:</td><td>found:</td>

<td>C%</td><td>39.27</td><td>39.41 to 39.36</td>

<td>H%</td><td>4.00</td><td>4,18- 4,20</td>

<td>N%</td><td>10.18</td><td>10.39 to 10.27</td>

5th Phase: Preparation of 1- [N- (β-phthalimidoethyl) amino] -2-nitro-4-methoxybenzene.

0.27 mole (74 g) of 1- [N- (β-bromoethyl) amino] -2-nitro-4-methoxybenzene are collected at 290 cm³ Dissolved dimethylformamide. To this solution is added 0.32 mol (59.5 g) of potassium phthalimide. The

Mixture is heated for 1 h at reflux condenser, then is filtered boiling. After cooling the

Filtrates are 79 g l- [N- (ß-Phthalimidoäthyl) amino] -2-nitro-4-methoxybenzene obtained after

Recrystallization from dioxane at 212 ° C melts.

Nr.277463

<td>Analysis:</td><td>calculated for^C17^H15^N3 °₅^:</td><td>found:</td>

<td>C%</td><td>59.82</td><td>59.61 to 59.73</td>

<td>H%</td><td>4.39</td><td>4,42- 4,60</td>

<td>N%</td><td>12.31</td><td>12.50 to 12.48</td>

6th Phase: Preparation of 1- [N- (β-aminoethyl) amino] -2-nitro-4-methoxybenzene.

A solution of 0.1 mol (34.1 g) of 1- [N- (β-phthalimido-ethyl) -amino] -2-niiro-4-methoxybenzene in 350 cm³ Propanol is co-refluxed with 0.2 mol (10.2 g) of hydrazine hydrate for 1 h. The boiling mixture is filtered to separate the phaeialhydrazide formed; to

Cooling of the filtrate, a small amount of unreacted starting material is recovered by filtration. The propanol solution is then saturated with gaseous hydrogen chloride to give 22.5 g of the desired product as a chlorohydrate, which is recrystallized from water.

<td>Analysis:</td><td>calculated for^C9^H14^NS ° 3^Cl!</td><td>found:</td>

<td>C%</td><td>43.63</td><td>43.79 to 43.80</td>

<td>H%</td><td>5.65</td><td>5.65-5.70</td>

<td>N%</td><td>16.96</td><td>17.05 to 17.08</td>

The 1- [N- (β-aminoethyl) amino] -2-nitro-4-methoxybenzene isolated from this chlorohydrate in a customary manner melts at 57 ° C.,

Protocol 5: Preparation of 1,4-diamino-5 - [(y-aminopropyl) amino] anthraquinone.

The reaction proceeds according to the following scheme:

O NH "

NH₂- &lt;CTV₃NH₂

NH O NH₂ (CH,)₃I ²

<img file="AT277463B_D0009.tif" />

<img file="AT277463B_D0010.tif" />

0.4 mol (113.2 g) of l, 4-diamino-5-nitroanthraquinone are heated to 90 ° C. in 6 mol (444 g) of 1,3-diaminopropane for h. The reaction mixture is poured into 2 liters of cold water to give 109 g of crude product, which is washed very carefully with water.

After two recrystallizations from propanol, 72 gl, 4-diamino-5- [(y-aminopropyl) -amino] -anthraquinone obtained, which melts at 165 ° C.

<td>Analysis:</td><td>calculated for^C17^H13 ° 2^N4^:</td><td>found:</td>

<td>C%</td><td>65,80</td><td>65.83 to 65.61</td>

<td>H%</td><td>5.80</td><td>5.95-6.03</td>

<td>N%</td><td>18.03</td><td>17.78 to 17.90</td>

Protocol 6: Preparation of the azo compound {[p-nitroaniline] - [N-ethyl-N- (β-aminoethyl) -aniline]}.

0.2 mol (27.6 g) of p-nitroaniline are diazotized in a hydrochloric acid medium in the usual manner. To a hydrochloric acid solution of the diazonium salt thus obtained, a solution of 0.2 mol (32.8 g) of N- (ethyl) 8

Nr.277463

-N- (O-aminoethyl) -aniline in 30 cm³ Acetic acid added dropwise at about 5 ° C. Hiebei g of the azo compound are obtained as monochlorohydrate.

This chlorhydrate is dissolved in boiling water and the solution made alkaline,

56.58 g of the azo compound are obtained, which, after recrystallization from alcohol uüd then from Ben5 zol at 134 ° C melts.

<td>Analysis:</td><td>calculated for ^CA ^NS ° 2^:</td><td>found:</td>

<td>C%</td><td>61.34</td><td>61.35 to 61.30</td>

<td>H%</td><td>6.07</td><td>6,14- 6,20</td>

<td>N%</td><td>22.36</td><td>22.44 to 22.29</td>

Protocol 7: Preparation of 2- [(O-aminoethyl) amino] anthraquinone. The reaction proceeds according to the following scheme:

O

KOH

BrCH₂-CH₂br

NH

-N ^C6^H5^SO2^C1

-N

CH₂-CH₂br

Ύ SO2^C6^H5

CH₂-CH₂-N &lt;_C

X.

^SO2^CS^H5

<img file="AT277463B_D0011.tif" />

-NH SO CH 2 β 5, e.g.

X

NK ^SOA

-&gt;

hydrazine hydrate

- 9 No. 277463

<img file="AT277463B_D0012.tif" />

nh-ch₂ch₂nh₂

Ο

1. Phase: Preparation of 2- [N- (benzenesulfonyl) -amino] -anthraquinone.

To a solution of 1 mole (223 g) of 2-aminoanthraquinone in 1800 cm³ Pyridine are added at 45 ° C gradually with stirring 1.32 mol (166 cm³) Benzenesulfonyl chloride added. After this addition, the reaction mixture is kept at 45 ° C for 4 hours and then cooled to 0 ° C. The crude product separated by filtration is washed first with water which has been slightly acidified with hydrochloric acid, then with water and finally with alcohol. There are thus obtained 320 g of virtually pure benzenesulfonamide, which melts at 276 ° C. From the pyridine filtrate can be obtained by dilution still 12 g slightly less pure benzenesulfonamide.

Second Phase: Preparation of 2- [N-benzenesulfonyl-N- (β-bromoethyl) amino] anthraquinone.

0.05 mole (18.15 g) of 2- [N-benzenesulfonylamino] -anthraquinone are added at 60 ° C in 90 cm³ Dissolved dimelhylformamide. To this solution is added a solution of 3.08 g KOH in 2 cm³ Water and 6 cm³ Alcohol and then, as quickly as possible, 0.1 mol (18.8 g) of 1,2-dibromoethane added. The reaction mixture is allowed to stand for 2 hours on the boiling water bath and then poured into 1 ice-water. The separated crude product is treated with π / 2-NaOH to remove small amounts of unreacted 2- [N-benzenesulfonylamino] anthraquinone and then washed with water. 15 g of 2- [N-benzenesulfonyl-N- ( ß-bromoethyl) -amino] -anthraquinone recovered, which melts after recrystallization from acetic acid at 155 ° C.

Third Phase; Preparation of 2- [N-benzenesulfonyl-N- (β-phthalimidoethyl) amino] anthraquinone.

0.317 moles (148 g) of 2- [N-benzenesulfonyl-N- (β-bromoethyl) -amino] -anthraquinone are in 675 cm³

Dissolved dimethylformamide. To this solution is added 0.412 mol (76.5 g) of potassium phthalimide. The reaction mixture is refluxed for 1 h, then cooled and poured into 6 l of ice-water. There are obtained 138 g of crude product, which melts after recrystallization from acetic acid at 236 ° C.

<td>Analysis:</td><td>calculated for^C3O^H2oW =</td><td>found:</td>

<td>C%</td><td>67.16</td><td>67.07 to 66.83</td>

<td>H%</td><td>3.73</td><td>3.87-3.80</td>

<td>N%</td><td>5.22</td><td>5,27- 5,20</td>

4th Phase: Preparation of 2- [N- (β-phthalimidoethyl) amino] anthraquinone.

0.225 mol (121 g) of 2- [N-benzenesulfonyl-N- (β-phthalimidoethyl) -amino] -anthraquinone are dissolved in

600 cm³ conc. Dissolved sulfuric acid, the temperature is maintained at 25 to 30 ° C. The reaction mixture is allowed to stand for 5 hours at room temperature and then poured onto 5 kg of crushed ice. 87 g of 2- [N- (β-phthalimidoethyl) amino] -anthraquinone are obtained, which is diluted at 270 °.

5th Phase: Preparation of 2- [N- (β-aminoethyl) amino] anthraquinone.

0.21 mole (83 g of 2- [N- (β-phthalimidoethyl) amino] anthraquinone are in 300 cm³ Dissolved diethylene glycol and with 0.42 mol (21.5 g) of hydrazine hydrate (98% g). The reaction mixture is heated to 110 ° C. for 2 hours, after cooling to 1500 cm³ Poured water, then stirring with conc. Acidified hydrochloric acid and heated in the boiling water bath until the dissolution of the chloroform hydrate formed. After cooling, 59 g of 2- [N- (β-aminoethyl) -amino] -anthraquinone chlorohydrate are obtained, which contains a small amount of phthalhydrazide chlorohydrate. The crude product is reacted with 350 cm? Treated 2n-KOH to give 45 g of virtually pure 2- [N- (ß-aminoethyl) amino] anthraquinone, which melts after recrystallization from pyridine at 180 ° C.

Nr.277463

<td>Analysis:</td><td>calculated for^CA^N4 &lt;V</td><td>found:</td>

<td>C%</td><td>72.18</td><td>72.43 to 72.35</td>

<td>H%,</td><td>5.26</td><td>5.42-5.35</td>

<td>N%&gt;</td><td>10.52</td><td>10.54 to 10.40</td>

Example 1: The following colorant is prepared:

1- [0- (aminoethyl) amino] -2-nitro-4-methoxybenzene 0.21 g

With 10.5 moles of ethylene oxide oxyäthylenierter lauryl alcohol 1.00 g

10% citric acid solution until a value of 9 is reached

Fill with water to 100 cm³

This remedy is used for dark blonde hair. The duration of exposure to the hair is 10 min, then rinsed and washed. It will receive an intense mahogany copper nuance.

Example 2; The following hair dye is produced:

4-Methylamino-1- [(y-aminopropyl) -amino] -anthraquinone 0.25 g

With 10.5 moles of ethylene oxide oxyäthylenierter lauryl alcohol 5.00 g

10% citric acid solution to a value of 7

Fill with water to 100 cm³

The remedy is used for brown hair with slightly ebony reflections. This agent is allowed to act on the hair for 10 minutes, then rinsed and washed.

It will get a blue-black color.

Example 3: The following colorant is prepared:

4-Methylamino-1- [y-aminopropyl] -amino] -anthraquinone 0.05 g

20th 1-Amino-2-nitro-4-meihylaminobenzene 0.17 g of 1-amino-3-nitro-6- [y- (N, N-diethylaminopropyl) -amino] -benzene. 0.11g

With 10.5 moles of ethylene oxide oxyäthylenierter lauryl alcohol 3.00 gn / 2-Na₂CO₃ Solution until a p ^ value of 9.5

Fill with water to 100 cm³

This remedy is used for 100% white hair. It is allowed to act on the hair for 10 minutes, then they are rinsed and washed. One holds a dark ash blond

Example 4: The following hair dye is prepared:

4-Methylamino-1- (y-aminopropyl) -amino] -anthraquinone 0.12 g of l - [(y-aminopropyl) -amino] -anthraquinone 0.33 g of 1-amino-2-methyl-4-nitro-5 - [(&amp; - aminoethyl) -amino] -benzene 0.07 g

Lauryl alcohol oxyethylenated with 10.5 moles of ethylene oxide 3.5 gn / 2-Na₂CO₃~ Solution until a pn "value of 9

Fill with water to 100 cm³

This remedy is used for 100% white hair. It is allowed to act on the hair for 10 minutes, then rinsed and washed. You get a strong steel gray.

Example 5: The following colorant is prepared:

1,4-diamino-5- [(y-aminopropyl) -amino] -anthraquinone 0.13 g

With 10.5 mol ethylene oxide oxyethylenated lauryl alcohol 5 g

Fill with water to 100 g

This remedy has a p_HValue of 9.5. It is used for light auburn hair with gold reflections. The agent is allowed to act on the hair for 10 minutes, then rinsed and washed. A maroon with strong ash reflexes is obtained.

Nr.277463

Example 6; The following hair dye is produced:

1,4-diamino-5 - [(y-aminopropyl) amino] anthraquinone 0.060 g

- [(y -aminopropyl) -amino] -anirachinone 0.075 g

4-Nitro-3 - [(β-aminoethyl) amino] - (N, N-dimethyl) -aniline 0.015 g

With 10.5 moles of ethylene oxide oxyäthylenierter lauryl alcohol 5 g

20% citric acid solution until a p_HValue of 7

Auffiillen with water to 100 g

This remedy is used for 90% white hair. It is allowed to act on the hair for 10 minutes, then they are rinsed and washed. It becomes a strong, slightly mauve color

Got gray.

Example 7: The following hair dye is prepared:

<td>Monoazo compound {[p-nitroaniline] - * [N-ethyl-N- (β-aminoethyl) -</td><td></td><td></td>

<td>-aniline]}</td><td>0.5</td><td>G</td>

<td>n-Butylätiier of ethylene glycol</td><td>25.0</td><td>G</td>

<td>With 6.4 moles of ethylene oxide oxyäüiyleniertes ß-naphthol</td><td>12.5</td><td>G</td>

<td>Fill up with water</td><td>100</td><td>G</td>

This remedy is used for natural gray hair, u. between about a volume of solution for the appropriate amount by weight of hair. The agent is allowed to act on the hair for 30 minutes at room temperature. After rinsing, washing and drying, a pale reddish Orange 20 color is obtained.

Example 8: The following solution A is prepared:

1,4-diamino-5- [N- (y-aminopropyl) -amino] -anthraquinone 2 g

Monoazo compound {[p-nitroaniline] - »[N-ethyl-N- (β-aminoethyl) -aniline]} 2 g

Make up to 100 g with Μοπο-n-butyl ether of ethylene glycol

The hair dye is obtained by the following dilution of solution A:

Volume with 6,4 moles of ethylene oxide oxyethylenated β-naphthol 5 volumes of water

Volumes of solution A.

This remedy is used for natural gray hair, u. between about one volume of solution to the appropriate amount by weight of hair. The agent is allowed to act on the hair for 30 minutes at room temperature. After rinsing, washing and drying, a magenta gray color is obtained.

Example 9: The following hair dye is prepared:

2 - [(β-aminoethyl) -amino] -anthraquinone 0.1 g

Iso-octyl-phenyl-polyethoxy-ethanol 5 g

Butoxyethanol 6 gn -Na₂CO₃ Solution until a ρ value of 8 is reached

Fill with water to 100 g

This remedy is used for 90% white hair. It is allowed to act on the hair for 20 minutes, then they are rinsed and washed. It will receive a mahogany blond.

Example 10: The following hair-dyeing water-lotion is prepared:

Polyvinylpyrrolidone 2 g

- [(y -aminopropyl) -amino] -anthraquinone 0.020 g

1,4-diamino-5 - [(y-aminopropyl) -amino] -anirachinone 0.028 g

2 - [(β-aminoethyl) -amino] -anthraquinone 0.036 g

Ethyl alcohol (96%) 50 cm³

Fill with water to 100 cm³

- 12 No. 277463

This lotion is made with n-Na ^ COg solution on a p_HValue of 7 set and used before laying the water waves. It is not rinsed and the hair before drying in the usual

Fashioned. On 70% white hair, a strong violet gray is obtained and at the same time a

Stiffening of the hair achieved.