US3558259A

US3558259A - Human hair dyeing with aminophenols

Info

Publication number: US3558259A
Application number: US645520A
Authority: US
Inventors: Gregoire Kalopissis; Andree Bugaut
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1962-07-11
Filing date: 1967-06-12
Publication date: 1971-01-26
Anticipated expiration: 1988-01-26
Also published as: US3666812A; DE1492064A1; US3546293A; US3738799A; GB987342A; CH415965A; NL295194A; BE634643A

Abstract

THE PROCESS OF USING AND COMPOSITIONS CONTAINING DYES, WHICH ARE SUITABLE FOR ONE STEP DYEING OF HAIR AND KERATIN FIBERS WITHOUT REQUIRING THE USE OF SEPARATE DYE MODIFIERS WHICH ARE EXCEPTIONALLY COLOR STABLE, HAVING THE FORMULA:

2-(R-NH-),4-R,R4-PHENOL

IN WHICH R IS SELECTED FROM THE GROUP CONSISTING OF HYDRO GEN AND ALKYL, R1 IS SELECTED FROM THE GROUP CONSISTING OF HYDROXY AND ALKYL, AND R4 WHICH CAN BE IN POSITION 5 OR 6 ON THE RING IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, HALOGEN, HYDROXY AND ALKYL.

Description

United States Patent 3,558,259 HUMAN HAIR DYEING WITH AMINOPHENOLS Gregoire Kalopissis, Paris, and Andree Bugaut, Boulognesur-Seine, France, assignors to LOreal, Paris, France No Drawing. Continuation-impart of application Ser. No.

293,282, July 8, 1963. This application June 12, 1967,

Ser. No. 645,520

Claims priority, application France, July 11, 1962,

903,703; July 3, 1963, 940,212 Int. Cl. A61k 7/12 US. Cl. 8-10.2 9 Claims ABSTRACT OF THE DISCLOSURE The process of using and compositions containing dyes, which are suitable for one step dyeing of hair and keratin fibers without requiring the use of separate dye modifiers which are exceptionally color stable, having the formula:

in which R is selected from the group consisting of hydrogen and alkyl, R, is selected from the group consisting of hydroxy and alkyl, and R, which can be in position or 6 on the ring is selected from the group consisting of hydrogen, halogen, hydroxy and alkyl.

This applicationvis a continuation-in-part of application 293,282 filed July '8, 1963, which has been abandoned.

This invention relates to improvements in processes for the dyeing of hair and to new compositions suitable for one step keratin fiber and hair dyeing.

A number of processes for dyeing keratinic fibers and notably hair are at present known, among the most commonly employed of these processes are those which are oxidation dyes whose coloration results from polymerization under oxidizing conditions.

In practice, the oxidation dyes employed are almost exclusively mixtures of aromatic diamines and aromatic aminophenols, generally known as bases, in combination with substances, generally called modifiers, such as substituted or unsubstituted monoand polyphenols. It is thus possible, by using a relatively limited number of aromatic bases and phenols, to obtain a fairly wide range of colorations, the proportions of the various constituents which enter into the composition of the dye bath being emperically varied. However, the formation of haircoloring pigments from these mixtures results from a series of very complex chemical reactions which necessitate either the use of an oxidizing substance, hydrogen peroxide, or the presence of a substance having an alkaline reaction, which is generally ammonia. It is also known that by increasing the hydrogen peroxide and ammonia content there is obtained what is known as a decolorizing dye, there being simultaneously produced a decoloration of the hair to be dyed and a hair coloration in the desired shade.

It is well known that the hair-dyeing processes mentioned above have many disadvantages arising out of the mode of formation of the pigments imparting the coloration to the hair. In the first place, the use of para-diamines is likely to produce dermatitis and even allergies in certain particularly sensitive people. On the other hand,

Patented Jan. 26, 1971 the necessary presence of alkali and of hydrogen peroxide leads to modifications of the structure of the hair, which may sometimes be undesirable. Moreover, the shades obtained by present techniques have a well known tendency to change in the course of time. Thus, the colorations often tend to turn towards red; this is an appreciable disadvantage.

If, in this state of the art, that is to say, when an aromatic base and a modifier are used in combination, only known bases were to be employed, either alone or in admixture, products would be obtained which would have the aforesaid disadvantages in a higher degree and which, in addition, would give very limited ranges of shades.

According to the present invention it has now been discovered that it is possible to dye living hair without the use of the modifiers hitherto traditionally employed, provided that the aromatic bases heretofore employed are replaced by other selected products capable of developing a characteristic shade, which never varies, without the aid of an oxidizing or modifying agent. It has also been discovered that it is possible to use for this purpose solutions of these selected products having a slightly basic pH value, which may be as low as 7.

In this way, each of the selected bases employed develops its own shade. Consequently, an extensive range of commercially necessary shades may be made available merely by employing a number of these products, the final shade obtained being the component of the individual shades of the starting materials.

The present invention provides a new hair-dyeing process which is essentially characterized by the fact that there is employed a dyeing solution containing at least one compound having the formula:

l H U \R in which R is selected from the group consisting of hydrogen and alkyl, R, is selected from the group consisting of hydroxy and alkyl, and R, which can be in position 5 or 6 on the ring is selected from the group con sisting of hydrogen, halogen, hydroxy and alkyl. Preferably when R, and R are alkyls they are low molecular Weight alkyls.

A number of preferred compounds used in the composition of this invention are: 4-methoxy-2-aminophenol, 6-bromo-4-methoxy-2-aminophenol, 6-methyl-4-methoxy- 2-aminophenol, 4-methyl 5 hydroxy 2 methylaminophenol, 4 methyl-5-hydroxy-2-aminophen0l, 5 chloro-4- hydroxy-Z-aminophenol, 5-methyl-4-hydroxy 2 aminophenol, S-methoxy 4 hydroxy 2 aminophenol and 6 methyl-4-hydroxy-2-aminophenol.

Accordinwg to a feature of the invention, the dyeing solution comprises no oxidizing agent and no modifier and its pH value is equal to or higher than 7, viz from 7 to 11, the necessary oxidation being induced by atmospheric oxygen.

According to a further feature of the invention, the dyeing solution contains, in addition to the aforesaid compound or compounds, hydrogen peroxide and an alkali, so as to efiect a decolorizing dyeing effect. However, it still contains no modifier.

The process according to the invention makes it possible to obtain greatly improved hair dyes by virtue of the fact that it is possible to use the coloring agents without a modifier since each of the aforesaid bases develops its own shade as the result of a simple oxidation, and it is possible to obtain all the shades required in practice by simply mixing two or more of these bases.

According to a preferred method of carrying out the invention, the aforesaid compounds which are utilized for hair dyeing are stocked and brought into solution in the form of their salts, for instance in the form. of their hydrochlorides or hydrobromides. When a base such as ammonia is also added to this solution, the compounds according to the invention are set free at the time of their utilization.

Preferred hair dye compositions are aqueous solutions containing 0.5 to by weight of the dye compound and which have a pH of 7 to 11.

In order that the invention may be more readily understood, there will now be described by Way of illustration a number of embodiments.

EXAMPLE 1 Preparation of 6-bromo-4-methoxy-2-aminophenol An ethereal solution of ortho-bromo-para-methoxyphenol is poured drop-by-drop into a solution consisting of an excess of concentrated nitric acid and ether, the temperature being maintained below C.

The corresponding nitro derivative crystallizes as it is formed and it is sufficient to separate it and to reduce it in the usual way by means of a mixture of tin and hydrochloric acid in order to obtain the hydrochloride of 6-bromo-4-methoxy-2-aminophenol which, when recrystallized from hydrochloric acid, takes the form of white crystals.

Analysis.-Calculated (percent): C, 33.00; H, 3.54; N, 5.50. Found (percent): C, 33.06-32.82; H, 3.79-3.46; N, 5.25-5.26.

EXAMPLE 2 Preparation of 5-chloro-4-hydroxy-2-aminophenol This compound is prepared from chloro-dimethylhydroquinone which is nitrated in the usual manner with a mixture of sulphuric and nitric acids. After hydrolysis with caustic soda and acidification, 5-chloro-4-hydroxy- 2-nitrophenol is filtered with suction. This nitro-derivative is reduced by hydrochloric acid and tin. After cooling the desired product, 'which crystallizes in the form of its hydrochloride with one molecule of water, is filtered with suction; it melts (dec.) at 163-166 C.

Analysis.-Calculated (percent): C, 33.62; H, 4.21; N, 6.55. Found (percent): C, 33.38-33.47; H, 4.22-4.18; N, 6.43-6.30.

EXAMPLE 3 Preparation of 5-methyl-4-hydroxy-2-aminophenol This product is prepared from dimethyltoluhydroquinone which is nitrated by a mixture of sulphuric and nitric acids. The corresponding nitro-derivative thus obtained is hydrolysed by means of a sodium hydroxide solution, then subjected to a reduction by means of a mixture of hydrochloric acid and tin; 5-methyl-4-hydroxy- 2-aminophenol is obtained in the form of its hydrochloride; it melts (dec.) at 188-190" C.

Analysis.-Calculated (percent): C, 47.87; H, 5.70; N, 7.98. Found (percent): C, 47.65-47.60; H, 5.50-5.44 N, 7.98-7.96.

EXAMPLE 4 Preparation of 4-methyl-5-hydroxy-2-aminophenol 4-methyl-5-hydroxy-2-aminophenol is prepared utilizing as starting product 2,4,5-trihydroxytoluene which is left for a period of five days in a 6 N ammonia solution in an air-tight container. After acidification by hydrochloric acid and evaporation to dryness under 'vacuum, the residue is taken up in absolute alcohol and the inorganic salts are separated by filtration. The alcoholic filtrate is evaporated to dryness and the residue is dissolved again under heating in hydrochloric acid. On cooling the 2,4-dihydroxy aminotoluene crystallizes out with one molecule of water in the form of its hydrochloride.

Analysis.Calculated (percent): C], 18.35; N, 7.23. Found (percent): Cl, 18.58-18.40; N, 7.01-7.96.

EXAMPLE 5 Preparation of 5-methoxy-4-hydroxy-2-aminophenol This product is prepared from methoxy-dimesylhydroquinone which is nitrated in the usual manner by means of a mixture of sulphuric and nitric acids, thus obtaining 2-methoxy-5-nitrodimesylhydroquinone. This compound is then hydrolysed with a sodium hydroxide solution at a temperature of about 50 C., acidification is effected and 5-methoxy-4-hydroxy-2-nitrophenol is obtained by filtration; this product is then reduced by a mixture of tin and hydrochloric acid. On cooling the desired product crystallizes out with one molecule of water in the form of its hydrochloride and melts at 131 C. (dec.),

Analysis.Calculated (percent): C, 40.10; H, 5.72; N, 6.67. Found (percent): C, 39.51-39.85; H, 5.58-5.69; N, 6.52.

EXAMPLE 6 Preparation of 4-methyl-S-hydroxy-2-methylaminophenol Trihydroxytoluene is left for a period of four days in an aqueous solution of monomethylamine in an air tight container. Acidification is then effected by means of hydrochloric acid, the solution is evaporated under vacuum and the residue is taken up in absolute alcohol. After filtration to eliminate the inorganic salts, the alcohol is evaporated and the desired product is obtained; it is recrystallized in the form of its hydrochloride in concentrated hydrochloric acid.

Analysis.-Calculated (percent): C, 50.66; H, 6.33; N, 7.39. Found (percent): C, 50.83-50.44; H, 6.45-6.42; N, 7.10-7.20.

EXAMPLE 7 Preparation of 6-methyl-4-methoxy-2-amlnophenol A solution of m-cresidine is nitrated by addition of nitric acid in a mixture of acetic acid and acetic anhydride and a mixture of two isomeric nitro-derivatives is obtained. After having deacetylated by refluxing with concentrated hydrochloric acid and after having cooled, the non-desired isomer is eliminated by filtration. By dilution of the mother-water, 6-methyl-4-hydroxy-2-nitroaniline is precipitated; it melts at C. This compound is dissolved in a diluted sodium hydroxide solution and it is deaminated by heating with reflux. 6-methyl-4-methoxy- Z-nitrophenol is then obtained, M.P. 94.5 C. The nitroderivative is then reduced into the corresponding amine by means of an alkaline sodium hydrosulfite solution. 6-methyl-4-methoxy-2-aminophenol is thus obtained; the hydrochloride melts with decomposition at 2l5-222 C.

Analysis of the hydrochl0ride.Calculated (percent): C, 50.66; H, 6.33; N, 7.39. Found (percent): C, 50.20- 50.45; H, 6.15-6.08; N, 7.08-7.17.

EXAMPLE 8 Preparation of 6-methy1-4-hydroxy-2-aminophenol 6-methyl-4-methoxy-2-aminophenol is refluxed with a concentrated hydrobromic acid solution. After cooling, the hydrobromide of 6-methyl-4-hydroxy-2-aminophenol is filtered and separated. M.P. 225-228 C. (dec.).

Analysis.Calculated (percent): C, 38.19; H, 5.54; N, 6.36. Found (percent): C, 37.97-38.22; H, 4.50-4.70; N, 6.32-6.20.

The following examples are of dyeing solutions applied in accordance with the invention to hair on the human head.

EXAMPLE 9 A dyeing solution according to the invention is prepared by mixing:

G. 4-methoxy-2-aminophenol hydrochloride 1.75 20% ammonium lauryl sulphate 6 Sodium carbonate q.s. for pH 7. Water q.s. for 100 cc.

By applying this solution to 90% White hair and leaving it in contact therewith for 20 minutes and thereafter rinsing and washing, a copper-tinged dark blond coloration is obtained.

EXAMPLE 10 A dyeing solution according to the invention is prepared by mixing:

4-methoxy-2-aminophenol hydrochloride g 2 20% ammonium lauryl sulphate g 5 20% ammonia cc 6 Diethylenetriaminepentaacetic acid, sodium salt g 0.5 Water q.s. for 100 cc.

A dyeing solution according to the invention is prepared by mixing:

G 6-bromo-4-rnethoxy-Z-aminophenol hyrdochloride 2.5 Sodium carbonate q.s. for pH 7. 20% ammonium lauryl sulphate Water q.s. for 100 cc.

This solution is applied to hair containing 90% of white hairs. It is left in contact therewith for to minutes and, after washing and rinsing, the hair has a blond coloration.

EXAMPLE 12 A dyeing solution according to the invention is prepared by mixing:

6-bromo-4-methoxy-2-aminophenol hydrochloride g 3 N/ 2 sodium carbonate q.s. for pH 7.

20% ammonium lauryl sulphate g 5 20% ammonia cc 5 Water q.s. for 100 cc.

To the mixture thusprepared are added 8 cc. of hydrogen peroxide (130 5/01.).

The solution obtained is applied to light brown hair containing 70% of white hairs. After a contact period of minutes, the hair is rinsed and shampooed. The hair thus treated has a gold-blond coloration.

'EXAMPLE 13 A dyeing solution according to the invention is prepared by mixing:

5 chloro 4-hydroxy 2 aminophenol, monohydrochloride, monohydrate 1.5 Ammonia q.s. for pH 7. Water q.s. for 100 cc.

By applying this solution to hair containing 90% of white hairs and leaving it in contact therewith for about 20 minutes, the hair is given after Washing and rinsing, a blond coloration.

6 EXAMPLE 14 A dyeing solution according to the invention is prepared -by mixing:

G. 5 methyl 4 hydroxy-Z-aminophenol, monohydrochloride Ammonia q.s. for pH 7. Water q.s. for 100 cc.

By applying this solution on hair containing of white hairs and leaving it in contact therewith for 20 minutes, the hair has, after washing and rinsing, a goldenorange tint.

EXAMPLE 15 A dyeing solution according to the invention is prepared by mixing:

G. 4 methyl-5-hydroxy 2 aminophenol monohydrochloride, monohydrate 2.5 Ammonia q.s. for pH 7. Water q.s. for cc.

By applying this solution to hair containing 90% of white hairs and leaving it in contact therewith for about 20 minutes, the hair has a brown violet tint.

EXAMPLE 16 A dyeing solution according to the invention is prepared by mixing:

G. 5-methoxy-4-hydroxy-2 aminophenol monohydrochloride, monohydrate 1.5 Ammonia q.s. for pH 7. Water q.s. for 100 cc.

This solution is applied to hair containing 90% of white hairs and left in contact therewith for about 20 minutes. After rinsing and shampooing the hair is given a strong orange coloration.

EXAMPLE 17 A dyeing solution according to the invention is prepared by mixing:

G. 4-methyl-5-hydroxy-2 methyl aminophenol monohydrochloride Ammonia q.s. for pH 7. Water q.s. for 100 cc.

This solution is applied to hair containing 90% of white hairs and left in contact therewith for about 20 minutes. After rinsing and shampooing the hair has a golden blond tint.

EXAMPLE 18 A dyeing solution according to the invention is prepared by mixing:

G. 6-methyl-4-methoxy-2-aminophenol hydrochloride 2.5 Ammonia q.s. for pH 7. Water q.s. for 100 cc.

This solution is applied to hair containing 90% of white hairs and left in contact therewith for about 20 minutes. After rinsing and shampooing the hair has a copper blond tint.

EXAMPLE 19 A dyeing solution according to the invention is prepared by mixing:

G. 6-methy1-4-hydroxy-2-aminophenol hydrobromide 2.5 Ammonia q.s. for pH 9.5. Water q.s. for 100 cc.

This solution is applied to hair containing 90% white hairs and left in contact therewith for about 20 minutes. After rinsing and shampooing, the hair has a mahogany tint.

7 EXAMPLE 20 A dyeing solution according to the invention is prepared by mixing:

4-methoxy-2-aminophenol hydrochloride 0.15 6-amino-4-diethylamino-2 aminophenol trihydrochloride 0.15

4-methoxy-2-arnino-(fi-hydroxyethyD-amiline 0.8

Sodium carbonate q.s. for pH 7. Water q.s. for 100 cc.

This solution is applied to light brown hair containing 80% of white hairs. It is left in contact therewith for 20 minutes and after washing and rinsing the hair has a light gold-brown tint.

EXAMPLE 21 A dyeing solution according to the invention is prepared by mixing:

There are added to this solution at the time of use 8 cc. of hydrogen peroxide (130 vol.), whereafter it is applied to brown colored hair containing 80% of white hairs. After a contact period of 25 minutes, rinsing and shampooing, a light red-brown coloration is obtained.

EXAMPLE 22 A dyeing solution according to the invention is prepared by mixing:

4-methoxy-2-aminophenol hydrochloride 0.5

4-methoxy-2-amino-(fl-hydroxyethyl)-aniline 0.3 -amino-4-methoxy 2 aminophenol dihydrochloride 0.2

Sodium carbonate q.s. for pH 7. Water q.s. for 100 cc.

By applying this solution to light brown hair containing 90% of white hairs and leaving it in contact therewith for 15 to 20 minutes and thereafter washing and rinsing it, there is imparted to the hair thus treated a mauvish dark ash-blond coloration.

EXAMPLE 23 The following solution is prepared:

4-methoxy-2-aminophenol hydrochloride g 2 20% ammonia cc 7 Water q.s. for 100 cc.

50 cc. of this solution are mixed with 50 cc. of hydrogen peroxide and applied to hair containing 90% of white hairs. After 25 minutes of contact, the hair is shampooed, rinsed and dried. It has a flat golden blond tint.

EXAMPLE 24 The following solution is prepared:

G. 4-methyl-5-hydroxy-2-aminophenol hydrochloride 0.5 4-methoxy-2-aminophenol hydrochloride 0.1

6-amino-4-methoxy-2-aminophenol hydrochloride 0.5 Sodium carbonate q.s. for pH 7. Water q.s. for 100 cc.

50 cc. of this solution are mixed with 50 cc. of a hydrogen peroxide solution and applied to hair containing 90% of white hairs. After 25 minutes of contact, the hair is shampooed, rinsed and dried.

It has a deep brown violet tint.

8 EXAMPLE 25 The following solution is prepared:

G. 4-methyl-5-hydroxy-Z-methylaminophenol hydrochlon'de 0.5 6-amino-4-diethylamino-2-aminophenol trihydrochloride 0.4 4-methoxy-2-amino- (B-hydroxyethyl) -aniline 0. 1

Sodium carbonate q.s. for pH 7. Water q.s. for 100 cc.

50 cc. of this solution are mixed with 50 cc. of a hydrogen peroxide solution and applied to hair containing of white hairs. After 25 minutes of contact, the hair is shampooed, rinsed and dried.

It has a light golden brown tint.

What is claimed is:

l. A human hair dye composition comprising water and an effective amount of 6-brom0-4-methoxy-2-aminophenol having a pH of about 7 to 11.

2. A human hair dye composition comprising water and an effective amount of 6-methyl-4-methoxy-2-aminophenol having a pH of about 7 to 11.

3. A human hair dye composition comprising water and an efiective amount of 4-methyl-5-hydroxy-2-aminophenol having a pH of about 7 to 11.

4. A human hair dye composition comprising water and an effective amount of 4-methyl-S-hydroxy-2-methylaminophenol having a pH of about 7 to 11.

5. A human hair dye composition comprising water and an effective amount of 5-chloro-4-hydroxy-2-aminophenol having a pH of about 7 to 11.

6. A human hair dye composition comprising water and an effective amount of 5-methyl-4-hydroxy-2-aminophenol having a pH of about 7 to 11.

7. A human hair dye composition comprising water and an effective amount of 5-methoxy-4-hydroxy-2-aminophenol having a pH of about 7 to 11.

8. A human hair dye composition comprising water and an effective amount of 6-methyl=4-hydroxy-2-aminophenol having a pH of about 7 to 11.

9. The process of dyeing human hair comprising applying thereton an effective amount of a hair dye composition comprising water and an effective amount of a dye having the formula:

in which R is selected from the group consisting of hydrogen and methyl, R is selected from the group consisting of hydroxy, methyl and methoxy, and R, which can be in position 5 or 6 on the ring is selected from the group consisting of halogen, hydrogen, hydroxy, methyl and methoxy, and R, can be methoxy only when R is hydroxy, which has a pH of about 7 to 11.

References Cited UNITED STATES PATENTS 3,011,858 12/1961 Lantz et al. 8-10.2 3,210,252 10/1965 Blanke et al. 810.2

FOREIGN PATENTS 479,865 2/ 1938 Great Britain 260-575 ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US. Cl. X.R. 811; 260-574, 575