Secondary para-phenylenediamines bearing an alkoxy group, dye composition comprising them, processes therefor and uses thereof Number:7,435,267 from the United States Patent and Trademark Office (PTO) owispatent

Title: Secondary para-phenylenediamines bearing an alkoxy group, dye composition comprising them, processes therefor and uses thereof

Abstract: The present invention relates to novel secondary para-phenylenediamines bearing an alkoxy group, to a process for preparing them, and to their use in the oxidation dyeing of hair. The invention also relates to a composition for dyeing keratin fibers, in particular human keratin fibers such as hair, containing, in a medium that is suitable for dyeing, at least one secondary para-phenylenediamine. Further, the invention relates to a process for dyeing keratin fibers using the aforementioned composition, and to a dyeing kit containing the composition.

Patent Number: 7,435,267 Issued on 10/14/2008 to Sabelle,   et al.

---

Inventors:	Sabelle; Stephane (Paris, FR), Vandenbossche; Jean-Jacques (Begaar, FR)
Assignee:	L'Oreal S.A. (Paris, FR)
Appl. No.:	11/066,449
Filed:	February 28, 2005

---

Related U.S. Patent Documents

---

	Application Number	Filing Date	Patent Number	Issue Date
	60568666	May., 2004

---

Foreign Application Priority Data

---

Feb 27, 2004 [FR]			04 02015

Current U.S. Class:	8/405 ; 564/382; 8/406; 8/408; 8/411; 8/414; 8/415
Current International Class:	A61K 8/00 (20060101)
Field of Search:	8/405,406,408,410,411,414,415,421 564/382

---

References Cited [Referenced By]

---

U.S. Patent Documents

3819708	June 1974	Manning et al.
RE30199	January 1980	Rose et al.
4277244	July 1981	Bugaut et al.
4823985	April 1989	Grollier et al.
5061289	October 1991	Clausen et al.
5380340	January 1995	Neunhoeffer et al.
5534267	July 1996	Neunhoeffer et al.
5663366	September 1997	Neunhoeffer et al.
5708151	January 1998	Mockli
5733343	March 1998	Mockli
5766576	June 1998	Lowe et al.
6099592	August 2000	Vidal et al.
6284003	September 2001	Rose et al.
6730789	May 2004	Birault et al.

Foreign Patent Documents

	23 59 399		Jun., 1975		DE
	38 43 892		Jun., 1990		DE
	41 33 957		Apr., 1993		DE
	195 43 988		May., 1997		DE
	0 081 790		Jun., 1983		EP
	0 714 954		Jun., 1996		EP
	0 770 375		May., 1997		EP
	2 126 314		Oct., 1972		FR
	2 362 112		Mar., 1978		FR
	2 421 872		Nov., 1979		FR
	2 586 913		Mar., 1987		FR
	2 733 749		Nov., 1996		FR
	2 801 308		May., 2001		FR
	1 026 978		Apr., 1966		GB
	1 048 790		Nov., 1966		GB
	1 153 196		May., 1969		GB
	2 018 302		Oct., 1979		GB
	2 018 808		Oct., 1979		GB
	63-169571		Jan., 1990		JP
	WO 94/08969		Apr., 1994		WO
	WO 94/08970		Apr., 1994		WO
	WO 95/01772		Jan., 1995		WO
	WO 95/15144		Jun., 1995		WO
	WO 96/15765		May., 1996		WO

Other References

STIC Search Report dated Feb. 6, 2007. cited by examiner . Foreign Patent Office Preliminary Search Report for priority application FR 04/02015, dated Oct. 14, 2004. cited by other . Synth. Commun. 1990 20 (22), pp. 3537-3545. cited by other . Synthesis, vol. 12, 1990, pp. 1147-1148. cited by other . Selva, M. et al. "Reaction of Primary Aromatic Amines with Alkyl Carbonates over NaY Faujasite: A Convenient and Selective Access to Mono-N-Alkyl Anilines" Journal of Organic Chemistry, vol. 66, No. 3, 2001, pp. 677-680. cited by other . Derwent Abstract to EP 081 790 (1983). cited by other . Derwent Abstract to EP 770 375 (1997). cited by other . Derwent Abstract to JP 63-169571 (JP 02-019576) (1990). cited by other . Chemical Abstracts XP002300693 (accession No. 2004:3592289; RN 346642-23-7). cited by other . Chemical Abstracts XP002300694 (accession No. 1962:32336; "The action of urea-formaldehyde resins, as used in the creaseproofing of textiles, on Azo dyes containing amino groups." cited by other.

Primary Examiner: Elhilo; Eisa
Attorney, Agent or Firm: Finnegan, Henderson, Farabow, Garrett, & Dunner, L.L.P.

---

Parent Case Text

---

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of U.S. Provisional Application No. 60/568,666, filed May 7, 2004, and French Application No. 04/02015, filed Feb. 27, 2004, both of which are herein incorporated by reference.

---

Claims

---

What is claimed is:

1. A compound, wherein the compound is chosen from secondary para-phenylenediamines of formula (I) and the addition salts thereof: ##STR00048## wherein: R is chosen from: a linear (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.5-C.sub.10)alkyl radical; a branched (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.3-C.sub.10)alkyl radical; a (branched (C.sub.3-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical; and a linear or branched ((C.sub.1-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical substituted with at least one group chosen from hydroxyl, C.sub.1-C.sub.15 alkoxy, amino, mono(C.sub.1-C.sub.15)alkylamino, di(C.sub.1-C.sub.15)alkylamino, (C.sub.1-C.sub.15)alkylcarbonyl, amido, (C.sub.1-C.sub.15)alkoxycarbonyl, mono(C.sub.1-C.sub.15)alkylaminocarbonyl and di(C.sub.1-C.sub.15)alkylaminocarbonyl groups; R.sub.1 is chosen from a hydrogen atom, a C.sub.1-C.sub.15 alkyl radical, a C.sub.1-C.sub.15 alkoxy radical, a ((C.sub.1-C.sub.15)alkoxy)C.sub.1-C.sub.15alkyl radical, a C.sub.1-C.sub.15 hydroxyalkoxy radical, a C.sub.1-C.sub.15 monohydroxyalkyl radical, a C.sub.1-C.sub.15 polyhydroxyalkyl radical, and a halogen atom; n is an integer ranging from 1 to 4; with the exception of the following compounds: N-(3-isopropoxypropyl)benzene-1,4-diamine; and N-(1-methylpropoxypropyl)benzene-1,4-diamine.

2. The compound of claim 1, wherein group R of formula (I) is chosen from: a linear (linear (C.sub.1-C.sub.5)alkoxy)(C.sub.5-C.sub.8)alkyl radical; a branched (linear (C.sub.1-C.sub.5)alkoxy)(C.sub.3-C.sub.7)alkyl radical; a (branched (C.sub.3-C.sub.7)alkoxy)(C.sub.2-C.sub.6)alkyl radical; and a linear or branched ((C.sub.1-C.sub.6)alkoxy)(C.sub.2-C.sub.6)alkyl radical substituted with at least one group chosen from hydroxyl, C.sub.1-C.sub.5 alkoxy, amino, mono(C.sub.1-C.sub.5)alkylamino, di(C.sub.1-C.sub.5)alkylamino, (C.sub.1-C.sub.5)alkylcarbonyl, amido, (C.sub.1-C.sub.5)alkoxycarbonyl, mono(C.sub.1-C.sub.5)alkylaminocarbonyl and di(C.sub.1-C.sub.5)alkylaminocarbonyl groups.

3. The compound of claim 1, wherein group R.sub.1 of formula (I) is chosen from: a hydrogen atom, a C.sub.1-C.sub.5 alkyl radical, a C.sub.1-C.sub.5 alkoxy radical, a ((C.sub.1-C.sub.5)alkoxy)(C.sub.1-C.sub.5)alkyl radical, a C.sub.1-C.sub.5 hydroxyalkoxy radical, a C.sub.1-C.sub.5 monohydroxyalkyl radical, a C.sub.1-C.sub.5 polyhydroxyalkyl radical, a chlorine atom, and a bromine atom.

4. A compound, wherein the compound is chosen from the following compounds: --N-(2-Methoxy-1-methylethyl)benzene-1,4-diamine; --N-(1-Methoxymethylpropyl)benzene-1,4-diamine; N-[3-(2-Ethylhexyloxy)propyl]benzene-1,4-diamine; -1-(4-Aminophenylamino)-3-methoxypropan-2-ol; --N-(4-Methoxybutyl) benzene-1,4-diamine; --N-(5-Methoxypentyl)benzene-1,4-diamine; --N-(6-Methoxyhexyl)benzene-1,4-diamine; --N-(6-Ethoxyhexyl)benzene-1,4-diamine; --N-(6-Isopropoxyhexyl)benzene-1,4-diamine; --N-(2-Isopropoxyethyl)benzene-1,4-diamine; --N-(2-tert-Butoxyethyl)benzene-1,4-diamine; --N-1-(2-Methoxy-1-methylethyl)-2-methylbenzene-1,4-diamine; --N-1-(1-Methoxymethylpropyl)-2-methylbenzene-1,4-diamine; --N-1-(3-Isopropoxypropyl)-2-methylbenzene-1,4-diamine; --N-1-[3-(2-Ethylhexyloxy)propyl]-2-methylbenzene-1,4-diamine; -1-(4-Amino-2-methylphenylamino)-3-methoxypropan-2-ol; --N-1-(4-Methoxybutyl)-2-methylbenzene-1,4-diamine; --N-1-(5-Methoxypentyl)-2-methylbenzene-1,4-diamine; --N-1-(6-Methoxyhexyl)-2-methylbenzene-1,4-diamine; --N-1-(6-Ethoxyhexyl)-2-methylbenzene-1,4-diamine; --N-1-(6-Isopropoxyhexyl)-2-methylbenzene-1,4-diamine; --N-1-(2-Isopropoxyethyl)-2-methylbenzene-1,4-diamine; --N-1-(2-tert-Butoxyethyl)-2-methylbenzene-1,4-diamine; --N-4-(2-Methoxy-1-methylethyl)-2-methylbenzene-1,4-diamine; --N-4-(1-Methoxymethylpropyl)-2-methylbenzene-1,4-diamine; --N-4-(3-Isopropoxypropyl)-2-methylbenzene-1,4-diamine; --N-4-[3-(2-Ethylhexyloxy)propyl]-2-methylbenzene-1,4-diamine; -1-(4-Amino-3-methylphenylamino)-3-methoxypropan-2-ol; --N-4-(4-Methoxybutyl)-2-methylbenzene-1,4-diamine; --N-4-(5-Methoxypentyl)-2-methylbenzene-1,4-diamine; --N-4-(6-Methoxyhexyl)-2-methylbenzene-1,4-diamine; --N-4-(6-Ethoxyhexyl)-2-methylbenzene-1,4-diamine; --N-4-(6-Isopropoxyhexyl)-2-methylbenzene-1,4-diamine; --N-4-(2-Isopropoxyethyl)-2-methylbenzene-1,4-diamine; --N-4-(2-tert-Butoxyethyl)-2-methylbenzene-1,4-diamine; and the addition salts thereof.

5. The compound of claim 1, wherein the addition-salts of formula (I) are chosen from the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates thereof.

6. A nitro compound, wherein the nitro compound has the structure (II) below: ##STR00049## in which: R is chosen from a linear (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.5-C.sub.10)alkyl radical, a branched (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.3-C.sub.10)alkyl radical, a (branched (C.sub.3-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical, and a linear or branched ((C.sub.1-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical substituted with at least one group chosen from hydroxyl, C.sub.1-C.sub.15 alkoxy, amino, mono(C.sub.1-C.sub.15)alkylamino, (C.sub.1-C.sub.15)alkylcarbonyl, amido, (C.sub.1-C.sub.15)alkoxycarbonyl, mono(C.sub.1-C.sub.15)alkylaminocarbonyl and di(C.sub.1-C.sub.15)alkylaminocarbonyl groups; R.sub.1 is chosen from a hydrogen atom, a C.sub.1-C.sub.15 alkyl radical, a C.sub.1-C.sub.15 alkoxy radical, a ((C.sub.1-C.sub.15)alkoxy)C.sub.1-C.sub.15alkyl radical, a C.sub.1-C.sub.15 hydroxyalkoxy radical, a C.sub.1-C.sub.15 monohydroxyalkyl radical, a C.sub.1-C.sub.15 polyhydroxyalkyl radical, and a halogen atom, and; n is an integer ranging from 1 to 4.

7. A process for preparing a compound of formula (I) below: ##STR00050## comprising reducing a nitro compound of formula (II) below: ##STR00051## wherein in both of said formula (I) and (II): R is chosen from a linear (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.5-C.sub.10)alkyl radical, a branched (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.3-C.sub.10)alkyl radical, a (branched (C.sub.3-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical, and a linear or branched ((C.sub.1-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical substituted with at least one group chosen from hydroxyl, C.sub.1-C.sub.15 alkoxy, amino, mono(C.sub.1-C.sub.15)alkylamino, (C.sub.1-C.sub.15)alkylcarbonyl, amido, (C.sub.1-C.sub.15)alkoxycarbonyl, mono(C.sub.1-C.sub.15)alkylaminocarbonyl and di(C.sub.1-C.sub.15)alkylaminocarbonyl groups; R.sub.1 is chosen from a hydrogen atom, a C.sub.1-C.sub.15 alkyl radical, a C.sub.1-C.sub.15 alkoxy radical, a ((C.sub.1-C.sub.15)alkoxy)C.sub.1-C.sub.15alkyl radical, a C.sub.1-C.sub.15 hydroxyalkoxy radical, a C.sub.1-C.sub.15 monohydroxyalkyl radical, a C.sub.1-C.sub.15 polyhydroxyalkyl radical, and a halogen atom, and; n is an integer ranging from 1 to 4, with the proviso that the following compounds are excluded from the compounds of formula (I): N-(3-isopropoxypropyl)benzene-1,4-diamine; and N-(1-methylpropoxypropyl)benzene-1,4-diamine.

8. A cosmetic composition for dyeing keratin fibers, comprising, in a medium that is suitable for dyeing, at least one compound chosen from secondary para-phenylenediamines of formula (I) and the addition salts thereof: ##STR00052## wherein: R is chosen from a linear (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.5-C.sub.10)alkyl radical, a branched (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.3-C.sub.10)alkyl radical, a (branched (C.sub.3-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical, and a linear or branched ((C.sub.1-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical substituted with at least one group chosen from hydroxyl, C.sub.1-C.sub.15 alkoxy, amino, mono(C.sub.1-C.sub.15)alkylamino, di(C.sub.1-C.sub.15)alkylamino, (C.sub.1-C.sub.15)alkylcarbonyl, amido, (C.sub.1-C.sub.15)alkoxycarbonyl, mono(C.sub.1-C.sub.15)alkylaminocarbonyl and di(C.sub.1-C.sub.15)alkylaminocarbonyl groups; R.sub.1 is chosen from a hydrogen atom, a C.sub.1-C.sub.15 alkyl radical, a C.sub.1-C.sub.15 alkoxy radical, a ((C.sub.1-C.sub.15)alkoxy)C.sub.1-C.sub.15alkyl radical, a C.sub.1-C.sub.15 hydroxyalkoxy radical, a C.sub.1-C.sub.15 monohydroxyalkyl radical, a C.sub.1-C.sub.15 polyhydroxyalkyl radical, and a halogen atom; and n is an integer ranging from 1 to 4.

9. A cosmetic composition for dyeing keratin fibers, comprising, in a medium suitable for dyeing, at least one compound chose from: --N-(2-Methoxy-1-methylethyl)benzene-1,4-diamine; --N-(1-Methoxymethylpropyl)benzene-1,4-diamine; --N-(3-Isopropoxypropyl)benzene-1,4-diamine; --N-[3-(2-Ethylhexyloxy)propyl]benzene-1,4-diamine; -1-(4-Aminophenylamino)-3-methoxypropan-2-ol; --N-(4-Methoxybutyl)benzene-1,4-diamine; --N-(5-Methoxypentyl)benzene-1,4-diamine; --N-(6-Methoxyhexyl)benzene-1,4-diamine; --N-(6-Ethoxyhexyl)benzene-1,4-diamine; --N-(6-Isopropoxyhexyl)benzene-1,4-diamine; --N-(2-Isopropoxyethyl)benzene-1,4-diamine; --N-(2-tert-Butoxyethyl)benzene-1,4-diamine; --N-1-(2-Methoxy-1-methylethyl)-2-methylbenzene-1,4-diamine; --N-1-(1-Methoxymethylpropyl)-2-methylbenzene-1,4-diamine; --N-1-(3-Isopropoxypropyl)-2-methylbenzene-1,4-diamine; --N-1-[3-(2-Ethylhexyloxy)propyl]-2-methylbenzene-1,4-diamine; -1-(4-Amino-2-methylphenylamino)-3-methoxypropan-2-ol; --N-1-(4-Methoxybutyl)-2-methylbenzene-1,4-diamine; --N-1-(5-Methoxypentyl)-2-methylbenzene-1,4-diamine; --N-1-(6-Methoxyhexyl)-2-methylbenzene-1,4-diamine; --N-1-(6-Ethoxyhexyl)-2-methylbenzene-1,4-diamine; --N-1-(6-Isopropoxyhexyl)-2-methylbenzene-1,4-diamine; --N-1-(2-Isopropoxyethyl)-2-methylbenzene-1,4-diamine; --N-1-(2-tert-Butoxyethyl)-2-methylbenzene-1,4-diamine; --N-4-(2-Methoxy-1-methylethyl)-2-methylbenzene-1,4-diamine; --N-4-(1-Methoxymethylpropyl)-2-methylbenzene-1,4-diamine; --N-4-(3-Isopropoxypropyl)-2-methylbenzene-1,4-diamine; --N-4-[3-(2-Ethylhexyloxy)propyl]-2-methylbenzene-1,4-diamine; -1-(4-Amino-3-methylphenylamino)-3-methoxypropan-2-ol; --N-4-(4-Methoxybutyl)-2-methylbenzene-1,4-diamine; --N-4-(5-Methoxypentyl)-2-methylbenzene-1,4-diamine; --N-4-(6-Methoxyhexyl)-2-methylbenzene-1,4-diamine; --N-4-(6-Ethoxyhexyl)-2-methylbenzene-1,4-diamine; --N-4-(6-Isopropoxyhexyl)-2-methylbenzene-1,4-diamine; --N-4-(2-Isopropoxyethyl)-2-methylbenzene-1,4-diamine; --N-4-(2-tert-Butoxyethyl)-2-methylbenzene-1,4-diamine; and the addition salts thereof.

10. The cosmetic composition of claim 8, wherein the compound of formula (I) is present in an amount ranging from 0.0001% to 20% by weight relative to the total weight of the composition.

11. The cosmetic composition of claim 10, wherein the compound of formula (I) is present in an amount ranging from 0.005% to 6% by weight relative to the total weight of the composition.

12. The cosmetic composition of claim 8, wherein the medium that is suitable for dyeing consists of water or comprises a mixture of water and at least one organic solvent chosen from branched or unbranched C.sub.1-C.sub.4 lower alcohols; polyols; polyol ethers; aromatic alcohols; and mixtures thereof.

13. The cosmetic composition of claim 8, further comprising at least one cosmetic adjuvant chosen from antioxidants; penetrating agents; sequestering agents; fragrances; buffers; dispersants; surfactants; conditioning agents; film-forming agents; polymers; ceramides; preserving agents; nacreous agents; opacifiers; and vitamins or provitamins.

14. The cosmetic composition of claim 13, wherein the amount of each cosmetic adjuvant contained in the composition ranges from 0.01% to 20% by weight relative to the total weight of the composition.

15. The cosmetic composition of claim 8, wherein the composition further comprises at least one oxidation coupler chosen from meta-phenylenediamines; meta-aminophenols; meta-diphenols; naphthalene-based couplers; heterocyclic couplers; and the addition salts thereof.

16. The cosmetic composition of claim 15, wherein the at least one coupler is present in an amount ranging from 0.0001% to 20% by weight relative to the total weight of the composition.

17. The cosmetic composition of claim 8, wherein the composition further comprises at least one additional oxidation base other than the compound of formula (I), chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof.

18. The cosmetic composition of claim 17, wherein the at least one additional oxidation base is present in an amount ranging from 0.0001% to 20% by weight relative to the total weight of the composition.

19. The cosmetic composition of claim 8, further comprising at least one natural or cationic direct dye.

20. A process for dyeing keratin fibers, comprising applying to keratin fibers, in the presence of an oxidizing agent and for a time sufficient to develop a desired coloration, a cosmetic composition, comprising, in a medium suitable for dyeing, at least one secondary para-phenylenediamine chosen from compounds of formula (I) and the addition salts thereof: ##STR00053## wherein: R is chosen from: a linear (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.5-C.sub.10)alkyl radical; a branched (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.3-C.sub.10)alkyl radical; a (branched (C.sub.3-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical; and a linear or branched ((C.sub.1-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical substituted with at least one group chosen from hydroxyl, C.sub.1-C.sub.15 alkoxy, amino, mono(C.sub.1-C.sub.15)alkylamino, di(C.sub.1-C.sub.15)alkylamino, (C.sub.1-C.sub.15)alkylcarbonyl, amido, (C.sub.1-C.sub.15)alkoxycarbonyl, mono(C.sub.1-C.sub.15)alkylaminocarbonyl and di(C.sub.1-C.sub.15)alkylaminocarbonyl groups; R.sub.1 is chosen from a hydrogen atom, a C.sub.1-C.sub.15 alkyl radical, a C.sub.1-C.sub.15 alkoxy radical, a ((C.sub.1-C.sub.15)alkoxy)C.sub.1-C.sub.15alkyl radical, a C.sub.1-C.sub.15 hydroxyalkoxy radical, a C.sub.1-C.sub.15 monohydroxyalkyl radical, a C.sub.1-C.sub.15 polyhydroxyalkyl radical, and a halogen atom; and n is an integer ranging from 1 to 4.

21. A ready-to-use composition, comprising: a dye composition comprising at least one secondary para-phenylenediamine compound chosen from the compounds of formula (I): ##STR00054## wherein: R is chosen from: a linear (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.5-C.sub.10)alkyl radical; a branched (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.3-C.sub.10)alkyl radical; a (branched (C.sub.3-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical; and a linear or branched ((C.sub.1-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical substituted with at least one group chosen from hydroxyl, C.sub.1-C.sub.15 alkoxy, amino, mono(C.sub.1-C.sub.15)alkylamino, di(C.sub.1-C.sub.15)alkylamino, (C.sub.1-C.sub.15)alkylcarbonyl, amido, (C.sub.1-C.sub.15)alkoxycarbonyl, mono(C.sub.1-C.sub.15)alkylaminocarbonyl and di(C.sub.1-C.sub.15)alkylaminocarbonyl groups; R.sub.1 is chosen from a hydrogen atom, a C.sub.1-C.sub.15 alkyl radical, a C.sub.1-C.sub.15 alkoxy radical, a ((C.sub.1-C.sub.15)alkoxy)C.sub.1-C.sub.15alkyl radical, a C.sub.1-C.sub.15 hydroxyalkoxy radical, a C.sub.1-C.sub.15 monohydroxyalkyl radical, a C.sub.1-C.sub.15 polyhydroxyalkyl radical, and a halogen atom; and n is an integer ranging from 1 to 4, and at least one oxidizing agent chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.

22. A multi-compartment kit comprising at least one first compartment comprising an oxidation dye composition, comprising, in a medium suitable for dyeing keratin fibers, at least one compound chosen from those of formula (I) and the addition salts thereof: ##STR00055## wherein: R is chosen from: a linear (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.5-C.sub.10)alkyl radical; a branched (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.3-C.sub.10)alkyl radical; a (branched (C.sub.3-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical; and a linear or branched ((C.sub.1-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical substituted with at least one group chosen from hydroxyl, C.sub.1-C.sub.15 alkoxy, amino, mono(C.sub.1-C.sub.15)alkylamino, di(C.sub.1-C.sub.15)alkylamino, (C.sub.1-C.sub.15)alkylcarbonyl, amido, (C.sub.1-C.sub.15)alkoxy-carbonyl, mono(C.sub.1-C.sub.15)alkylaminocarbonyl and di(C.sub.1-C.sub.15)alkylaminocarbonyl groups; R.sub.1 is chosen from a hydrogen atom, a C.sub.1-C.sub.15 alkyl radical, a C.sub.1-C.sub.15 alkoxy radical, a ((C.sub.1-C.sub.15)alkoxy)C.sub.1-C.sub.15 alkyl radical, a C.sub.1-C.sub.15 hydroxyalkoxy radical, a C.sub.1-C.sub.15 monohydroxyalkyl radical, a C.sub.1-C.sub.15 polyhydroxyalkyl radical, and a halogen atom; and n is an integer ranging from 1 to 4, and at least one second compartment comprising at least one oxidizing agent.

---

Description

---

FIELD OF THE INVENTION

The present disclosure relates to a novel family of secondary para-phenylenediamines bearing an alkoxy group, to their preparation and to their use in the oxidation dyeing of hair.

BACKGROUND OF THE INVENTION

It is known practice to dye keratin fibers, and in particular human hair, with dye compositions containing oxidation dye precursors, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic compounds, which are generally referred to as oxidation bases. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, may give rise to colored compounds by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or coloration modifiers, the latter being chosen, for example, from aromatic meta-diaminobenzenes, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds.

The variety of molecules used as oxidation bases and couplers makes it possible to obtain a wide range of colors.

The "permanent" coloration obtained by means of these oxidation dyes should, moreover, satisfy a number of requirements. The dyes should have no toxicological drawbacks, should allow shades of the desired intensity to be obtained, and/or should have good resistance to external agents such as light, bad weather, washing, permanent waving, perspiration and rubbing.

The dyes should also allow white hairs to be covered and, ideally, be as unselective as possible, i.e., allow the smallest possible differences in coloration to be produced over the entire length of the same keratin fiber, which is generally differently sensitized (i.e., damaged) between its end and its root.

SUMMARY OF THE INVENTION

The present inventor has discovered that it is possible to obtain a novel family of secondary para-phenylenediamines bearing an alkoxy group, capable of giving strong, aesthetic, and sparingly-selective colorations in varied shades, and which show good resistance to the various attacking factors to which the fibers may be subjected. The present disclosure relates to these novel secondary paraphenylenediamines, to a process for their preparation, and to their use in the oxidation dyeing of hair.

Another aspect of the present disclosure relates to compositions for dyeing keratin fibers, in particular human keratin fibers such as hair, comprising at least one secondary para-phenylenediamine bearing an alkoxy group which makes it possible to obtain dyes having the abovementioned advantages. In addition, these compositions have a good toxicological profile.

The present disclosure also relates to a dyeing process using this composition for the dyeing of keratin fibers, in particular human keratin fibers such as hair, and a multi-compartment device or dyeing "kit".

The composition disclosed herein makes it possible in particular to obtain very powerful, sparingly selective and fast, in particular light-fast, dyeing of keratin fibers, while at the same time avoiding the degradation of these fibers.

The above recited advantages of the present disclosure are non-limiting. Other aspects, subjects and advantages of the present disclosure will emerge even more clearly upon reading the description and the non-limiting examples that follow.

DETAILED DESCRIPTION OF THE INVENTION

The novel secondary para-phenylenediamines according to the present disclosure are chosen from compounds of formula (I) and the addition salts thereof:

##STR00001## in which:

R is chosen from a linear (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.4-C.sub.10)alkyl radical; a branched (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.3-C.sub.10)alkyl radical; a (branched (C.sub.3-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical; and a linear or branched ((C.sub.1-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical substituted with at least one group chosen from hydroxyl, C.sub.1-C.sub.15 alkoxy, amino, mono(C.sub.1-C.sub.15)alkylamino, di(C.sub.1-C.sub.15)alkylamino, (C.sub.1-C.sub.15)alkylcarbonyl, amido, (C.sub.1-C.sub.15)alkoxycarbonyl, mono(C.sub.1-C.sub.15)alkylaminocarbonyl and di(C.sub.1-C.sub.1 5)alkylaminocarbonyl groups.

R.sub.1 is chosen from a hydrogen atom, a C.sub.1-C.sub.15 alkyl radical, a C.sub.1-C.sub.15 alkoxy radical, a ((C.sub.1-C.sub.15)alkoxy)C.sub.1-C.sub.15alkyl radical, a C.sub.1-C.sub.15 hydroxyalkoxy radical, a C.sub.1-C.sub.15 monohydroxyalkyl radical, a C.sub.1-C.sub.15 polyhydroxyalkyl radical, and a halogen atom;

n is an integer ranging from 1 to 4;

with the exception of the following compounds: N-(3-isopropoxypropyl)benzene-1,4-diamine; and N-(1-methylpropoxypropyl)benzene-1,4-diamine.

In one non-limiting embodiment, the group R in formula (I) is chosen from a linear (linear (C.sub.1-C.sub.5)alkoxy)(C.sub.4-C.sub.8)alkyl radical; a branched (linear (C.sub.1-C.sub.5)alkoxy)(C.sub.3-C.sub.7)alkyl radical; a (branched (C.sub.3-C.sub.7)alkoxy)(C.sub.2-C.sub.6)alkyl radical; and a linear or branched ((C.sub.1-C.sub.6)alkoxy)(C.sub.2-C.sub.6)alkyl radical substituted with at least one group chosen from hydroxyl, C.sub.1-C.sub.5 alkoxy, amino, mono(C.sub.1-C.sub.5)alkylamino, (C.sub.1-C.sub.5)alkylcarbonyl, amido, (C.sub.1-C.sub.5)alkoxycarbonyl, mono(C.sub.1-C.sub.5)alkylaminocarbonyl and di(C.sub.1-C.sub.5)alkylaminocarbonyl groups; and the group R.sub.1 of formula (I) is chosen from a hydrogen atom, a C.sub.1-C.sub.5 alkyl radical, a C.sub.1-C.sub.5 alkoxy radical, a ((C.sub.1-C.sub.5)alkoxy)(C.sub.1-C.sub.5)alkyl radical, a C.sub.1-C.sub.5 hydroxyalkoxy radical, a C.sub.1-C.sub.5 monohydroxyalkyl radical, a C.sub.1-C.sub.5 polyhydroxyalkyl radical, a chlorine atom and a bromine atom.

The compounds of formula (I) may be chosen from but are not limited to:

TABLE-US-00001 ##STR00002## N-(2-Methoxy-1-methylethyl)benzene-1,4-diamine ##STR00003## N-4-(2-tert-Butoxyethyl)-2-methylbenzene-1,4-diamine ##STR00004## 1-(4-Aminophenyl-amino)-3-methoxypropan-2-ol ##STR00005## N-(5-Methoxypentyl)-benzene-1,4-diamine ##STR00006## N-(6-Ethoxyhexyl)-benzene-1,4-diamine ##STR00007## N-(2-Isopropoxy-ethyl)benzene-1,4-diamine ##STR00008## N-1-(2-Methoxy-1-methylethyl)-2-methylbenzene-1,4-diamine ##STR00009## N-1-(3-Isopropoxy-propyl)-2-methyl-benzene-1,4-diamine ##STR00010## 1-(4-Amino-2-meth-ylphenylamino)-3-methoxypropan-2-ol ##STR00011## N-1-(5-Methoxy-pentyl)-2-methyl-benzene-1,4-diamine ##STR00012## N-1-(6-Ethoxyhexyl)-2-methylbenzene-1,4-diamine ##STR00013## N-1-(2-Isopropoxy-ethyl)-2-methyl-benzene-1,4-diamine ##STR00014## N-4-(2-Methoxy-1-methylethyl)-2-methylbenzene-1,4-diamine ##STR00015## N-4-(3-Isopropoxy-propyl)-2-methyl-benzene-1,4-diamine ##STR00016## 1-(4-Amino-3-meth-ylphenylamino)-3-methoxypropan-2-ol ##STR00017## N-4-(5-Methoxy-pentyl)-2-methyl-benzene-1,4-diamine ##STR00018## N-4-(6-Ethoxyhexyl)-2-methylbenzene-1,4-diamine ##STR00019## N-4-(2-Isopropoxy-ethyl)-2-methyl-benzene-1,4-diamine ##STR00020## N-(1-Methoxy-methylpropyl)-benzene-1,4-diamine ##STR00021## N-[3-(2-Ethylhexyl-oxy)propyl]benzene-1,4-diamine ##STR00022## N-(4-Methoxy-butyl)benzene-1,4-diamine ##STR00023## N-(6-Methoxy-hexyl)benzene-1,4-diamine ##STR00024## N-(6-Isopropoxy-hexyl)benzene-1,4-diamine ##STR00025## N-(2-tert-Butoxy-ethyl)benzene-1,4-diamine ##STR00026## N-1-(1-Methoxy-methylpropyl)-2-methylbenzene-1,4-diamine ##STR00027## N-1-[3-(2-Ethyl-hexyloxy)propyl]-2-methylbenzene-1,4-diamine ##STR00028## N-1-(4-Methoxybutyl)-2-methylbenzene-1,4-diamine ##STR00029## N-1-(6-Methoxy-hexyl)-2-methyl-benzene-1,4-diamine ##STR00030## N-1-(6-Isopropoxy-hexyl)-2-methyl-benzene-1,4-diamine ##STR00031## N-1-(2-tert-Butoxy-ethyl)-2-methyl-benzene-1,4-diamine ##STR00032## N-4-(1-Methoxy-methylpropyl)-2-methylbenzene-1,4-diamine ##STR00033## N-4-[3-(2-Ethyl-hexyloxy)propyl]-2-methylbenzene-1,4-diamine ##STR00034## N-4-(4-Methoxy-butyl)-2-methyl-benzene-1,4-diamine ##STR00035## N-4-(6-Methoxy-hexyl)-2-methyl-benzene-1,4-diamine ##STR00036## N-4-(6-Isopropoxy-hexyl)-2-methyl-benzene-1,4-diamine

In general, the addition salts that can be used for the oxidation bases and the couplers are chosen from acid addition salts, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The compounds of formula (I) according to the present disclosure may be prepared according to a method which comprises: nucleophilic substitution of the halogen in the para position of the para-halonitrobenzene derivative with a primary amine of formula RNH.sub.2 in the presence of a base, R being defined as above; reduction of the nitro function of the compound obtained in the preceding step into an amine function, to obtain the compound of formula (I).

##STR00037##

The first step of the synthesis is described in scientific reviews, such as Synthesis 1990 (12), 1147-1148 and Synth. Commun. 1990, 20 (22), 3537-3545.

The second step is a reduction step that may be accomplished with a hydrogenation reaction via heterogeneous catalysis in the presence of Pd/C, Pd(II)/C or Raney Ni, or alternatively by performing a reduction reaction with a metal, such as zinc, iron, tin, etc. (Advanced Organic Chemistry, 4.sup.th edition, 1992, J. March, Wiley Interscience; Reduction in Organic Chemistry, M. Hudlicky, 1983, Ellis Honwood series Chemical Science).

The present disclosure also concerns the nitro compounds of formula (II) below, and processes for preparing the secondary para-phenylenediamine compounds of formula (I), in which a reduction of the corresponding nitro compound of formula (II) is performed:

##STR00038## wherein: R is chosen from a linear (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.4-C.sub.10)alkyl radical, a branched (linear (C.sub.1-C.sub.10)alkoxy)(C.sub.3-C.sub.10)alkyl radical, a (branched (C.sub.3-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical, and a linear or branched ((C.sub.1-C.sub.10)alkoxy)(C.sub.2-C.sub.10)alkyl radical substituted with at least one group chosen from hydroxyl, C.sub.1-C.sub.15 alkoxy, amino, mono(C.sub.1-C.sub.15)alkylamino, (C.sub.1-C.sub.15)alkylcarbonyl, amido, (C.sub.1-C.sub.15)alkoxycarbonyl, mono(C.sub.1-C.sub.15)alkylaminocarbonyl and di(C.sub.1-C.sub.15)alkylaminocarbonyl groups;

R.sub.1 is chosen from: a hydrogen atom, a C.sub.1-C.sub.15 alkyl radical, a C.sub.1-C.sub.15alkoxy radical, a ((C.sub.1-C.sub.15)alkoxy)C.sub.1-C.sub.15alkyl radical, a C.sub.1-C.sub.15hydroxyalkoxy radical, a C.sub.1-C.sub.15 monohydroxyalkyl radical, a C.sub.1-C.sub.15 polyhydroxyalkyl radical, and a halogen atom; and

n is an integer ranging from 1 to 4.

The present disclosure also relates to the use, for the oxidation dyeing of hair, of the above mentioned compound of formula (I) or the addition salt salts thereof

The disclosure also relates to a cosmetic composition for dyeing fibers, e.g., human keratin fibers such as hair, comprising, in a medium that is suitable for dyeing, at least one compound of formula (I) as has just been described.

In a non-limiting embodiment, the composition comprises the compound of formula (I) chosen from the following compounds: --N-(2-Methoxy-1-methylethyl)benzene-1,4-diamine; --N-(1-Methoxymethylpropyl)benzene-1,4-diamine; --N-(3-Isopropoxypropyl)benzene-1,4-diamine; --N-[3-(2-Ethylhexyloxy)propyl]benzene-1,4-diamine; --1-(4-Aminophenylamino)-3-methoxypropan-2-ol; --N-(4-Methoxybutyl)benzene-1,4-diamine; --N-(5-Methoxypentyl)benzene-1,4-diamine; --N-(6-Methoxyhexyl)benzene-1,4-diamine; --N-(6-Ethoxyhexyl)benzene-1,4-diamine; --N-(6-Isopropoxyhexyl)benzene-1,4-diamine; --N-(2-Isopropoxyethyl)benzene-1,4-diamine; --N-(2-tert-Butoxyethyl)benzene-1,4-diamine; --N-1-(2-Methoxy-1-methylethyl)-2-methylbenzene-1,4-diamine; --N-1-(1-Methoxymethylpropyl)-2-methylbenzene-1,4-diamine; --N-1-(3-Isopropoxypropyl)-2-methylbenzene-1,4-diamine; --N-1-[3-(2-Ethylhexyloxy)propyl]-2-methylbenzene-1,4-diamine; --1-(4-Amino-2-methylphenylamino)-3-methoxypropan-2-ol; --N-1-(4-Methoxybutyl)-2-methylbenzene-1,4-diamine; --N-1-(5-Methoxypentyl)-2-methylbenzene-1,4-diamine; --N-1-(6-Methoxyhexyl)-2-methylbenzene-1,4-diamine; --N-1-(6-Ethoxyhexyl)-2-methylbenzene-1,4-diamine; --N-1-(6-Isopropoxyhexyl)-2-methylbenzene-1,4-diamine; --N-1-(2-Isopropoxyethyl)-2-methylbenzene-1,4-diamine; --N-1-(2-tert-Butoxyethyl)-2-methylbenzene-1,4-diamine; --N-4-(2-Methoxy-1-methylethyl)-2-methylbenzene-1,4-diamine; --N-4-(1-Methoxymethylpropyl)-2-methylbenzene-1,4-diamine; --N-4-(3-Isopropoxypropyl)-2-methylbenzene-1,4-diamine; --N-4-[3-(2-Ethylhexyloxy)propyl]-2-methylbenzene-1,4-diamine; -1-(4-Amino-3-methylphenylamino)-3-methoxypropan-2-ol; --N-4-(4-Methoxybutyl)-2-methylbenzene-1,4-diamine; --N-4-(5-Methoxypentyl)-2-methylbenzene-1,4-diamine; --N-4-(6-Methoxyhexyl)-2-methylbenzene-1,4-diamine; --N-4-(6-Ethoxyhexyl)-2-methylbenzene-1,4-diamine; --N-4-(6-Isopropoxyhexyl)-2-methylbenzene-1,4-diamine; --N-4-(2-Isopropoxyethyl)-2-methylbenzene-1,4-diamine; --N-4-(2-tert-Butoxyethyl)-2-methylbenzene-1,4-diamine; and the addition salts thereof.

In a non-limiting embodiment, the the compound of formula (I) is present in the composition in an amount ranging from 0.0001% to 20% by weight, such as from 0.005% to 6% by weight, relative to the total weight of the composition.

The medium that is suitable for dyeing may be water or a mixture of water and at least one organic solvent, such as branched or unbranched C.sub.1-C.sub.4 lower alcohols, such as ethanol and isopropanol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol; propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, glycerol, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvents of the medium may be present in amounts ranging from 1% to 40%, such as from 5% to 30%, by weight relative to the total weight of the dye composition.

The cosmetic composition may further comprise at least one cosmetic adjuvant chosen from: antioxidants; penetrating agents; sequestering agents; fragrances; buffers; dispersants; surfactants; conditioning agents; film-forming agents; polymers; ceramides; preserving-agents; nacreous agents; opacifiers; vitamins; or provitamins.

The above adjuvants may be present in an amount for each of them ranging from 0.01% to 20% by weight relative to the weight of the composition.

The composition according to the invention may additionally contain at least one oxidation coupler.

Oxidation couplers that may be mentioned include but are not limited to: meta-phenylenediamines; meta-aminophenols; meta-diphenols; naphthalene-based couplers; heterocyclic couplers; and the addition salts thereof.

Among these oxidation couplers, non-limiting examples that may be mentioned include: 2-methyl-5-aminophenol; 5-N-(.beta.-hydroxyethyl)amino-2-methylphenol; 6-chloro-2-methyl-5-aminophenol; 3-aminophenol; 1,3-dihydroxybenzene (resorcinol); 1,3-dihydroxy-2-methylbenzene; 4-chloro-1,3-dihydroxybenzene; 2,4-diamino-1-(.beta.-hydroxyethyloxy)benzene; 2-amino-4-(.beta.-hydroxyethylamino)-1-methoxybenzene; 1,3-diaminobenzene; 1,3-bis(2,4-diaminophenoxy)propane; 3-ureidoaniline; 3-ureido-1-dimethylaminobenzene; sesamol; 1-.beta.-hydroxyethylamino-3,4-methylenedioxybenzene; .alpha.-naphthol; 2-methyl-1-naphthol; 6-hydroxyindole; 4-hydroxyindole; 4-hydroxy-N-methylindole; 2-amino-3-hydroxypyridine; 6-hydroxybenzomorpholine; 3,5-diamino-2,6-dimethoxypyridine; 1-N-(.beta.-hydroxyethyl)amino-3,4-methylenedioxybenzene; 2,6-bis(.beta.-hydroxyethylamino)toluene; and the addition salts thereof.

Generally, the at least one oxidation coupler, if present, may be present in an amount ranging from 0.0001% to 20%, such as from 0.005% to 6%, by weight relative to the total weight of the composition.

The composition according to the invention may further contain at least one additional oxidation base other than the compound of formula (I).

The additional oxidation bases may be chosen from: para-phenylenediamines; bis(phenyl)alkylenediamines; para-aminophenols; ortho-aminophenols; heterocyclic bases; and the addition salts thereof.

Among the para-phenylenediamines, non-limiting mention may be made of: para-phenylenediamine; para-tolylenediamine; 2-chloro-para-phenylenediamine; 2,3-dimethyl-para-phenylenediamine; 2,6-dimethyl-para-phenylenediamine; 2,6-diethyl-para-phenylenediamine; 2,5-dimethyl-para-phenylenediamine; N,N-dimethyl-para-phenylenediamine; N,N-diethyl-para-phenylenediamine; N,N-dipropyl-para-phenylenediamine; 4-amino-N,N-diethyl-3-methylaniline; N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine; 4-amino-N,N-bis(.beta.-hydroxyethyl)-2-methylaniline; 4-amino-2-chloro-N,N-bis(.beta.-hydroxyethyl)aniline; 2-.beta.-hydroxyethyl-para-phenylenediamine; 2-fluoro-para-phenylenediamine; 2-isopropyl-para-phenylenediamine; N-(.beta.-hydroxypropyl)-para-phenylenediamine; 2-hydroxymethyl-para-phenylenediamine; N,N-dimethyl-3-methyl-para-phenylenediamine; N-ethyl-N-(.beta.-hydroxyethyl)-para-phenylenediamine; N-(.beta.,.gamma.-di-hydroxypropyl)-para-phenylenediamine; N-(4'-aminophenyl)-para-phenylenediamine; N-phenyl-para-phenylenediamine; 2-.beta.-hydroxyethyloxy-para-phenylenediamine; 2-.beta.-acetylaminoethyloxy-para-phenylenediamine; N-(.beta.-methoxyethyl)-para-phenylenediamine; 4-aminophenylpyrrolidine; 2-thienyl-para-phenylenediamine; 2-.beta.-hydroxyethylamino-5-aminotoluene; 3-hydroxy-1-(4'-aminophenyl)pyrrolidine; 6-(4-aminophenylamino)hexan-1-ol; and the acid addition salts thereof.

In some embodiments, the at least one additional oxidation base is chosen from, para-phenylenediamines chosen from para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-.beta.-hydroxyethyl-para-phenylenediamine, 2-.beta.-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-.beta.-acetylaminoethyloxy-para-phenylenediamine and the acid addition salts thereof

Among the bis(phenyl)alkylenediamines, non-limiting mention may be made, by way of example, of: N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropano- l; N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine; N,N'-bis(4-aminophenyl)tetramethylenediamine; N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4-amino-phenyl)tetramethylenediami- ne; N,N'-bis(4-methylaminophenyl)tetramethylenediamine; N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine; 1,8-bis(2,5-diamino-phenoxy)-3,6-dioxaoctane; and the acid addition salts thereof.

Among the para-aminophenols, non-limiting mention may be made, by way of example, of: para-aminophenol; 4-amino-2-methylphenol; 4-amino-3-methylphenol; 4-amino-3-fluorophenol; 4-amino-3-chlorophenol; 4-amino-3-hydroxymethylphenol; 4-amino-2-methylphenol; 4-amino-2-hydroxymethylphenol; 4-amino-2-methoxymethylphenol; 4-amino-2-aminomethylphenol; 4-amino-2-(.beta.-hydroxyethyl-aminomethyl)phenol; 4-amino-2-fluorophenol; 4-amino-2,6-dichlorophenol; 4-amino-6[((5'-amino-2'-hydroxy-3'-methyl)phenyl)methyl]-2-methylphenol; bis(5'-amino-2'-hydroxy)phenylmethane; and the acid addition salts thereof.

Among the ortho-aminophenols, non-limiting mention may be made, by way of example, of: 2-aminophenol; 2-amino-5-methylphenol; 2-amino-6-methylphenol; 5-acetamido-2-aminophenol; and the acid addition salts.

Among the heterocyclic bases, non-limiting mention may be made, by way of example, of: pyridine derivatives; pyrimidine derivatives; and pyrazole derivatives.

Non-limiting examples of suitable pyridine derivative include the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, as well as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 3,4-diaminopyridine, and the acid addition salts thereof.

Other non-limiting examples of pyridine oxidation bases that may be used in the present disclosure include the 3-aminopyrazolo[1,5-a]pyridine oxidation bases or the addition salts thereof described, such as those described in French Patent application FR 2801308including: pyrazolo[1,5-a]pyrid-3-ylamine; 2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine; 2-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine; 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid; 2-methoxypyrazolo[1,5-a]pyrid-3-ylamine; (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol; 2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol; 2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol; (3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol; 3,6-diaminopyrazolo[1,5-a]pyridine; 3,4-diaminopyrazolo[1,5-a]pyridine; pyrazolo[1,5-a]pyridine-3,7-diamine; 7-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine; pyrazolo[1,5-a]pyridine-3,5-diamine; 5-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine; 2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)-(2-hydroxyethyl)amino]ethanol; 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)-(2-hydroxyethyl)amino]ethanol; 3-aminopyrazolo[1,5-a]pyrid-5-ol; 3-aminopyrazolo[1,5-a]pyrid-4-ol; 3-aminopyrazolo[1,5-a]pyridine-6-ol; and 3-aminopyrazolo[1,5-a]pyrid-7-ol; and the acid addition salts thereof.

Among the pyrimidine derivatives, non-limiting mention may be made of the compounds described in patents DE 23 59 399; JP 88169571; JP 0563124; EP 0 770 375, or patent application WO 96/15765, such as: 2,4,5,6-tetraaminopyrimidine; 4-hydroxy-2,5,6-triaminopyrimidine; 2-hydroxy-4,5,6-triaminopyrimidine; 2,4-dihydroxy-5,6-diaminopyrimidine; 2,5,6-triaminopyrimidine; the acid addition salts thereof; and the tautomeric forms thereof when tautomeric equilibrium exists.

Among the pyrazole derivatives, non-limiting mention may be made of the compounds described in patents DE 38 43 892, DE 41 33 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733749 and DE 195 43 988, including: 4,5-diamino-1-methylpyrazole; 4,5-diamino-1-(.beta.-hydroxyethyl)pyrazole; 3,4-diaminopyrazole; 4,5-diamino-1-(4'-chlorobenzyl)pyrazole; 4,5-diamino-1,3-dimethylpyrazole; 4,5-diamino-3-methyl-1-phenylpyrazole; 4,5-diamino-1-methyl-3-phenylpyrazole; 4-amino-1,3-dimethyl-5-hydrazinopyrazole; 1-benzyl-4,5-diamino-3-methylpyrazole; 4,5-diamino-3-tert-butyl-1-methylpyrazole; 4,5-diamino-1-tert-butyl-3-methylpyrazole; 4,5-diamino-1-(.beta.-hydroxyethyl)-3-methylpyrazole; 4,5-diamino-1-ethyl-3-methylpyrazole; 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole; 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole; 4,5-diamino-3-hydroxymethyl-1-methylpyrazole; 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole; 4,5-diamino-3-methyl-1-isopropylpyrazole; 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole; 3,4,5-triaminopyrazole; 1-methyl-3,4,5-triaminopyrazole; 3,5-diamino-1-methyl-4-methylaminopyrazole; 3,5-diamino-4-(.beta.-hydroxyethyl)amino-1-methylpyrazole; and the addition salts thereof.

Generally, if present, the at least one additional oxidation base is present in an amount ranging from 0.0001% to 20% by weight, such as from 0.005% to 6% by weight, relative to the total weight of the composition.

Addition salts that can be used for the oxidation bases and the couplers include acid addition salts, such as: hydrochlorides; hydrobromides; sulfates; citrates; succinates; tartrates; lactates; tosylates; benzenesulfonates; phosphates; and acetates.

The dye composition in accordance with the present disclosure may also contain at least one direct dye, which may be chosen from: neutral, acidic or cationic nitrobenzene dyes; neutral, acidic or cationic azo direct dyes; neutral, acidic or cationic quinone, such as anthraquinone direct dyes; azine direct dyes; methine, azomethine, triarylmethane or indoamine direct dyes; and natural direct dyes. In one non-limiting aspect of the present disclosure, the composition according to the invention comprises at least one direct dye chosen from cationic direct dyes and natural direct dyes.

Among the cationic direct dyes that may be used according to the present disclosure, mention may be made of the cationic azo direct dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714 954, such as: 1,3-dimethyl-2-[[4-(dimethylamino)phenyl]azo]-1H-imidazolium chloride; 1,3-dimethyl-2-[(4-aminophenyl)azo]-1H-imidazolium chloride; and 1-methyl-4-[(methylphenylhydrazono)methyl]pyridinium methyl sulfate.

Among the natural direct dyes that may be used according to the present disclosure, mention may be made of: lawsone; juglone; alizarin; purpurin; carminic acid; kermesic acid; purpurogallin; protocatechaldehyde; indigo; isatin; curcumin; spinulosin; and apigenidin. Extracts or decoctions containing these natural dyes, such as henna-based poultices or extracts, may be used.

In one non-limiting embodiment, the at least one direct dye may be contained in an amount from 0.001% to 20% by weight, such as from 0.005% to 10% by weight, relative to the total weight of the ready-to-use composition.

A ready-to-use dye composition of the present disclosure may be obtained by adding at least one oxidizing agent conventionally used for the oxidation dyeing of keratin fibers such as, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes. Of these oxidizing agents, mention may be made of: hydrogen peroxide; peroxidases; two-electron oxidoreductases such as uricases; and four-electron oxygenases, for instance laccases. In one embodiment, hydrogen peroxide is used.

The above examples are non-limiting. One of ordinary skill in the art would know to take care to select the adjuvant(s), additional oxidation dye precursor(s), oxidation coupler(s), and direct dye(s) such that the advantageous properties intrinsically associated with the presently disclosed oxidation dye composition are not, or are not substantially, adversely affected by the envisaged addition(s).

The pH of the dye composition in accordance with the present disclosure may be from 3 to 12, such as from 5 to 11. The pH may be adjusted to a desired value using acidifying or basifying agents that usually used in the dyeing of keratin fibers, or by using standard buffer systems.

Among the acidifying agents that may be mentioned, for example, are mineral or organic acids other than carboxylic diacids, such as: hydrochloric acid; orthophosphoric acid; and sulfuric acid; carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid; and sulfonic acids.

Among the basifying agents that may be mentioned, for example, are aqueous ammonia; alkali metal carbonates; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine and derivatives thereof; sodium hydroxide; potassium hydroxide; and the compounds of formula:

##STR00039## wherein W is a propylene residue optionally substituted with a hydroxyl group or a C.sub.1-C.sub.4 alkyl radical; and R.sub.a, R.sub.b, R.sub.c and R.sub.d, which may be identical or different, represent a hydrogen atom; a C.sub.1-C.sub.4 alkyl; or C.sub.1-C.sub.4 hydroxyalkyl radical.

The dye composition according to the present disclosure may be in various forms, such as a liquid, a cream, a gel, or in any other form that is suitable for dyeing keratin fibers.

Another aspect of the present disclosure relates to a process in which the composition as described above is applied to the fibers and the color is developed using an oxidizing agent. The color may be developed at acidic, neutral or alkaline pH. The oxidizing agent may be added to the composition of the invention just at the time of use. Further, the oxidizing agent may be present in an oxidizing composition that is applied simultaneously with or sequentially to the composition of the invention.

According to one particular embodiment, the composition according to the present, disclosure is mixed, for example at the time of use, with a composition containing, in a medium that is suitable for dyeing, at least one oxidizing agent, wherein the oxidizing agent is present in an amount that is sufficient to develop a desired coloration. The resultant mixture is then applied to the keratin fibers. After an action time of 3 to 50 minutes, for example 5 to 30 minutes, the keratin fibers are rinsed, washed with shampoo, rinsed again, and then dried.

The oxidizing composition may contain various adjuvants conventionally used in hair dye compositions and as defined above.

The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers may range from 3 to 12, such as from 5 to 11. The pH of the oxidizing composition may be adjusted to a desired value through the use of acidifying or basifying agents that are typically used in the dyeing of keratin fibers and as described above.

The ready-to-use composition that is finally applied to the keratin fibers may be in various forms, such as in the form of a liquid, a cream, a gel, or any other form that is suitable for dyeing keratin fibers.

The present disclosure also relates to the use of the cosmetic composition comprising, in a medium that is suitable for dyeing, at least one compound of formula (I) for dyeing fibers, such as hair.

A further aspect of the present disclosure is a multi-compartment device or dyeing "kit", in which a first compartment contains the dye composition described above and a second compartment contains an oxidizing composition. This device may be equipped with a means for applying the desired mixture to hair, such as the devices described in patent FR-2 586 913.

Using this device, it is possible to dye keratin fibers via a process that includes mixing a dye composition in accordance with the invention with an oxidizing agent as described above, and applying the resultant mixture to the keratin fibers for a time that is sufficient to develop a desired coloration.

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.

Notwithstanding the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in its respective testing measurement.

The examples that follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES

Example 1

Synthesis of N-(2-methoxy-1-methylethyl)benzene-1,4-diamine dihydrochloride (2)

##STR00040## Step 1: Preparation of (2-methoxy-1-methylethyl)(4-nitrophenyl)amine (1)

21 g (0.15 mol) of 1-fluoro-4-nitrobenzene and 42 ml of 2-amino-1-methoxypropane were introduced into a 150 ml three-necked flask. The mixture was stirred for 15 minutes and brought to the boiling point. After reaction for 2 to 3 hours, the reaction medium was poured onto ice. A yellow precipitate formed. This precipitate was filtered off, washed with water, and then successively washed with a minimum amount of ethanol, isopropyl ether, and petroleum ether. 27.8 g of expected product were isolated.

TABLE-US-00002 THEORY FOUND C 57.13 56.94 H 6.71 6.70 N 13.32 13.04 O 22.83 22.80

Step 2: Preparation of N-(2-methoxy-1-methylethyl)benzene-1,4-diamine dihydrochloride (2)

21 g (0.1 mol) of (1) were placed in a mixture of 42 ml of 96.degree. alcohol. 42 ml of cyclohexene and 4.4 ml of water. 4.2 g of 10% palladium-on-charcoal were added thereto. The mixture was refluxed for 2 hours. The catalyst was filtered off and then washed with ethanol. The filtrate was concentrated to dryness and then dissolved in 40 ml of absolute ethanol. This solution was cooled to -10.degree. C. and 50 ml of 7N hydrochloric ethanol was added. A white precipitate formed and was filtered off at 0.degree. C. and then washed successively with ethanol, acetone, isopropyl ether and petroleum ether. 2.5 g of expected product were obtained.

TABLE-US-00003 THEORY FOUND C 47.43 47.30 H 7.11 7.12 N 11.07 10.94 O 6.32 6.57 Cl 28.06 28.06

The proton NMR and mass spectra were in accordance with the expected structure of the product.

Example 2

Synthesis of N-(1-methoxymethylpropyl)benzene-1,4-diamine dihydrochloride (4)

##STR00041## Step 1: Preparation of (1-methoxymethylpropyl)(4-nitro-)amine (3)

23 g of 1-methoxymethylpropylamine was added to 11.3 g (0.08 mol) of 1-fluoro-4-nitrobenzene. The mixture was refluxed for 6 hours and was then poured onto ice. A yellow precipitate formed; this precipitate was filtered off and washed with water, with a minimum amount of ethanol, with isopropyl ether, and then with petroleum ether. After the precipitate was dried, 15 g of a yellow solid were obtained.

TABLE-US-00004 THEORY FOUND C 58.91 58.81 H 7.19 7.22 N 12.49 12.46 O 21.40 21.31

Step 2: Preparation of N-(1-methoxymethylpropyl)benzene-1,4-diamine dihydrochloride (4)

0.1 mol of (3) (22.4 g) was placed in a mixture of 42 ml of 96.degree. alcohol, 42 ml of cyclohexene and 4.4 ml of water. 4.2 g of 10% palladium-on-charcoal was added thereto. The mixture was refluxed for 2 hours. The catalyst was filtered off and washed with alcohol. The filtrate was concentrated to dryness and then dissolved in 40 ml of absolute ethanol. This solution was cooled to -10.degree. C. and 50 ml of 7N hydrochloric ethanol was added. A white precipitate formed. This precipitate was filtered off at 0.degree. C. and then washed successively with ethanol, acetone, isopropyl ether and finally petroleum ether. 2.4 g of product were obtained.

TABLE-US-00005 THEORY, H.sub.2O FOUND C 46.32 46.42 H 7.77 7.75 N 9.82 9.86 O 10.22 10.53 Cl 24.86 25.43

The proton NMR and mass spectra were in accordance with the expected structure of the product.

Example 3

Synthesis of N-(3-isopropoxypropyl)benzene-1,4-diamine dihydrochloride (6)

##STR00042## Step 1: Preparation of (3-isopropoxypropyl)(4-nitrophenyl)amine (5)

42 ml of 3-isopropoxypropylamine was added to 21 g (0.15 mol) of 1-fluoro-4-nitrobenzene. As the reaction is exothermic, the temperature was maintained at 90.degree. C. by cooling slightly. After 30 minutes, the reaction was complete. The medium was poured onto ice, and an oil appeared. This oil