US3546293A

US3546293A - Amino phenols

Info

Publication number: US3546293A
Application number: US645522A
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: 1970-12-08
Anticipated expiration: 1987-12-08
Also published as: US3666812A; DE1492064A1; US3558259A; CH415965A; US3738799A; NL295194A; BE634643A; GB987342A

Abstract

Compounds suitable for use in one step hair and keratin fiber dyeing compositions which do not require the use of separate dye modifiers and are exceptionally color stable, having the formula IN WHICH R is selected from the group consisting of hydrogen and alkyll R1 is selected from the group consisting of alkyl, alkoxy, and dialkylamino, R4 which can be in position 5 or 6 on the ring is selected from the group consisting of hydrogen, halogen, hydroxy, alkyl, alkoxy and NH2, and at least one of said R1 and R4 is said dialkylamino or said NH2 .

Description

United States Patent 3,546,293 AMINO PHENOLS Gregoire Kalopissis, Paris, and Andree Bugaut, Boulognesur-Seine, France, assignors to Societe Auonyme dite: LOreal, Paris, France No Drawing. Continuation-impart of application Ser. No.

574,860, July 11, 1966, which is a division of application Ser. No. 293,282, July 8, 1963. This application June 12, 1967, Ser. No. 645,522 Claims priority, application France, July 11, 1962, 903,703; July 3, 1963, 940,212. Int. Cl. C07c 91/44 US. Cl. 260-574 9 Claims ABSTRACT OF THE DISCLOSURE New compounds suitable for use in one step hair and keratin fiber dyeing compositions which do not require the use of separate dye modifiers and 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 application is a continuation-in-part of application 574,860 filed July 11, 1966 which is a division of application 293,282 filed July 8, 1963. Both of these applications have been abandoned.

This invention relates to improved compounds suitable for use in one step keratin fiber and hair dyeing.

A number of compounds for dyeing keratinic fibers and notably hair are at present known, among the most commonly employed of these compounds 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 empirically varied. However, the formation of hair-coloring 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, 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 coloration 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 new compounds which have 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 5 or 6 on the ring is selected from the group consisting 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: 6 bromo- 4-methoxy-2- aminophenol, 6 methyl 4 methoxy Z-aminophenol, 4-methyl 5 hydroxy Z-methylaminophenol, 4-methyl- S-hydroxy 2 aminophenol, S-chloro 4 hydroxy-2- aminophenol, S-methyl 4 hydroxy 2 aminophenol, S-methoxy 4 hydroxy 2 aminophenol and 6-methyl- 4-hydroxy-2-aminophenol.

Used in dyeing solutions containing no oxidizing agent and no modifier and having a pH value equal to or higher than 7, viz from 7 to 11, the compounds are reduced by atmospheric oxygen. Furthermore, the dyeing solution may contain, in addition to the aforesaid compound or compounds, hydrogen peroxide and an alkali, in amounts which effect a decolorizing dyeing effect without modifying the dye compounds.

The compounds of this invention make it possible to obtain greatly improved hair dyes that are color stable and do not require a modifier since each of the aforesaid bases develops its own shade as the result of air oxidation and it is possible to obtain all the shades required in practice by simply mixing two or more of these bases.

In using these compounds for hair dyeing they may be 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 3 added to this solution the compounds are set free or activated at the time of use.

Preferred hair dye compositions are aqueous solutions containing 1.75 to 3% by weight of the dye compound and which have a pH of 7 to 11.

The following examples illustrate a number of preferred embodiments of this invention.

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 suflicient 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 S-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 EXAMPLE 4 Preparation of 4-methyl-5-hydroxy-2-aminophenol 4-methy1-5-hydroxy-2-aminophenol is prepared using 2,4,5-trihyd roxytoluene which is left for a period of five days in a 6 N ammonia solution in an air-tight container. After acidification with 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.

AnaIysis.Calculated (percent): Cl, 18.35; N, 7.23. Found (percent): CI, 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 4 2-methoxy-5-nitrochlorodimesylhydroquinone. This compound is then hydrolysed with a sodium hydroxide solution at a temperature of about 50 C., acidified and filtered to obtain 5-methoxy-4-hydroxy-Z-nitrophenol. This is then reduced with a mixture of tin and hydrochloric acid. On cooling the 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-5-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-aminophenol 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 desacetylated by refluxing with concentrated hydrochloric acid and after having cooled, the non-desired isomer is eliminated by filtration. By dilution of the mother liquid, 6-methy1-4-hydroxy-2-nitroaniline is precipitated; it melts at 130 C. This compound is dissolved in a diluted sodium hydroxide solution and it is deaminated by heating with reflux. 6-methyl-4-methoxy- 2-nitrophenol is then obtained, M.P. 94.5 C. The nitro derivative is then reduced into the corresponding amine by means of an alkaline sodium hydrosulfite solution. 6- methyl-4-methoxy-2-aminopheno1 is thus obtained; the hydrochloride melts with decomposition at 215-222 C.

Analysis of the hydrochloride.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-methyl-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, 4.54; 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 g1 ajccordance with the invention to hair on the human EXAMPLE 9 A dyeing solution according to the invention is prepared by mixing:

4-methoxy-2-aminophenol hydrochloride-1.75 g. 20% ammonium lauryl sulphate-6 g.

Sodium carbonate q.s. for pH 7.

Water q.s. for 100 cc.

By applying the solution to white hair and leaving it in contact therewith for 20 minutes and thereafter rins ing and washing, a copper-tinged dark blond coloration is obtained.

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

4-methoxy-2-aminophenol hydrochloride2 g.

20% ammonium lauryl sulphate-5 g.

20% ammonia6 cc.

Diethylenetriaminepentaacetic acid, sodium salt0.5 g. Water, q.s. for 100 cc.

There are added thereto at the time of use 100 grams of the addition product of hydrogen peroxide and urea, commercially known under the name urea peroxide or carbamide peroxide. The resulting solution is applied to light brown hair containing 60% of white hairs. After a contact period of from 20 to 25 minutes, the hair is rinsed and then shampooed. A gold-tinged blond coloration is thus obtained.

EXAMPLE 11 A dyeing solution according to the invention is prepared by mixing:

6-bromo-4-methoxy-2-aminophenol hydrochloride-2.5 g. Sodium carbonate q.s. for pH 7.

20% ammonium lauryl sulphate-5 g.

Water q.s. for 100 cc.

This solution is applied to hair containing 90% 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-amin0phenol hydrochloride3 g. N/2 sodium carbonate, q.s. for pH 7.

20% ammonium lauryl sulphate5 g.

20% ammonia-5 cc.

Water q.s. for 100 cc.

To the mixture thus prepared are added 8 cc. of hydrogen peroxide (130 vol.).

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,

monohydratel.5 g. 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.

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

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

By applying this solution on hair containing 90% of white hairs and leaving it in contact therewith for 20 minutes, the hair has, after washing and rinsing, a golden-orange tint.

6 EXAMPLE 1s By applying this solution to hair containing 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:

S-methoxy 4 hydroxy-Z-aminophenol monohydrochloride, monohydrate--l.5 g. Ammonia q.s. for pH 7. Water q.s. for 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:

4-methyl 5 hydroxy-2-methyl aminophenol monohydrochloride-2 g.

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:

6-methy1 4 methoxy-2-aminophenol hydrochloride- 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 pre pared by mixing: 6-methyl-4-hydroxy-2-aminophenol hydrobromide-2.5 g. 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.

EXAMPLE 20 A dyeing solution according to the invention is prepared by mixing: 4-methoxy-2-aminophenol hydrochloride-0.15 g. 6-amino-4-diethylamino 2 aminophenol trihydrochloride0.15 g.

4 methoxy-Z-amino-(fi-hydroxyethyl) aniline-0.8 g. 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.

7 EXAMPLE 21 A dyeing solution according to the invention is prepared by mixing: 4-methoxy-2-aminophenol-hydrochloride0.15 g. 6-amino-4 diethylamino 2 aminophenol trihydrochloride-0.15 g. 4-methoxy-2-amino-(fi-hydroxyethyl) aniline0.8 g.

N/ 1 sodium hydroxide, q.s. for pH 7. 20% ammonia5 cc. Water q.s. for 100 cc.

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 g.

4-methoxy-2-amino-(fl-hydroxyethyl) aniline-0.3 g.

5-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--2 g. 20% ammonia7 cc. 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 fiat golden blond tint.

EXAMPLE 24 The following solution is prepared:

4-methyl-5-hydroxy-2-aminophenol hydrochloride.5 g. 4-methoxy-2-aminophenol hydrochloride0.l g. 6-amino-4-methoxy-2-aminophenol hydrochloride-O.5 g. Sodium carbonate q.s. for pH 7.

Water q.s. for 100 cc.

55 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.

EXAMPLE 25 The following solution is prepared:

4-methyl hydroxy 2 methylaminophenol hydrochloride0.5 g.

6-amino-4 diethylamino 2 aminophenol trihydrochloride0.4 g.

4-methoxy-2-amino (fi-hydroxyethyl) aniline-0.1 g.

Sodium carbonate q.s. for pH 7.

Water q.s. for 100 cc.

50 cc. of this solution are mixed with 55 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:

1. A compound 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 chloride, bromine, hydroxy, methyl and methoxy, in which R can be methoxy only when R; is bromo or methyl in the 6 position, and R can be methoxy only when R is hydroxy.

2. The compound of claim 1, wherein said compound is 6-bromo-4-methoxy-2-aminophenol.

3. The compound of claim 1, wherein said compound is 6-methyl-4-methoxy-2-aminophenol.

4. The compound of claiml, wherein said compound is 4-methyl-5-hydroxy-2-methylaminophenol.

5. The compound of claim 1, wherein said compound is 4-methyl-5-hydroxy-2-aminophenol.

6. The compound of claim 1, wherein said compound is 5-chl0ro-4-hydroxy-2-aminophenol.

7. The compound of claim 1, wherein said compound is S-methyl-4-hydroxy2 aminophenol.

8. The compound of claim 1, wherein said compound is 5-methoxy-4-hydroxy-2-aminophenol.

9. The compound of claim 1, wherein said compound is 6-methyl-4-hydroxy-2-aminophenol.

References Cited UNITED STATES PATENTS 3,011,858 12/1961 Lantz et a1. 810.2

FOREIGN PATENTS 479,865 2/1938 Great Britain.

CHARLES B. PARKER, Primary Examiner C. F. WARREN, Assistant Examiner US. Cl. X.R.