Primary intermediates for oxidative coloration of hair

Details Primary intermediates for oxidative coloration of hair Primary intermediates for oxidative coloration of hair

2001-08-15

2003-05-13

Gupta, Yogendra N. (Department: 1751)

Bleaching and dyeing; fluid treatment and chemical modification

Dyeing involving animal-derived natural fiber material ,...

Hair dyeing

C008S405000, C008S406000, C008S407000, C008S408000, C008S409000, C008S412000, C008S421000, C564S307000, C564S324000, C546S290000, C546S246000, C546S312000

Reexamination Certificate

active

06562080

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to new 2-arylaminomethyl-4-aminophenol compounds and compositions containing these compounds as primary intermediates for oxidative coloring of hair fibers.
BACKGROUND OF THE INVENTION
Coloration of hair is a procedure practiced from antiquity employing a variety of means. In modem times, the method most extensively to color hair is an oxidative dyeing process utilizing one or more oxidative hair coloring agents in combination with one or more oxidizing agents.
Most commonly a peroxy oxidizing agent is used in combination with one or more oxidative hair coloring agents, generally small molecules capable of diffusing into hair and comprising one or more primary intermediates and one or more couplers. In this procedure, a peroxide material, such as hydrogen peroxide, is employed to activate the small molecules of primary intermediates so that they react with couplers to form larger sized complexes in the hair shaft to color the hair in a variety of shades and colors.
A wide variety of primary intermediates and couplers have been employed in such -oxidative hair coloring systems and compositions. Among the primary intermediates employed there may be mentioned p-phenylenediamine, p-toluenediamine, p-aminophenol, 4-amino-3-methylphenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 1-(2-hydroxyethyl)-4,5-diaminopyrazole and as couplers there may be mentioned resorcinol, 2-methylresorcinol, 3-aminophenol, 2,4-diaminophenoxyethanol, and 5-amino-2-methylphenol.
There are numerous additional requirements for oxidation dye compounds that are used to dye human hair besides the color or the desired intensity. Thus, the dye compounds must be unobjectionable in regard to toxicological and dermatological properties and must provide the desired hair color with a good light fastness, fastness to a permanent wave treatment, acid fastness and fastness to rubbing. The color of the hair dyed with the dye compounds in each case must be stable for at least 4 to 6 weeks to light, rubbing and chemical agents. Furthermore, an additional requirement is the production of a broad palette of different color shades using different developer and coupler substances. It is not possible to fulfill all the above-mentioned requirements with the currently known dye compounds. There is, therefore, a need for new primary intermediate compounds to meet one or more of the desired properties.
SUMMARY OF THE INVENTION
It is therefore an object of this invention to provide new primary intermediate compounds useful in place of p-aminophenol to provide a wide range of different color shades with various combinations of primary intermediates and couplers.
It has been discovered that new 2-arylaminomethyl-4-aminophenol compounds are suitable primary intermediates for hair coloring compositions and systems for providing good oxidative coloration of hair and for providing acceptable light fastness, fastness to shampooing, fastness to permanent wave treatment, and suitable for providing a wide variety of different color shades with various primary intermediate and coupler compounds.
The invention provides new 2-arylaminomethyl-4-aminophenol compounds of Formula (1):
wherein R is a moiety selected from formulae (2), (3) or (4)
wherein R
1
, R
2
, R
3
, R
4
and R
5
are each independently selected from a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a C
1
-C
6
alkyl or haloalkyl group, a C
1
-C
6
alkoxy or haloalkoxy group, and a nitrile group, and R
6
is a hydrogen atom, a halogen atom, a C
1
-C
4
alkyl or a C
1
-C
4
alkoxy group.
Preferably R
6
is hydrogen; R
1
and R
5
are each independently hydrogen methyl, ethyl, methoxy, ethoxy, or chlorine; R
2
and R
4
are each independently hydrogen, chlorine, fluorine, methyl, ethyl, methoxy, trifluoromethyl, or trifluoromethoxy; and R
3
is hydrogen, hydroxy, fluorine, methyl, ethyl, propyl, methoxy, ethoxy or trifluoromethyl.
The new 2-arylaminomethyl-4-aminophenols of this invention can be made in a solid-phase organic synthesis reaction process utilizing a brominated Wang resin according to the following reaction scheme where R and R
6
are as defined hereinbefore.
In a first step 2-hydroxy-5-nitrobenzaldehyde is attached to a brominated polystyrene Wang resin as follows.
A mixture of 4-(bromomethyl)phenoxymethyl polystyrene (40.22 g, 51.48 mmole, Wang bromopolystyrene, 1.28 mmole/g, Novabiochem®), 2-hydroxy-5-nitrobenzaldehyde of Formula (5) (43.45 g, 26 mmole) where R
6
represents hydrogen, cesium carbonate (50.83 g, 156 mmole), and sodium iodide (7.79 g, 52 mmole) in dimethylformamide (DMF) (350 mL) was stirred at 50° C. for 5 h. The resin was filtered and washed with 2:1 DMF/water (×3), 9:1 DMF/water (×3), DMF (×3) and alternating MeOH and dichloromethane (DCM) (×4). After drying under high vacuum overnight, the polymer-bound aldehyde of Formula (6) (42.748 g) was obtained. To determine the bonding of benzaldehyde onto the Wang resin, to determine molarity for subsequent reactions, the cleavage of resin (500 mg of the polymer-bound aldehyde) was carried out by treatment with 50% trifluroacetic acid (TFA)/DCM (5/5 mL) for 1.5 h at room temperature and filtered, washed with DCM and concentrated to give 2-hydroxy-5-nitrobenzaldehyde of Formula (5) (73.2 mg). Therefore, loading was determined to be 0.876 mmole/g.
After attachment of 2-hydroxy-5-nitrobenzaldehyde to the brominated Wang resin, the following is the general procedure for preparation of arylaminomethyl-aminophenol compounds of Formula (1).
Polymer bound nitrobenzaldehyde of Formula (6)(R
6
═H) (300 mg, 0.263 mmole) was then treated with an aromatic amine of the formula RNH
2
(1.315 mmole each) in 1% AcOH-DCE (dichloroethane) (9 mL). A polypropylene tube (10 mL reservoir) was used as a reaction vessel in a 48-vessel reactor block. An orbital shaker was used for agitation. The mixture was agitated for 1 h at room temperature and sodium triacetoxyborohydride (1.315 mmole, 5 equiv.) was added to each reaction well. The mixture was agitated for 23 h. The solvent was filtered and the same washing protocol described above was followed. The resin was dried under vacuum overnight to give compound of Formula (7). The resin was treated with a 0.438 M SnCl
2
2H
2
O solution (6 mL, 10 equiv.) in DMF and the mixture was shaken for 24 h at room temperature. After the filtration of the solvent, the resin was washed three times each with DMF and alternating MeOH and DCM (×3). The resin was dried under vacuum overnight to afford a compound of Formula (8). The resin was cleaved with 5 mL of 50% TFA/DCM at room temperature for 1.5 h. After collection of the filtrate, the resin was washed with 1 mL of TFA/DCM and the combined filtrate was concentrated in vacuum to yield the target compound of Formula (1). The crude product was purified by preparative RP-HPLC using a gradient of 10% MeOH—90% H
2
O—0.1% TFA (A) and 90% MeOH—10% H
2
O—0.1% TFA (B) with a flow rate of 30 mL/min and gradient time 6 min. Start % B is 6 and final % B is 100. Evaporation of the solvents gives the target compounds of Formula (1).
Among the compounds of Formula (1) of this invention that can be prepared according to the aforedescribed general synthesis method, there can be mentioned, for example, 4-amino-2-phenylaminomethyl-phenol; 4-amino-2-[(3-chloro-phenylamino)-methyl]-phenol; 4-amino-2-[(4-fluoro-phenylamino)-methyl phenol; 4-amino-2-[(2-ethoxy-phenylamino)-methyl]-phenol; 4-amino-2-[(4-ethoxy phenylamino)-methyl]-phenol; 4-amino-2-[(3-fluoro-4-methoxy-phenylamino)-methyl]phenol; 4-amino-2-[(3-methoxy-phenylamino)-methyl]-phenol; 4-amino-2-[(3,4dimethyl-phenylamino)-methyl]-phenol; 4-amino-2-[(3-fluoro-phenylamino)-methyl]phenol; 4-amino-2-[(2-methoxy-5-methyl-phenylamino)-methyl]-phenol; 4-amino-2[(4-methoxy-2-methyl-phenylamino)-methyl]-phenol; 4-amino-2-[(5-methoxy methyl-phenylamino)-methyl]-phenol; 3-(5-amino-2-hydroxy-benzylamino benzonitrile;

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