Untitled record

PATENT

PV Il 913.810 (îk ^{422 016}

FRENCH REPUBLIC

MINISTRY OF INDUSTRY

INDUSTRIAL PROPERTY SERVICE

International classification:

<img file="FR1422016A_D0001.tif" />

C 09 &amp;

New anthraquinone dyes and their application to hair dye.

(Invention: Grégoire Kalopissis, Jacques Bertrand and M ™ Bugaut, née Andrée Ormancey.)

Public limited company called: LORÊAL residing in France (Seine).

Requested on October 29, 1962, at 4 p.m.^h 48^m, in Paris.

Issued by decree of November 15, 1965.

(Official bulletin of industrial property, n ° 52 of 1965.) (Patent of invention whose delivery was postponed in execution of article 11, § 7, of the law of July 5, 1844 modified by the law of 7 April 1902.)

The subject of the present invention is, on the one hand, certain new chemical compounds derived from anthraquinone and, on the other hand, the use of both these new compounds and other already known compounds, for dyeing living hair.

In general, the compounds which are the subject of the invention can be represented by the following general formula:

·+

- (CH₂)_not-N &lt;—R '^ XR

ÆH-CH

- (CH₂)_not-N &lt;\ o

AA-

<img file="FR1422016A_D0002.tif" />

ch₂—Ch₂ , CH₂-CH₂.

formula in which one of the NH — Z groups can occupy positions 4, 5 or 8, while the other NH — Z group always remains in position 1.

In addition, in this formula, the letter Z represents a group:

(CH₂)_not-N &lt;|, where R and R 'are the same or different lower alkyls, such as —CH3, —C₂H₅, etc., R and R ′ which may moreover form part of a heterocyclic residue such as, for example, a morpholine or piperidine residue; the tertiary amine function of these groups can also be present in the form of quaternary ammonium, and n being an integer between 2 and 6.

When the tertiary amine function is quaternized, the group Z can be represented for example by the following formulas:

- (CH₂) „R

CH.—CH.

: ch „

In which n, R and R 'have the abovementioned meaning, R represents a lower alkyl radical and A is an anion, such as for example a halogen or a methosulfate, etc.

Although the textile industry has already used dyes derived from amino-anthraquinone having quaternary ammonium groups for the dyeing of certain synthetic fibers, the use of compounds bis, N, N - alkyl alkylene - amino - anthraquinone Quaternary or not has never been reported so far for dyeing live hair.

The Applicant has discovered that the chemical compounds of formula (I) are well suited as dyes for dyeing, preferably at ordinary temperature, hair.

Indeed, these dyes, due to the presence of the two basic groups, ternary or quaternary, have a great affinity for the hair and this in a range very

2191 0 73 843 3

Price of the booklet î 2 francs [1.422.016]. . - pH range which can range from 3 to 10 and preferably from 4.5 to 9.5, depending on whether their ternary or quaternary derivatives are used.

In addition, their solubility in water by the accumulation of basic groups is considerably increased, thus making it possible to obtain aqueous dye solutions whose concentration can exceed even 10%.

Another advantage, very appreciable in the hair art, is the resistance that the dyes obtained using these dyes exhibit to sunlight.

Their solidity is therefore roughly comparable to that of standard 4, which is part of the range established by the Association for the determination of the solidity of dyes and textile prints (see Solidity Code, published by the Continettal Study Group European, 2^e edition (1958), p. 31), when this standard and the dyes obtained are simultaneously exposed and under the same conditions to sunlight.

Note that the range of standards extends from 1 to 8, 8 representing, of course, the strongest solidity. On the other hand, by an adequate choice of the respective position of the two amino groups of the anthraquinone molecule, it is possible to obtain dyes leading to very varied shades, which can range from red to blue and to blue- green. Therefore, by mixing between. them these dyes, we can easily obtain natural shades very appreciated by the user.

It should be noted that among all the aforementioned compounds, some are particularly suitable as is the case. for the dyes of formula I containing morpholine or piperidine residues which, when applied to the dyeing of the hair, do not give off any unpleasant odor.

The present invention therefore also relates to a composition for dyeing the hair, a composition characterized in that it contains one or more compounds of the general formula I indicated above.

The dye composition in accordance with the invention may contain only dyes corresponding to the general formula indicated above and, in this case, shades ranging from red to blue-green are obtained.

It is however possible to mix the dyes in accordance with the invention with other dyes usually used for dyeing the hair.

The dye composition in accordance with the invention is generally in the form of an aqueous solution and it can be very easily prepared by dissolving in water one or more compounds of formula I mentioned above as a mixture will go non with others -

known dyes. It is possible to incorporate into these dye solutions various products usually used in the field of cosmetics, such as dispersing agents, emollients, perfumes, etc. The pH of these dye solutions can oscillate within wide limits and it is generally between 3 and 10 and preferably between 4.5 and 9.5.

The compositions in accordance with the invention are applied to the hair in the usual way, preferably at ordinary temperature. The dye concentrations of formula I can vary within wide limits, depending on the particular aim sought.

The new compounds in accordance with the invention are obtained from quinizarin or from 1,5 - or 1,8 - dichloroanthraquinone by the action of a. N, N - dialkyl - alkylene - diamine of formula:

. . . NH_at- (CH₂)_not--N &lt;*_z in which: n, R and R 'have the meaning indicated for the above general formula.

The quaternization of the tertiary anthraquinone derivatives thus obtained can be carried out very easily in the usual manner by the action of a quaternization agent such as methyl sulphate or an aleoyl halide, in the presence or not of an appropriate solvent.

The nonlimiting examples below illustrate:

On the one hand, the process for preparing the new chemical compounds;

On the other hand, the application of these compounds as dyes to hair dye.

Examples of preparation

Example 1. - Preparation of 1,4 - (β morpholinoethyl) - amino - anthraquinone.

<img file="FR1422016A_D0003.tif" />

A mixture of 0.06 mol / g of quinizarin, 0.06 atom / gram of zinc and 0.2 mol / g of β-aminoethylmorpholine in 100 cm is brought to reflux for three hours.³ isohutanol.

After having oxidized the intermediate leuco derivative thus formed and filtered the zinc, the mixture thus obtained is evaporated to dryness and the residue dissolved in benzene. The benzene solution is then washed with a 10 / a sodium hydroxide solution and then dried and evaporated to dryness.

The sought product is thus obtained with a - [1,422,016] yield of 90%. This product, recrystallized from hexane, melts at 157 ° C.

(See table in column opposite)

Example II. - Preparation of bis - methyi [(1,4 - anthraquinonyl - amino - ethyl) - methyl - morpholinium] sulfate.

<td>Analysis</td><td>Calculated</td><td>Find</td>

<td>vs, % ..................</td><td> 67,24</td><td> 67,15-66,93</td>

<td>H,% ..................</td><td> 6,89</td><td> 7,00- 6,91</td>

<td>not; % ..................</td><td> 12,06</td><td>1L87-1L77</td>

<img file="FR1422016A_D0004.tif" />

This product is easily obtained from the corresponding spondant base by the action of methyl sulphate, using, as solvent, toluene, at reflux, in the usual manner. The product, recrystallized from methanol, melts, as it decomposes, at 240-245 ° C.

(See table in column opposite)

CH-CH₂&lt;CH. ^

CH₂-

<img file="FR1422016A_D0005.tif" />

This product is obtained by the action of β amino ethylmorpholine, in slight excess, on the

1,5 - dichloroanthraquinone, using isobutanol as solvent and at reflux for 6 hours. After cooling, the precipitated crude product is purified by repeated recrystallization from alcohol. Mp = 203 ° C.

(See table in column opposite)

<td>Analysis</td><td>Find</td><td>Calculated</td>

<td>H,% ..................</td><td rowspan="2"> 7,82</td><td rowspan="2"> 7,77-7,60</td>

<td></td>

Example III. - Preparation of 1,5 - di - (β morpholinoethyl) - aminoanthraquinone.

<td>Analysis</td><td>Calculated</td><td>Find</td>

<td>vs, % ..................</td><td> 67,24</td><td> 67,12-67,23</td>

<td>H,% ....... ..........</td><td> 6,89</td><td> 6,75- 6,78</td>

<td>not; % ..................</td><td>12'6</td><td>Ιΐ'δδ-Ιΐ'δΟ</td>

Example IV. - Preparation of bis - methyi [(1,5 - anthraquinonyl - amino - ethyl) methylmorpholinium] tallow.

++

O:

<img file="FR1422016A_D0006.tif" />

<img file="FR1422016A_D0007.tif" />

2 (N / A₄CH-) [1.422.016] -

This product is obtained from the corresponding base above, in the usual manner, by the action of methyl sulfate in toluene. I melts, with decomposition, at 250 ° C.

<td>Analysis</td><td>Calculated</td><td>Find</td>

<td>NOT, % ..................</td><td rowspan="2"> 7,54</td><td rowspan="2"> 7,56-7,65</td>

<td></td>

Example V. - Preparation of 1,4 (ω - morpholinohexyl) - aminoantbraqninone.

Q NH (CH₂) -NOT:

<img file="FR1422016A_D0008.tif" />

Is brought to reflux, with stirring, in the same manner as in Example I, a mixture of quinizarin, zinc powder and aminohexylmorpholine in isobutanol, for four hours. After evaporation, etc., the sought product is obtained with a yield of 50 ° / o. After recrystallization from heptane, the product melts at 71 ° C.

<td>Analysis</td><td>Calculated</td><td>Find</td>

<td>vs, % ..................</td><td> 70,83</td><td> 70,87-70,98</td>

<td>H,% ..................</td><td> 8^33</td><td> 7,97- 8,27</td>

<td>not; % ..................</td><td> 9,72</td><td> 9,57- 9,50</td>

Example VI. - Preparation of bis - methyl [(1,4 - antbraquinonylaminobexyl) - methyl morpholinium] sulfate.

<img file="FR1422016A_D0009.tif" />

This product is obtained from the corresponding ternary base, described above, by quaternization using methyl sulfate in toluene, at reflux. The product is very bygroscopic and, therefore, it is used immediately, without purification.

Example VII. - Preparation of 1,8 (β morpholinoethyl) - aminoanthraquinone.

^ CH₂-CH₂„; N — CH„ —CH, —NH O NH — CH „—CH„ —N:

<img file="FR1422016A_D0010.tif" />

-CH₂-CH₂.

~ ch₂here₂This product is obtained in the same way as the product of Example HI, starting from 1,8 - dichloroanthraquinone and by causing the aminoethylmorpholine to act. Recrystallized from bexane, it melts at 170 ° -171 ° C.

<td>Analysis</td><td>Calculated</td><td>Find</td>

<td>vs, % ..................</td><td> 67,24</td><td> 67,27-67,03</td>

<td>H,% ..................</td><td> 6,89</td><td> 7,-16 6,96</td>

<td>NOT î / 0 ......... · ..... · · ·</td><td> 12,06</td><td> 12,37-12,25</td>

Example VIII. - Preparation of bis - methyl [(1,8 - antbraquinonyl - aminoethyl) - methyl morpholinium] tallow.

(See formula on next page)

This product is obtained in the usual way, from the corresponding base, by the action of methyl sulfate.

Recrystallized from alcohol, the product melts at 200-201 ⁰ by decomposing.

- 5 - [1.422.016] ++ ^ ch₂-ch₂.

CH „

<img file="FR1422016A_D0011.tif" />

2 (N / A₄CH₃-)

Example IX. - Preparation of 1,4 (γ - piperidino - propyl) aminoanthraquinone.

<img file="FR1422016A_D0012.tif" />

Is brought to reflux, with stirring, in the same manner as in Example I, a mixture of quinizarin, zinc powder and γ - aminopropyl - piperidine in isobutanol, for 10 hours. After evaporation, etc., the sought product is obtained with a yield of approximately 50%. Recrystallized from petroleum ether and alcohol, it melts at 123 °.

<td>Analysis</td><td>Calculated</td><td>Find</td>

<td>VS, % ..................</td><td> 73,77</td><td> 73-83-73,82</td>

<td>TT tl "/ o ..................</td><td> 8,19</td><td> 8,18-8,23</td>

Example X. Preparation of (1,4-anthraquinonyl-aminopropyl) benzyl piperidinium dichloride.

<img file="FR1422016A_D0013.tif" />

This product is obtained from the corresponding base by the action of henzyl chloride, using toluene as solvent, at reflux, in the usual manner. The product melts, decomposing at 165-170 ° C.

Examples of dyes:

Example XI. - The following mixture is prepared:

1,4 (β - morpholino - ethyl) - amino anthraquinone .................. 4.6 g

Acetic acid qs .............. pH 4.8

Water qs ........................ 100 cm³

This solution is applied to 95% white hair. It is left in contact for 10 to 15 minutes, at ordinary temperature. Rinse thoroughly with water and dry. A blue-green coloration is obtained.

Example XII. - The following mixture is prepared:

Bis - methyl [(1,4 - anthraquinonyl amino - ethyl) methyl - morpholinium] sulfate .................... 1 g

Fatty alcohol C₁₂-Ci4 (copra) condensed with 10 molecules of ethylene oxide 10 g

N / A₂CO₃ qs .................... pH 7

Water qs ........................ 100 cm³

This solution, applied under the same conditions as the above example, gives gray hair an intense blue shade.

Example XIII. - The following mixture is prepared:

Bis - methyl - [(1,8 - anthraquinonyl aminoethyl) - methyl - morpholinium] sulfate .................... 0.5 g

Bis - methyl [(1,4 - anthraquinonyl aminoethyl) - trimethyl - ammonium] sulfate .................... 2 g

Octylphenol condensed with 10 to 11 molecules of ethylene oxide ........ 2 g

N / A₂CO₃ qs .................... pH 8

Water qs ........................ 100 cm³ [1.422.016]

Octylphenol condensed with 10 to 11 molecules of ethylene oxide ........ 2.5 g

N / A₂CO₃ qs.p .................... pH 9.5

Water qs ............. 100 cm³

This solution applied to gray hair and left in contact for 10 to 15 minutes at ordinary temperature, gives, after rinsing, a purple color.

Example XIV. - The following mixture is prepared:

Bis - methyl [(1,8 - anthraquinonyl amino - propyl) - trimethvl - ammonium] sulfate .................... 4 g

20% ammonia qs .......... pH 9

Water qs ........................ 100 cm³

Under the same dyeing conditions as above, a purple violet coloration is obtained.

Example XV. - The following mixture is prepared:

Bis - methyl [(1,5 - anthraquinonyl amino - propyl) - tri - methyl - ammonium] sulfate .................. 1 g

Octylphenol condensed with 10 to 11 molecules of ethylene oxide ........ 2.5 g

N / A₂COs qs .................... pH 9

Water qs ........................ 100 cm³

Under the same application conditions as the previous examples, a purplish pink coloration is obtained.

Example XVI. - The following mixture is prepared:

Bis - methyl [(1,5 - anthraquinonyl amino - ethyl) - methyl - morpholinium] sulfate ....... · ............. 4 g

N / A₂CO₃ qs .................... pH 9

Water qs ........................ 100 cm³

Under the same application conditions, a shade comparable to the previous one is obtained.

Example XVII. - The following mixture is prepared:

1,5 (β - morpholino - ethyl) - amino anthraquinone .................. 4 g

Lactic acid qs .............. pH 4.8

Water qs ........................ 100 cm³

Under the same application conditions as in the examples above, a pink shade is obtained.

Example XVIII. - The following mixture is prepared:

1,4 - (γ - dimethyl - amino - propyl) amino - anthraquinone .......... 3 g

Lactic acid qs .............. pH 6

Water qs ........................ 100 cm³

This solution applied to the hair under the same conditions as in the examples mentioned above, gives a bluish coloration.

Example XIX. - The following mixture is prepared:

This solution applied to hair containing 90% white hairs, under the same conditions as in the above-mentioned examples, gives a deep blue color.

Example XX. —- The following mixture is prepared:

1,8 - [dimethyl - amino - propyl) - aminoanthraquinone ................ 1 g

Lactic acid qs .............. pH 3.5

Water qs ........................ 100 cm³

After application under the same conditions as above, on white hair, a beautiful purple coloration.

Example XXI. - The following mixture is prepared:

1,4 - (γ - piperidino - propyl) - aminoanthraquinone .................. 3 g

Lactic acid qs .............. pH 4.8

Water qs ............ 100 cm³

This solution applied as before, gives a pale blue shade.

Example XXII. - The following mixture is prepared:

(1,4 - anthraquinonyl amino - propyl) - henzyl - piperidinium dichloride ............................ 4.5 g

N / A₂CO₃ qs .......... pH 9

Water qs ........................ 100 cm³

This solution is applied in accordance with the previous examples, for 15 minutes and an azure color is obtained.

Example XXIII. - The following mixture is prepared:

- nitro - m - phenylene - diamine .... 0.1 g

Bis - methyl [(1,8 - anthraquinonyl aminoethyl) - methyl - morpholinium] sulfate .................... 1 g

Bis - methyl [(1,4 - anthraquinonyl aminoethyl) - methyl - morpholinium] sulfate .................... 1.5 g

Bis - methyl [(1,5 - anthraquinonyl aminoethyl) - methyl - morpholinium] sulfate .................... 1 g

NH₃ qs ........................ pH 8

Water qs ........................ 100 cm³

This solution is applied to 100% white hair. It is left in contact for 10 minutes, at room temperature. After rinsing, shampooing and drying, a beautiful brown color with slightly pink reflections is obtained.

Example XXIV. - The following mixture is prepared:

- nitro - m - phenylene - diamine .... 0.3 g

1,4 - (γ - dimethyl - amino - propyl) amino - anthraquinone ........ 1 g

1.8 - (γ - dimethyl - amino - propyl) amino - anthraquinone .......... 1.5 gp - nitrophenylenediamine .......... 0.3 g

Citric acid solution at 4% qs pH 5

Water qs ........................ 100 cm³

Under the same conditions as in the above example, on hair containing 90% white hairs, a chestnut color with copper highlights is obtained.