MXPA99009955A - Novedos primary intermediaries in the oxidative coloration of the p - Google Patents

Abstract

The present invention relates to 5-nitroisatino which is reacted with sodium hydroxide to produce a sodium salt of the α-keto acid which is reduced with a borane-tetrahydrofuran complex and then hydrogenated to produce 1- (2,5- diaminophenyl) ethylene glycol, a novel useful compound as a primary intermediate in the production of oxidative hair dyes

Description

TNTERf € DTARIOS PRTWR? OS ROVEDO OS IN THE OXIDAPVA COLORATION OF THE HAIR Field of Invention The invention relates to l- (2,5-diaminophenyl) ethylene glycol (1), to a process for preparing the same and to its use in compositions for the coloration of human hair.

Background of the Invention The compositions for the oxidative coloring of the hair comprise primary intermediates (such as p-phenylenediamine, p-toluenediamine, p-aminophenol, -amino-3-methyl phenol) and couplers (such as resorcinol, 2-methylresorcinol, 3-aminophenol, 5). -amino-2-methylphenol). A majority of shades can be produced with dyes based Ref: 031382 in p-phenylenediamine. However, as noted in U.S. Patent Nos. 5,599,353 and 5,538,516, the use of p-phenylenediamine is questioned for reasons of toxicity, mainly due to its potential sensitization.

Due to the alleged toxicological sequelae published for its use, the technique is looking for substitutes for p-phenylenediamine.

EP 400,330 Bl (GB 2,239,264 A) describes the use of 2- (2-hydroxyethyl) -p-phenylenediamine as a replacement for p-phenylenediamine.

Pyrimidine derivatives, such as tre taaminopi rimidine, have also been suggested as alternatives to p-phenylenediamine (see US Re. 30,199 [US 4,003,699]). However, GB 2,239,265 A points out that although the use of pyrimidine derivatives as developers has reduced toxicological problems, the pyrimidine derivatives are not completely satisfactory with respect to the performance of coloration.

US 5,421,833 discloses hair coloring compositions stating that they are without potential sensitization. The coloring compositions are described to possess improved coloring properties for all shades. The compositions only comprise 2- (2'-hydroxyethyl) amino-5-aminotoluene in combination with the usual coupling agents (excluding 1-me toxy-2,4-diamonobenzene and 1-ethoxy-2, -diaminobenzene).

The object of the present invention is to develop an alternative p-phenylenediamone having low potential sensitization. This is a difficult task. Since the relationship between structure-sensitization is not known, this makes it difficult to predict whether a hair coloring molecule may exhibit much less potential for sensitization than p-phenylenediamine. Surprisingly and unexpectedly, it has been found that 1- (2, 5-diaminophenyl) ethylene glycol weakens sensitization much more than p-phenylenediamine.

Description of the invention.

The present invention provides the novel compound, 1- (2, 5-diaminophenyl) ethylene glycol, a process for preparing it, its use as a primary intermediate in the coloration of oxidative hair and hair coloring compositions containing it.

In contrast to p-phenylenediamine, 1- (2, 5-diaminophenyl) ethylene glycol was surprisingly found to weaken sensitization.

Current technology generally requires p-phenylenediamine or p-toluenediamine to produce red and black tones (see US 5,538,516).

The present invention allows one skilled in the art to formulate a natural black hue and a dark red hue through the use of 1- (2,5-diaminophenyl) ethylene glycol without reliance on p-phenylenediamine (see Table 2).

Advantageously, the shades obtained through the use of 1- (2, 5-diaminophenyl) ethylene glycol have good washing and light fastness.

The process for the preparation of l- (2,5-diaminopheni 1) ethylene glycol is new and commercially possible. The synthesis of compound 1 requires three steps: (1) opening a ring of 5-nitroisatin with sodium hydroxide, (2) borane reduction of keto acid, and (3) hydrogenation. 1- (2, 5-diaminophenyl) ethylene glycol has excellent solubility in water. Four grams of 1- (2,5-diamonophenyl) ethylene glycol sulfate salt are completely dissolved in 100 ml of water at room temperature. The p-toluenediamine sulfate salt is partially soluble under the same conditions. The solubility in water is important because the hair coloring formulations employed for hair coloring are in a large part of water.

Detailed description of the invention.

The following examples are intended to illustrate the present invention and not to limit the same in any aspect. It will be noted that the percentages are used, unless otherwise indicated, in percent by weight and based on the total weight. 1. The synthesis of 1- (2, 5-diaminophenyl) ethylene glycol (compound 1): The synthesis of compound 1 was carried out according to the following scheme.

A solution of 5-nitroisantino, compound 2, (96.07 g, 500 mmol) with sodium hydroxide solution (200 mL, 5.5 M solution) in ethanol (200 mL) was stirred at room temperature for 1 hour. The resulting solid was collected and washed with acetone to give compound 3 (116.71 g, 100% yield): m.p. 281 ° C decomposed; 1 H NMR (300 MHz, DMS0-d 6) d 6.80 (d, 1H, J = 9.3 Hz), 8.01 (dd, 1H, J = 9.3, 2.7 Hz), 8.46 (d, 1H, J = 2.7 Hz), 8.75 (bs, 2H).

Borane-THF (l.OM, 1.2 L) was added dropwise over a period of 2.5 hours to a stirred suspension of the sodium salt of a-keto acid (3) (92.86 g, 400 mmol) in 400 mL of tetrahydrofuran (THF) at 4 ° C. After the addition of borane was complete, the reaction mixture was warmed to room temperature and stirred for 16 hours. The excess borane was quenched at 4 ° C with methanol and the reaction mixture was evaporated under vacuum. The residue was dissolved in 400 mL of water and acidified to a pH of 2-3 with concentrated hydrochloric acid. The resulting precipitate was collected and dried in air to provide compound 4 (78.15 g, 98.6% yield): m.p. 154-156 ° C: 1 H NMR (300 MHz, DMSO-d 6) d 3.44 (m, 2 H), 4.65 (q, 1 H, J = 10, 4.8 Hz), 4.70 (t, 1 H, J = 6.0 Hz), 5.47 (d, 1H, J = 4.2 Hz), 6.47 (s, 2H), 6.62 (d, lH, J = 9.0 Hz), 7.84 (dd, 1H, J = 9.0, 2.7 Hz), 8.04 (d, 1H , J = 2.7 Hz); MS m / z 198 (M +).

A mixture of compound 4 (21.80 g, 110 mmol) and 10% Pd / C (2.2 g) in CH3OH / acetic acid (150/15 mL) was hydrogenated at 60 psi for 2.5 hours. The mixture was filtered over a Celite layer and washed with methanol. The combined filtrate was neutralized with concentrated ammonium hydroxide. The resulting precipitate was filtered to give compound 1 (15.11 g, 81.8% yield): m.p. 153-154 ° C; 1 H NMR (300 MHz, DMSO-d 6) d 3.40 (m, 2 H), 4.12 (s, 2 H), 4.17 (s, 2 H), 4.49 (t, 1 H, J = 6 Hz), 4.60 (s, 1 H) , 5.05 (s, 1H), 6.24 (dd, 1H, J = 8.1, 2.7 Hz), 6.35 (d, 1H, J = 8.1 Hz), 6.44 (d, 1H, J = 2.4 Hz); MS m / z 168 (M +). 2. Compositions The coloration compositions containing 1- (2, 5-diaminophenyl) ethylene glycol can also contain other primary intermediates and couplers.

It will be noted that for certain dark shades, including shades of dark brown and black, it is desirable to include a meta diamine as one of the couplers. Suitable meta diamines include m-phenylenediamine, 2-diaminophenoxyethanol and 4,6-bis (2-hydroxyethoxy) -m-phenylenediamine.

Appropriate primary intermediaries include: P-Phenylenediamine derivatives such as: p-toluenediamine; p-phenylenediamine; 2-chloro-p-phenylenediamine; N-phenyl-p-phenylenediamine; N-2-metoxyl-p-phenylenediamine; N, N-bis (2-hydroxyethyl) -p-phenylenediamine; 2-hydroxymethyl-p-phenylenediamine; 2-hydroxyethyl-p-phenylenediamine; 4,4'-diaminodiphenyla ina; 2,6-dimethyl-p-phenylenediamine; 2-isopropyl-p-phenylenediamine; N- (2-hydroxypropyl) -p-phenylenediamine; 2-propyl-p-pheni lendiamine; 1,3-bis (N-hydroxyethyl) -N- (4-aminophenyl) amino-2-propanol and 2-methyl-4-dimethylaminoaniline; P-aminophenol derivatives such as: p-aminophenyl; p-methylaminophenol; 3-methyl-p-aminophenol; 2-hydroxymethyl-p-aminophenyl; 2-methyl-p-aminophenol; 2- (2 '-hydroxyethylaminomethyl) -p-aminophenol; 2-methoxymethyl-p-aminophenyl; 5-aminosalicylic acid and 1 - (-amino-2-hydroxy phenyl) -ethane-1,2-diol; Ortho developers such as: catechol; pyrogallol; o-aminophenol; 2,4-di-amino phenol; 2,4,5-trihydroxytoluene; 1, 2, 4-trihydroxybenzene; 2,3-dihydroxynaphthalene; 5-methyl-o-aminophenol; 6-methyl-o-aminophenol and 2-amino-5-acetaminophenol and; Heterocyclic derivatives such as: 2,4,5,6-tetra-aminopyrimidine; 4,5-di-amino-1-methyl-1-yl-pi-zol and 2-dimethylaraine-5-aminopyridine; Appropriate couplers include: Derivatives of phenols, resorcinols and naphthols such as: 1,7-dihydroxynaphthalene; resorcinol; 4-chlororesorcinol; 1-naphthol; 2-me til-1-naf t ol; 1-acetoxy-2-methyl naphthalene; 1,5-dihydroxynaphthalene; 2,7-dihydroxynaphthalene; hydroquinone; 2 -methresorcinol; 1-hydroxy-6-aminonaphthalene-3-sulfonic acid; (2-isopropyl-5-methylphenol) thymol; 1, 5-dihydroxy-l, 2,3,4-tetrahydronaphthalene; 2-chlororesorcinol; 2, 3-dihydroxy-l, 4-naphthoquinone and l-naphthol-4-sulfonic acid; m-phenylenediamines such as: m-phenylenediamine; 2,4-diaminophenoxy t anol; N, N-bis (2-hydroxyethyl) -m-phenylenediamine; 2,6-di-amino toluene; 2-N, N-bis (hydroxyethyl) -2,4-diaminophenotol; bis (2,4-diaminophenoxy) -1,3-propane; 1-hydroxyethyl-2,4-diaminobenzene; 2-amino-4-hydroxyethylaminoanisole; l-aminoethoxy-2,4-diaminobenzene; 2,4-diaminophenoxyacetic acid; 4, 5-bis (hydroxyethoxy) -m-phenylenediamine; 2,4-diamino-5-methyl tilfenetol; 2, 4-diamino-5-hydroxyethoxytoluene; 2,4-dimethoxy-1,3-diaminobenzene and 2,6-bis (hydroxyethylamino) -toluene; m-aminophenols such as: m-aminophenol; 2-hydroxyphenol; 2-hydroxy-4-carbamoylmethylamino toluene; m-carbamoylmet ilaminophenyl; 6-hydroxybenzomorpholine; 2-hydroxy-4-aminotoluene; 2-hydroxy-4-hydroxyethylaminotoluene; 4,6-dichloro-m-aminophenol; 2-methyl-m-aminophenol; 2-chloro-6-methyl-m-aminophenol; 2-hydroxy-toxy-5-aminophenol; 2-chloro-5-trifluoeoethylaminophenol; -chloro-6-methyl-m-aminophenol; N-cyclopentyl-3-aminophenol; N-hydroxyethyl-4-methoxy-2-methyl-m-aminophenol and 5-amino--me toxy-2-methylphenol and Heterocyclic derivatives such as: 1-phenyl-3-methyl-5-pi raz olin; 6-methoxy-8-aminoquinoline; 2,6-dihydroxy-4-methylpyridine; 5-hydroxy-l, 4-benzodioxane; 3, 4-methylodoxy-phenol; 4-hydroxyethyleneamino-1,2-methylenedioxybenzene; 2,6-dihydroxy-3, 4-dimime ti Ipi ridine; 5-chloro-2,3-dihydroxypyridine; 3, 5-diamino-2,6-dimethoxy-pyridine; 2-hydroxyethylamino-6-methoxy-3-aminopyridine; 3, -me t ilendioxianilina; 2,6-bis (2-hydroxyethoxy) -3,5-diaminopyridine; -hydroxyindole; 3-amino-5-hydroxy-2,6-dimet oxypyridine; 5,6-dihydroxyindole; 7-hydroxyindole; 5-hydroxyindole; 2-bromo-4,5-methyledioxyphenol; 6-hydroxyindole; 3-amino-2-methylamino-6-methoxypyridine; 2-amino-3-hydroxypyridine; 2,6-diaminopyridine; 5- (3,5-di-amino-2-pyridyl oxy) -1,3-dihydroxypentane; 3- (3, 5-diamino-2-pyridyloxy) -2-hydroxypropanol and 4-hydroxy-2, 5, 6- t ri ami opi rimidi na.

Preferred primary intermediaries include P-Phenylenediamine derivatives such as: p-toluenediamine; p-phenylenediamine; N-2-methoxyethyl-p-phenylenediamine; N, -bis (2-hydroxyethyl) -p-phenylenediami a; 2-hydroxyethyl-p-phenylenediamine; P-aminophenol derivatives such as: p-aminophenol; p-methylaminophenol; 3-methyl-p-aminophenol; 2-methoxymethyl-p-aminophenol and l- (5-amino-2-hydroxy phenyl) -ethane-1,2-diol; Ortho developers such as: o-aminophenol; 1, 2, 4-1 Rihydroxybenzene; 2-e-tilamino-p-cresol; 5-methyl-2-aminophenol; β-methyl-2-aminophenol and 2-amino-5-acetaminophenol and; Heterocyclic derivatives such as: 2,4,5,6-tetra-aminopyrimidine and, 5-diamino-1-methyl-pyrazole.

Preferred couplers include: Derivatives of phenols, resorcinols and naphthols such as: 2-methyl-1-naphthol; l-acetoxy-2-methylnaphthalene; 1,7-dihydroxynaphthalene; resorcinol; 4-chlororesorcinol; 1-naphthol; 1,5-dihydroxynaphthalene; 2,7-dihydroxynaphthalene; hydroquinone; 2-methylresorcinol and (2-isopropyl-5-methylphenol) thymol; m-phenylenediamines such as: m-phenylenediamine; 2,4-diaminophenoxy tannol; 1,3-bis (2,4-diaminophenoxy) propane; 2-amino-4-hydroxyethylamino anisole and 4,6-bis (hydroxyethoxy) -m-phenylenediamine; m-aminophenols such. as; m-aminophenol; 6-hydroxyze zomorpholine; 2-hydroxy-4-aminotoluene; 2-hydroxy-hydroxyethylaminotoluene and 2-methyl-m-aminophenol and Heterocyclic derivatives such as: 4,5-diamino-1-methylpyrol-zol; 2-dimethylamino-5-aminopyridine; 1-phenyl-1 -3-methyl-5-pyrazolone; 3,4-methylenedioxyphenol; 3, 4-methylenioxyaniline; 4-hydroxyindo1; 5,6-dihydroxyindole; 7-hydroxyindole; 5-hydroxyindole; 6-hydroxyindole; 2,6-diaminopyridine and 2-amino-3-hydroxypyridine.

Most preferred primary intermediaries include: P-Phenylenediamine derivatives such as: p-toluenediamine; p-phenylenediamine; N, N-bis (2-hydroxyethyl) -p-phenylenediamine and 2-hydroxyethyl-p-pheni lendiamine; P-aminophenol derivatives such as: p-aminophenol; p-methylaminophenol; 3-methyl-p-aminophenol and 1- (5-amino-2-hydroxyphenyl) -ethane-1,2-diol; Ortho developers such as: o-aminophenol; 1,2,4-trihydroxybenzene; 2-ethylamine-p-cresol; 5-methyl-2-aminophenol; 6-met il -2-aminophenol and 2-amino-5-acet aminophenol.

More preferred couplers include: Derivatives of phenols, resorcinols and naphthols such as: 2-met il-1-naphthol; l-acetoxy-2-methylnaphthale or; resorcinol; 4-chlororesorcinol; 1-naphthol and 2-methylresorcinol; m-phenylenediamines such as: 2,4-diaminophenoxyethanol; and 4,6-bis (hydroxyethoxy) -m-phenylenediamine; Y Heterocyclic derivatives such as: 4,5-di-amino-1-methyl-tyl-zol; 1-pheny1-3-methy1-5-pyrazolone; 2-amino-3-hydroxypyridine and 6-hydroxyindole.

Preferred combinations employing 1- (2,5-diaminophenol) ethane-1,2-diol as a replacement for p-phenylenediamine include combinations 1-24 shown in Table 1 below: The combination 1 of Table 1 is a mixture of 1- (2, 5-diaminophenol) and toluene-1,2-diol; 2 - [(4-aminophenol) - (2-hydroxy-ethyl) -amino] -ethanol; 2-amino-phenol; benzene-1, 3-diol; naphthalene-1-ol; 3-amino-phenol; and -amino-phenol.

In the reading of Table 1, the components of combination 2 that are indicated by X are read below header column 2.

The composition of each of the remaining combinations is similarly determined Table 1 COMBINATIONS 3. General coloring procedure The test composition (according to Table 2 and Table 3) is mixed with 100 g of 20 volume of hydrogen peroxide. The resulting mixture is applied in gray hair and it is allowed to remain in contact with the hair for 30 minutes. The colored hair is washed with shampoo and rinsed with water and dried.

Table 2. Composition to color the hair of ro.

Table 3. Composition to color hair black or brown. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (13)

Claims

1. 1 - (2,5-diaminophenyl) ethylene glycol.

2. In an oxidative hair coloration system, wherein a primary intermediate of a mixture of primary intermediates and a coupler or a mixture of couplers is reacted, in a cosmetically acceptable vehicle and in the presence of an oxidizing agent, to produce at least one oxidative hair dye, wherein the improvement comprises the primary intermediate, and at least one of the primary intermediates in the mixture of primary intermediates, which is l- (2,5-diaminophenyl) ethylene glycol.

3. A method for producing l- (2,5-diaminophenyl) ethylene glycol, characterized in that it comprises: reacting the 5-nitro tin with alkali metal hydroxide to produce a sodium salt of a-keto acid of the formula 3; (3) reduce the sodium salt of a-keto acid of formula 3 to produce a compound of formula 4 (4); then hydrogenating the compound of formula 4 to convert the nitro group to an amino group, by means of which l- (2,5-diaminophenyl) ethylene glycol is produced.

4. The process according to claim 3, characterized in that the hydrogenation step of formula 4 is carried out in the presence of 10% Pd / C at 60 psi and for about 2.5 hours.

5. The process according to the rei indication 3, characterized in that the sodium salt of a-keto acid of formula 3 is reduced with a borane-trahydrofuran complex.

6. The process according to claim 3, characterized in that the alkali metal hydroxide is sodium hydroxide, potassium hydroxide or lithium hydroxide.

7. A method for reducing the potential sensitization of an oxidative hair coloring system, wherein the p-phenylenediamine and at least one coupler are reacted in the presence of an oxidizing agent to produce an oxidative hair dye, the method characterized in that it comprises replacing at least a part of the p-phenylenediamine in the system by at least an equimolar amount of 1- (2, 5-diaminophenyl) ethylene glycol.

8. In a system for coloring the hair with an oxidative hair dye, wherein a primary intermediate and a coupler are reacted in the presence of an oxidizing agent, and in a cosmetically acceptable vehicle, to produce a composition containing an effective dye amount of a oxidative hair dye, the improvement comprises that the primary intermediate is l- (2,5-diaminophenyl) ethylene glycol and, where a dark brown or black hue of the oxidative hair dye is desired, the composition further contains an ethaphenylenediamine.

9. The system according to claim 8, characterized in that the metaphenylenediamine is selected from the group consisting of m-phenylenediamine, 2,4-diaminophenoxyethanol and 4,6-bis (2-hydroxyethoxy) -m-phenylenediamine.

10. The system according to claim 8, characterized in that the l- (2,5-diaminophenyl) ethylene glycol and the metaphenylenediamine are present in the composition in a molar ratio of about 1: 1.

11. The system according to claim 8, characterized in that the composition contains from about 0.1% up to about 2% of the mephenylenediamine.

12. The system according to claim 9, characterized in that l- (2,5-diaminophenyl) ethylene glycol and metaphenylenediamine are present in the composition in a molar ratio of about 1: 1.

13. The system according to claim 9, characterized in that the composition contains from about 0.1% to about 2% of the metaphenylenediamine.