Composition and Dyestuffs for use in the Dyeing of Keratinic Fibres

The present invention relates to novel compounds. dyeing operations for dyeing hair¹;

'The subject of the present invention is the new industrial product which constitutes a tinotorial composition for human hair, essentially characterized in that it contains, in solution, at least one compound having the following general formula t

À - NR - (CH_) «NÏÏRli (I) m IL in which R and R 'are the same or different and represent a hydrogen atom, a lower alkyl radical or /

a hydroxy-lower alkyl radical J in which n is an integer from 2 to 6 inclusive; in which the radioal A represents t - 2 "," or else an anthraquinone radical of formula (II)

<img file="LU50233A1_D0001.tif" />

where Z represents a hydrogen atom or an NRR group ”,

R having the meanings indicated above and R being a hydrogen atom, a lower alkyl group or a group - (CltPn “NHRt, R” and n having the meanings above indicated, it being understood that on the anthraF p quinone nucleus , the chain NR - (®2 ^ nt which ^es^ explained in formula (l) can exclusively occupy either the position 1, in which case the radical Z, if it represents something other than a hydrogen atom, can exclusively occupy the positions numbered 4, 5 and 8, or the position 2, in which case the radical Z represents exclusively an atom

F * * of hydrogen J - or an azo radical of formula t

- NN - B₂ (III) formula in which and Bg each represent an aromatic oyole substituted or not by one or more nitro, halogen, alkyl, hydroxy, or amino-acyl groups j

- or else a henzene nucleus corresponding to formula I

GOLD"":

RUA _ / \ (IV) ψ- »ο₂ in which R · represents a hydrogen or a lower alkyl, the ohaine NR * (OH-) - NHR "being placed in position

I ΰΥ &amp; ϊ'Μ 'dirétbüxa para with respect to the dirétboxyy group and in which B represents a hydrogen atom and B' has the meanings indicated below

The dyes of formula (i) have many advantageous advantages. We can cite, for example, the great affinity they have for keratin fibers, which gives the dyes thus produced, great resistance to damage. live shampoos¹· In addition, using these dyes, one can obtain on the hair a very gum and '·' range of shades, ranging from yellow to blue, / with great stability è. light as a function of time. In addition, the dyes used for obtaining the dye compositions according to the invention have the advantage of being soluble in water for a wide r

pH range which can range from 4 to 10 and, preferably, from 7 to 9 hours. For an increase in pH, an organic or mineral acid such as lactic acid or hydrochloric acid can be used as the acid. ·

The contact time of said dye solutions with hair can vary within wide limits but is preferably between 5 and 30 minutes ^ The temperature of application of said dye solutions can also be varied, but, in most cases , they are used ^ preferably ^ at room temperature. The concentration of the dye compositions in colorants of formula (1) can be varied appreciably, but this concentration is preferably between 0.01 $ £ f

and yfib

It should be noted that the new colorants can be mixed with one another and also used in mixture with other colorants usually used for dyeing hair;

In addition, the tinotorial compositions according to the invention may contain the ingredients generally used such as dispersing or wetting agents, thickeners, detergents, emollients, “L” perfumes.

The present invention also relates to a process for dyeing keratinous fibers which is essentially oaraoterized by the fact that the fibers to be treated are treated, and in particular the hair, with a dye composition according to the invention which is left act on said composition for 5 to 30 minutes, then rinse and dry the hair *

The compounds of formula (I) for which the radical A represents a radical of formula (II) above indicated, can be prepared, in known manner, by condensing a diamine of formula NHß-NIR on a monohalogen derivative. or dihalogenated with anthraquinone or quinizarin ·

The compounds of formula (i), for which the radical A represents a radical of formula (III) above indicated, can be obtained, in known manner, by making the diazonium salt of the amine Bj-NEL, aveo the mine

B₂ - NR r (CH₂)_not- NHR *.

The compounds of formula (I) for which the radical A represents a radical of formula (XV) above indicated, can be obtained, according to known methods, /

t · è, starting from the amines of formula t · »5 · * by attachment to the NHg group of the aromatic ring of the NHE ** group;

To better understand the present invention, we will describe "by way of non-limiting illustration, some examples of preparation and use of dyes of formula (i)";

EXAMPLE I

Preparation of methylamino-1, (Λ-aminoethyl) -amino-4, r ·. ,::

anthraquinone \

The preparation reaction used can be t''4 schematically as follows:,

<img file="LU50233A1_D0002.tif" />

A toluene solution of methylamino-1, bromo-4, anthraquinone was heated for several hours under reflux in the presence of an excess of ethylenediaraine.¹; After cooling, the toluene solution is treated several times with a solution of normal hydrochloric acid.¹; 'j These hydrochloric extracts are combined and then made alkaline in order to release the oherched base, which is recovered by | extraotion è, using ethyl acetate, £ κχχκ &amp;&amp; χ £ χαχ ji

- SkXVMKXflaCKliqHKXkxKâritkKXxadaxjucfltnxdxRXxkkxicâixtKxdjcKihyJcK ·

By adding oxalic acid to this solution in ethyl acetate, the expected amine is preoipitated in the form&gt;

d * oxalate, which is wrung;

The corresponding base is released by making | the aloaline medium and isolated in the usual way¹; She ί ί

t bottom K 168 ° C after crystallization from toluene. ΐ

<img file="LU50233A1_D0003.tif" />

From this base, methylamino-1, (p -acetylaminoethyl) -amino-4, anthraquinone was prepared by adding acetic anhydride to a solution of methylamino-1, (£ -aminoethyl) -amino-4, anthraquinone in ethyl acetate * This mono-acetate, recrystallized from alcohol.

normal propyl, background k 220 ° C j its analysis gives the following j results t:

Analysis

Calculated for C ^^ H ^^ N ^ O ^

Find

<td>vs%</td><td>I t</td><td> 67,65</td><td>I 67.50 - J</td><td> 67,44</td>

<td>H%</td><td>1 I t</td><td> 5,64</td><td> ! 5,86 1</td><td> 5,84</td>

<td>NOT</td><td>I I</td><td> ^2,46</td><td> ! 12,20 -</td><td> 12,22</td>

J EXAMPLE II

Preparation of methylamino-1. (o -aminopropyl) -amino-4 * anthraquinone j

The preparation reagent, which is used, can i

be schematized as follows tj

<img file="LU50233A1_D0004.tif" />

A solution of methylainino-1, bromo-4, anthraquinone in a solvent such as toluene is heated for several hours under reflux in the presence of an excess of 1,3-diaminopropane. "After treating the reaction mixture in a similar manner to that which was described in Example 1, methylamino-1, (Y ~ aminopropyl) -amino-4, anthraquinone, is isolated, which after crystallization from toluene, background k 142®0 *

For this compound, the calculated molecular weight is 309 and that found experimentally by potentiometric determination is 303 * 4

The monoacetate obtained from this base base at 224 "di

EXAMPLE III

Preparation of (T-arainopropyl) -amino-l, anthraquinone

Q ·

Ιθ The preparation reaction which is used can be sohematized as follows:. .

<img file="LU50233A1_D0005.tif" />

A solution of 1-chloro, anthraquinone in a solvent such as toluene is heated for several hours at reflux in the presence of an excess of 1,3-diamino-propane. After cooling, the toluene solution is treated for several times. taken up with a normal hydrochloric acid solution¹· The hydrochloric extracts are combined and then made aloaline in order to release the sought base, which crystallizes · It is wrung out After reoristallization in tolene, it melts at 152 ° C.

From this base, (y-aoéty- 'laminopropyl) -emino-4, anthraquinone is prepared by adding acetic anhydride to a solution of (Y-aminopropyl) amino-4, anthraquinone in acetate. ethyl. This monoacetate, recrystallized from ethyl alcohol, melts at 202 ° C?

3B 'its analysis gives the following results t /

<td>Analysis</td><td colspan="2">j Calculated for ®ΐ9^Ηχθ ^ 2 ° 3 1 I!</td><td>I Find ¹</td>

<td>VS %</td><td>I I I 1</td><td>70.81 I</td><td> 70,73 - 70,70</td>

<td>H%</td><td>i I t</td><td>5.59 I J</td><td> 5,61 - 5,62</td>

<td> NOT%'</td><td>1 I</td><td> 8,69 !</td><td> 8,54 ~ 8,45</td>

<td></td><td>-L</td><td>The</td><td></td>

EXAMPLE IV

Preparation of -aminoethyll-amino-1 "nitro-2, methoxy&gt; -4" benzene

The synthesis process used can be structured as follows s

<img file="LU50233A1_D0006.tif" />

<img file="LU50233A1_D0007.tif" />

Born. CH₂m CH₂ Br k₂- &lt;5&gt; οπ₃ &lt;So₂- &lt;dd2&gt; CH ~₃

<img file="LU50233A1_D0008.tif" />

Μ 9 * &lt;*

It is found that the chromated derivative obtained at the end of the fourth phase of the preparation is, here, manufactured according to the process described in a Luxembourg patent application No. 49 "213 filed on July 30, 1965i We will, however, give below after the detail of all the stages of this synthesis process.

1st -phase t Preparation of N - ^ - toluene-sulfonylamino-1, nitro-2, methoxy-4, benzene

To a solution of 0.1 mole of amino-l, ni, tro-2, methoxy-4, benzene (i.e. 16.8 g) in 60 cm3 of pyridine, the following is added at -30 ° C, little by little and with stirring,

0.12 moles of ^ -toluene sulfochloride (i.e. 22.86 g). When the addition is complete, the reaction mixture is kept for 6 hours at room temperature, it is poured onto 300 g of ice with 30 cm 3 of hydrochloric acid added and it is filtered. The crude product is redissolved in a sodium hydroxide solution._lE * -normal^,ô The sodium solution is filtered (4 g of starting product insoluble in soda are recovered) then neutralized with hydrochloric acid. 25 g of N - /? - toluene-sulfonylamino-1, 2-nitro, methoxy- are wrung out 4, benzene which, after recrystallization in

<td colspan="5">the aloool, melts at 102 ° (j. The results of the analysis of this product are as follows t</td>

<td>Analysis</td><td>l 1 Calculated for</td><td>l l l t</td><td>Find</td><td></td>

<td> 0 $</td><td>l 52.17 t</td><td>l l t</td><td> 52,09 -</td><td> 52,28</td>

<td>H $</td><td>l 4.34</td><td>1 î f</td><td> 4,43 -</td><td> 4,44</td>

<td>NOT #</td><td>I 8.69</td><td>l l</td><td> 8,74 ~</td><td> 8,92</td>

<td></td><td></td><td>JJL ·</td><td></td><td></td>

I

10.10

2nd Phase t Preparation of the sodium derivative of Np-toluenesulfo'ilylamino-1, nitro-2 _tmethoxy-4.benzène.

Orçdissout 0.155 mole of Np-toluenesulfonylamino-1 / nitro-2, methoxy-4, benzene in 600 cn? semi-normal soda, jf

. 3 * then 250 cm of sodium hydroxide ten times normal is added to this solution, with stirring. 48 g of sodium derivative are wrung out and · washed with a little alcohol, then a little acetone.

3rd Phase I Preparation of Npt.oluenesulfonyl, Np-bromoethyl "amino-1, nltro-2, methoxy-4, benzene.

'0.0103 mole of the sodium derivative -dissolved!

N -p-toluene'sulfonylamino-l, nitro-2, methoxy-4, benzene (ie 3.56g) in 5cm ^ of dimethylformarnide * 0.023 male is added

Λ} of dibromo-l, 2-ethane (i.e. 2 cm^J), we bring to reflux

J quarter of an hour, pour the reaction mixture into 50 in? Of water. After extraction with ethyl acetate, the ethyl acetate solution is washed with semi-normal soda to remove a little Np-toluenesiXLfonylamino-1, nitro-2, methoxy-4, benzene J y * ο ί then wash with water. We then concentrate about 10 cm,, t

a little hexane is added and 2.7 g of (Np-toluenesulfonyl, N - ^ - bromoethyl) amino-1, 2-nitro, 4-methoxy, benzene are filtered off which, J after recrystallization from alcohol, absolute, background at 117 * C. The results of the analysis are as follows:

<td>B = = oaaaaoa year ==== annc Analysis</td><td>passaasseassssassssssssaBSsac: Calculated for ^VSJL6^hi7^NOT2°5^{S Br}</td><td>Find</td>

<td>VS #</td><td>44.75 'L</td><td> 44,79 - 44,9^</td>

<td>H .. £</td><td> 3.96</td><td> 4,17 - 4,1^</td>

<td>N $ t t</td><td> 6,52</td><td> 6,73 - · 6,62</td>

• «/· ·

114th PHASE i Preparation of N - ^ - bromoethylamino-l, nitro-2. 4-methoxy, benzene *

0.093 mole of (Np-toluene sulfonyl, N - ^ - bromoé thyl) amino -1, nit ro-2, methoxy-4, benzene (that is to say 4θ g) are dissolved in stirring in ÎÔO cn? sulfuric acid concentrated in. now the temperature between 0 and 5^eC. The reaction mixture is left for three hours at 0 ° C. and then poured onto 1.2 kg of crushed ice. 25.1 g of N - bromoethylamino-1 are drained_f2-nitro, 4-methoxy, benzene which, after recrystallization from the benzene-hexane mixture, melts at 57^βθ ·

The results of the analysis are as follows t

<td>p = 3 22Baaaa == == 3 = 3C2 = Analysis</td><td>SCSS 8 S S3 S X3 &amp; 2 S 3 S S3 S3 8 B 8 S Bt S CS SSSS SS s: Calculated for C ^ H ^ N ^ O ^ Br</td><td>t Find</td>

<td>c fi</td><td> 39, 27</td><td> 39,41 - 39,36</td>

<td>H fi</td><td> 4, 00</td><td> 4,18 - 4,20</td>

<td>N fi</td><td> 10, 18</td><td> 10,39 - 10,27</td>

5th PHASE t Preparation of N-ft-phthalimidoethylamino-1. .

nitro-2-methoxy 4.benzène. ,

0.27 mole of N-JJ-bromoethylamino-1, 2-nitro, 4-methoxy, benzene (i.e. 74 g.) Are dissolved in 290 in? ₍ dimethylformamide. 0.32 mole of potassium phthalimide (i.e. 59.5 g) is added and the reaction mixture is heated at reflux for one hour. We filter boiling; the filtrate is cooled and wrung 79 g. of N - ^ "- phthalimido- ethylamino-1, nitro-2, methoxy-4, benzene, which, after recrystallization from dioxane, melts at 212 * 0. The results of the analysis of the product obtained are the following t

Aaao3sas5 bs = = = n = aace ananC33a ssa = 03 = =! = == born ö "= 22: 2 == = a = 23c s = dc = ace

<td></td><td>Analysis</td><td>Calculated for H ^ N ^ O ^</td><td>Find</td>

<td></td><td>/ C fi ”</td><td> 59,82</td><td> 59,61 - 59,73</td>

<td></td><td>H fi</td><td> 4,39</td><td> 4,42 - 4,60</td>

<td></td><td>N fi</td><td> 12,31</td><td>la., 50 - 12,48</td>

t

I

12.6th PHASE | Preparation of N-jà-aminoethylainino 1, nitro-2, methoxy-4, benzene.

0.1 mol of N - phthalimidoethylamino-1, nitro-2, 4-methoxy-benzene o (that is to say 34.1 g.) Dissolved in 350 cnr te is heated at reflux for one hour. propanol with 0.2 mole of hydrazine hydrate (i.e. 10.2 g).

The reaction mixture is boiled dry to remove the phthalhydiazide formed. After the filtrate has cooled, a little untransformed initial product is recovered by filtration. The propanolic solution of gaseous hydrochloric acid is then saturated and 22.5 g of the expected product is drained in the form of the hydrochloride. This hydrochloride, after recrystallization from water, is given to the analysis. The results of

<td colspan="3">the analysis are as follows x aaasaaoaocaanaaoos = s = a33x = aaaatiBa22222ac2cns =======: = n3aan == ^</td>

<td>Analysis</td><td>Calculated for C ^ H ^ N ^ O ^ Cl</td><td>Find</td>

<td>VS %</td><td>J 43.63</td><td>43.79 - 43, ÔO</td>

<td>H%</td><td> 5,65</td><td> 5,65 - 5, 70</td>

<td>NOT %</td><td> 16,96</td><td> 17,05 - 17, 08</td>

lté Np-aminoethylamino-1, nitro-2, methoxy-4, benzene isolated in the usual way from this monoohlorhydrate melts at 57'0.

EXAMPLE V

The following tinotorial composition is prepared x

- (p-aminoethyl) -amino-1_t 2-nitro, 4-methoxy, benzene. "0.21 g ·· oxy-ethylene lauric alcohol containing 10.5 moles of ethylene oxide .......... ** ··. ·" .A "····· *. ·. · ............ 1.00 g

- citric acid in 10% solution q.Sop '. ........ pH "9

- water q'is; p »*» «* · **. ·« «* ·. ··« ·· «·· ... ···. ····.« ....... 100cm3 • 30

<img file="LU50233A1_D0009.tif" />

ie

Ec?

This composition is applied to hair t&gt;

dark blond ; leave to act for 10 minutes; we rinse and wash with shampoo¹* We obtain a shade ACHYMOGRAPH INTENSE COPPER¹«

EXAMPLE VI

The following dye composition is prepared t

ΧΟ • Η- methylamino-1, (P -aminopropyl) —amino-4, anthraquinone. ₀ ....... _e ........ ............... 0.25 g *&gt; oxy-ethylenic lauric alcohol h 10.5 moles of ethylene oxide 5.00 g

- citric acid in solution at 10 # qs' * .... pH "7 t water q'is' * p '* ...................... ............... 100 om3

This composition is applied to brown hair

è. slightly auburn reflections; leave to act for 10 r minutes) rinoe and wash with shampoo · We obtain a

BLACK BLUE¹*

<img file="LU50233A1_D0010.tif" />

EXAMPLE VII 'P, · \ · ;, i *' 'i * t. X.

I ''

cp 'ΐί:

The following dye composition is prepared t '7 "- methylamino-1, (/? - aminopropyl) -amino-4, anthraquinone ···········" ········· * · ··. ·· ** ··· 0.05 g - amino-1, nitro-2, methylamino-4, benzene. ··· * ·· 0.17 g '·; - amino-1, nitro- * 3, (V-NyN-diethylaminopropyl) amino-6, benzene ·····. ········· * ····. * ...... ... 0.11 g - lauryl alcohol oxy-ethylene with 10.5 moles of oxide. · ”* Ethylene ··· '··················“ ···. ······ ...... 3.00 g / sodium carbonate in semi-normal solution qWip ** ... ♦ * ·.;. ·. *. *. Λ .................. .pH - 9.5 - water q'iaip **. *. * »··« ····. ·····. ·. ··········· ..... 100 cm3

This composition is applied to 30,100 # white hair; leave to act for 10 minutes on rinoe and wash with shampoo ** We obtain an ASH PONCE BLOND ** i

· * 14 · »'· EXAMPLE VIII ^: "ΝΜΜΜΜΜΜΜΜΜΜΜΜΜΜΜ ​​·

The following dye composition is prepared: t .vy · * methyl amino-1, (j8-aminopropyl) -amino-4, '' '* 1 r anthraquinone ··········· “···· * ·· "* ·· · '· ··" ···· * 0.12 g. / 5. 'Λ · (V-çminopropyl) -amino-1, · anthraquinone ·· «* ·« ·· 0.33 g. 'ν'- amino-1, methyl-2, nitro-4, ($ -aminoethyl) &lt;?^: 5-amino, benzene 'b ···· “··” “··“ · “·“ * ·· ”·“ ··· “·“ * 0.07 g / ·! · oxy-ethylene lauric alcohol , 10.5 moles ......

¹ * “” Of ethylene oxide ···· * ““ ··· “··· * ·· ** ·····“ ··· 3.5 g

- 10 - sodium carbonate 'in semi-normal solution' '' q'is'in'i hb ········· ♦ ·· * ······ “·! · '··· ···. ··· pH ** 9. 'g. water q'ftS ^ p'i i "" · "** ·· * ·· * ·· * ········; · ;; ·; ·; ·; ·; 100 cm3 * • s ·:

This composition is applied to hair

100% hlanos j left agip for 10 minutes; we rinse 15 and oh l, with shampoo att. You get a POWERFUL STEEL GRAY^w