Composition for dyeing keratin fibres, comprising a cationic para-phenylenediamine derivative substituted with a diazacyclohexane or diazacycloheptane ring Number:7,186,277 from the United States Patent and Trademark Office (PTO) owispatent In one embodiment, the disclosure relates to a composition for dyeing keratin fibres, for example, human keratin fibres such as the hair, comprising at least one para-phenylenediamine derivative substituted with a diazacyclohexane or diazacycloheptane ring, the nitrogen in position 4 of which is a quaternary ammonium. The present disclosure may make it possible, for example, to obtain at least one of chromatic, strong, relatively unselective, fast coloration of keratin fibres.<H diazacycloheptane, diazacyclohexane, Composition, for, 7186277.html, Patent, pto, 7186277

Title: Composition for dyeing keratin fibres, comprising a cationic para-phenylenediamine derivative substituted with a diazacyclohexane or diazacycloheptane ring

Abstract: In one embodiment, the disclosure relates to a composition for dyeing keratin fibres, for example, human keratin fibres such as the hair, comprising at least one para-phenylenediamine derivative substituted with a diazacyclohexane or diazacycloheptane ring, the nitrogen in position 4 of which is a quaternary ammonium. The present disclosure may make it possible, for example, to obtain at least one of chromatic, strong, relatively unselective, fast coloration of keratin fibres.

Patent Number: 7,186,277 Issued on 03/06/2007 to Genet, et al.

Inventors: Genet; Alain (Aulnay Sous Bois, FR), Sabelle; Ste (Paris, FR)
Assignee: L'Oreal SA (Paris, FR)

Appl. No.: 10/807,167

Filed: March 24, 2004

Foreign Application Priority Data


Mar 24, 2003 [FR]			03 03547

Current U.S. Class: 8/405 ; 514/341; 540/575; 544/394; 8/406; 8/410; 8/411; 8/421; 8/567; 8/573; 8/602; 8/606

Current International Class: A61K 8/00 (20060101)

Field of Search: 8/405,406,410,411,421,567,573,602,606 540/575 544/394 514/341

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

Parent Case Text

This application claims benefit of U.S. Provisional Application No. 60/506,766, filed Sep. 30, 2003.

Claims

What is claimed is:

1. A composition for dyeing keratin fibres, comprising, in a cosmetic medium that is suitable for dyeing, at least one para-phenylenediamine derivative chosen from formula (Ia), formula (Ib), and their addition salts: ##STR00039## wherein: R.sub.1 is chosen from: a halogen atom; and saturated and unsaturated C.sub.1 C.sub.8 aliphatic and alicyclic hydrocarbon-based chains, wherein at least one carbon atom is optionally replaced with at least one entity chosen from oxygen, nitrogen, silicon, sulphur, and SO.sub.2 groups; and wherein R.sub.1 does not comprise peroxide bonds or diazo, nitro or nitroso radicals; n ranges from 0 to 4, wherein, when n is greater than 1, each R.sub.1 may be identical or different; R.sub.2 and R'.sub.2, which may be identical or different, are chosen from: saturated and unsaturated alkyl radicals, wherein saturated and unsaturated alkyl radicals may optionally be substituted with at least one radical chosen from carboxyls, alkylcarbonyls, alkoxycarbonyls, carbamoyls, monoalkylcarbamoyls and dialkylcarbamoyls, and saturated and unsaturated heterocyclic radicals comprising 4, 5, 6 or 7 atoms, wherein at least one hetero atom is chosen from nitrogen, oxygen, and sulphur; and --CH.sub.2R radicals, wherein R is chosen from saturated and unsaturated alkyl radicals, substituted with at least one radical chosen from hydroxyls, alkoxys, thiols, halogens, aminos, monoalkylaminos, dialkylaminos and amino radicals with the amine substituted with a radical chosen from alkylcarbonyls, carbamyls and alkylsulphonyls; aryl radicals; and benzyl radicals; R.sub.3 is chosen from: a hydrogen atom; optionally unsaturated alkyl radicals; hydroxyl radicals; hydroxyalkyl radicals; alkoxy radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; amino radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; alkyl radicals substituted with at least one hydroxy radical and at least one amino radical; monoalkylamino radicals; dialkylamino radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; R.sub.4 is chosen from: saturated and unsaturated alkyl radicals; hydroxyalkyl radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; hydroxy radicals aminoalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; m ranges from 0 to 4, wherein when m is greater than 1, each R.sub.4 may be identical or different; and X.sup.- is a counterion.

2. The composition according to claim 1, wherein n is equal to 0 or R.sub.1 is chosen from alkyl radicals, hydroxyalkyl radicals, aminoalkyl radicals, alkoxy radicals, and hydroxyalkoxy radicals.

3. The composition according to claim 2, wherein n is equal to 0 or R.sub.1 is chosen from methyl radicals, hydroxymethyl radicals, 2-hydroxyethyl radicals, 1,2-dihydroxyethyl radicals, methoxy radicals, isopropyloxy radicals, and 2-hydroxyethoxy radicals.

4. The composition according to claim 1, wherein n is equal to 0 or 1.

5. The composition according to claim 1, wherein R.sub.2 is chosen from alkyl radicals and alkyl radicals substituted with a saturated or unsaturated heterocyclic radical comprising 4, 5, 6 or 7 atoms, wherein at least one hetero atom of which is chosen from nitrogen; oxygen; sulphur; and --CH.sub.2R radicals, wherein R is an alkyl radical substituted with at least one hydroxyl radical.

6. The composition according to claim 5, wherein R.sub.2 is chosen from a 2-hydroxyethyl radical, a 2,3-dihydroxypropyl radical, a 3-(1-pyrrolidinyl)propyl radical, and a methyl radical.

7. The composition according to claim 1, wherein R'.sub.2 is chosen from saturated and unsaturated alkyl radicals and --CH.sub.2R radicals, wherein R is an alkyl radical substituted with at least one group chosen from hydroxyls, aminos, monoalkylaminos and dialkylaminos.

8. The composition according to claim 7, wherein R'.sub.2 is chosen from a methyl radical, an ethyl radical, and a 2-hydroxyethyl radical.

9. The composition according to claim 1, wherein R.sub.3 is chosen from a hydrogen atom, alkyl radicals, hydroxyalkyl radicals, aminoalkyl radicals, carboxyl radicals, carbamoyl radicals, hydroxyl radicals, alkoxy radicals, amino radicals, monoalkylamino radicals, and dialkylamino radicals.

10. The composition according to claim 9, wherein R.sub.3 is chosen from a hydrogen atom, hydroxyl radicals, carboxyl radicals, carbamoyl radicals, amino radicals, hydroxymethyl radicals, and aminomethyl radicals.

11. The composition according to claim 1, wherein m is equal to 0 or R.sub.4 is chosen from alkyl radicals, hydroxyalkyl radicals, aminoalkyl radicals, carboxyl radicals, carbamoyl radicals, monoalkylcarbamoyl radicals, and dialkylcarbamoyl radicals.

12. The composition according to claim 11, wherein m is equal to 0 or 1.

13. The composition according to claim 1, wherein the at least one para-phenylenediamine derivative is chosen from 4-(4-aminophenyl)-1-ethyl-1-methylpiperazin-1-ium chloride, 4-(4-aminophenyl)-1,1-dimethylpiperazin-1-ium chloride 4-(4-aminophenyl)-1,1-dimethyl[1,4]diazepan-1-ium chloride 4-(4-aminophenyl)-1,1-bis-(2-hydroxyethyl)-[1,4]diazepan-1-ium chloride 4-(4-aminophenyl)-6-hydroxy-1,1-dimethyl[1,4]diazepan-1-ium chloride 4-(4-aminophenyl)-1-(2-methoxyethyl)-1-methylpiperazin-1-ium chloride 4-(4-aminophenyl)-1-(2-hydroxyethyl)-1-methyl[1,4]diazepan-1-ium chloride 4-(4-aminophenyl)-1,2-dimethyl-1-m-tolylpiperazin-1-ium chloride 4-(4-aminophenyl)-1-(2-hydroxyethyl)-1-methylpiperazin-1-ium chloride 4-(4-aminophenyl)-1,1-bis-(2-hydroxyethyl)piperazin-1-ium chloride 4-(4-aminophenyl)-1,2-dimethyl-1-m-tolylpiperazin-1-ium chloride 4-(4-aminophenyl)-1-ethyl-1-(2-hydroxyethyl)piperazin-1-ium chloride 4-(4-aminophenyl)-1-(2-hydroxyethyl)-1-ethyl[1,4]diazepan-1-ium chloride 4-(4-aminophenyl)-1-methyl-1-(3-pyrrolidin-1-ylpropyl)[1,4]diazepan-1-ium chloride 4-(4-aminophenyl)-1-methyl-1-(3-pyrrolidin-1-ylpropyl)piperazin-- 1-ium chloride 4-(4-aminophenyl)-1-carbamoylmethyl-1-methylpiperazin-1-ium chloride 4-(4-amino-3-methylphenyl)-1-ethyl-1-methylpiperazin-1-ium chloride 4-(4-amino-3-methylphenyl)-1,1-dimethylpiperazin-1-ium chloride 4-(4-amino-3-methylphenyl)-1,1-dimethyl[1,4]diazepan-1-ium chloride 4-(4-amino-3-methylphenyl)-1,1-bis-(2-hydroxyethyl)[1,4]diazepan-1-ium chloride 4-(4-amino-3-methylphenyl)-6-hydroxy-1,1-dimethyl[1,4]diazepan-1- -ium chloride 4-(4-amino-3-methylphenyl)-1-(2-methoxyethyl)-1-methylpiperazin-1-ium chloride 4-(4-amino-3-methylphenyl)-1-(2-hydroxyethyl)-1-methyl-[1,4]diaz- epan-1-ium chloride 4-(4-amino-3-methylphenyl)-1,2-dimethyl-1-m-tolylpiperazin-1-ium chloride, 4-(4-amino-3-methylphenyl)-1-(2-hydroxyethyl)-1-methylpiperazin- -1-ium chloride, 4-(4-amino-3-methylphenyl)-1,1-bis-(2-hydroxyethyl)piperazin-1-ium chloride, 4-(4-amino-3-methylphenyl)-1,2-dimethyl-1-m-tolylpiperazin-1-iu- m chloride, 4-(4-amino-3-methylphenyl)-1-ethyl-1-(2-hydroxyethyl)piperazin-1-ium chloride, 4-(4-amino-3-methylphenyl)-1-(2-hydroxyethyl)-1-ethyl[1,4]diaze- pan-1-ium chloride, 4-(4-amino-3-methylphenyl)-1-methyl-1-(3-pyrrolidin-1-ylpropyl)[1,4]diaze- pan-1-ium chloride, 4-(4-amino-3-methylphenyl)-1-methyl-1-(3-pyrrolidin-1-ylpropyl)piperazin-- 1-ium chloride, and 4-(4-amino-3-aminophenyl)-1-carbamoylmethyl-1-methylpiperazin-1-ium chloride.

14. The composition according to claim 13, wherein the at least one para-phenylenediamine derivative is chosen from 4-(4-aminophenyl)-1,1-dimethyl[1,4]diazepan-1-ium chloride, 4-(4-aminophenyl)-1,1-dimethylpiperazin-1-ium chloride, and 4-(4-aminophenyl)-1-(2-hydroxyethyl)-1-methylpiperazin-1-ium chloride.

15. The composition according to claim 1, further comprising at least one coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers, and heterocyclic couplers, and the addition salts thereof.

16. The composition according to claim 15, wherein the amount of the at least one coupler ranges from 0.001% to 10% by weight relative to the total weight of the dye composition.

17. The composition of claim 16, wherein the amount of the at least one coupler ranges from 0.005% to 6% by weight relative to the total weight of the dye composition.

18. The composition according to claim 1, further comprising at least one additional oxidation base other than the the at least one para-phenylenediamine derivative, chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, ortho-phenylenediamines and heterocyclic bases, and the addition salts thereof.

19. The composition according to claim 18, wherein the amount of the at least one additional oxidation base ranges from 0.001% to 10% by weight relative to the total weight of the dye composition.

20. The composition according to claim 19, wherein the amount of the at least one additional oxidation base ranges from 0.005% to 6% by weight relative to the total weight of the dye composition.

21. A process for dyeing keratin fibres comprising applying a composition to keratin fibres in the presence of an oxidizing agent, for a time that is sufficient to develop a desired coloration, the composition comprising, in a cosmetic medium that is suitable for dyeing, at least one para-phenylenediamine derivative chosen from formula (Ia), formula (Ib), and their addition salts: ##STR00040## wherein: R.sub.1 is chosen from: a halogen atom; and saturated and unsaturated C.sub.1 C.sub.8 aliphatic and alicyclic hydrocarbon-based chains, wherein at least one carbon atom is optionally replaced with at least one entity chosen from oxygen, nitrogen, silicon, sulphur, and SO.sub.2 groups; and wherein R.sub.1 does not comprise peroxide bonds or diazo, nitro or nitroso radicals; n ranges from 0 to 4, wherein, when n is greater than 1, each R.sub.1 may be identical or different; R.sub.2 and R'.sub.2, which may be identical or different, are chosen from: saturated and unsaturated alkyl radicals, wherein saturated and unsaturated alkyl radicals may be optionally be substituted with at least one radical chosen from carboxyls, alkylcarbonyls, alkoxycarbonyls, carbamoyls, monoalkylcarbamoyls and dialkylcarbamoyls, and saturated and unsaturated heterocyclic radicals comprising 4, 5, 6 or 7 atoms, wherein at least one hetero atom is chosen from nitrogen, oxygen, and sulphur; and --CH.sub.2R radicals, wherein R is chosen from saturated and unsaturated alkyl radicals, substituted with at least one radical chosen from hydroxyls, alkoxys, thiols, halogens, aminos, monoalkylaminos, dialkylaminos and amino radicals with the amine substituted with a radical chosen from alkylcarbonyls, carbamyls and alkylsulphonyls; aryl radicals; and benzyl radicals; R.sub.3 is chosen from: a hydrogen atom; optionally unsaturated alkyl radicals; hydroxyl radicals; hydroxyalkyl radicals; alkoxy radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; amino radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; alkyl radicals substituted with at least one hydroxy radical and at least one amino radical; monoalkylamino radicals; dialkylamino radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; R.sub.4 is chosen from: saturated and unsaturated alkyl radicals; hydroxyalkyl radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; hydroxy radicals aminoalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; m ranges from 0 to 4, wherein when m is greater than 1, each R.sub.4 may be identical or different; and X.sup.- is a counterion.

22. The process according to claim 21, wherein the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.

23. A multi-compartment device comprising a first compartment comprising a composition for dyeing keratin fibres, and a second compartment comprising an oxidizing agent, the composition for dyeing keratin fibres comprising, in a cosmetic medium that is suitable for dyeing, at least one para-phenylenediamine derivative chosen from formula (Ia), formula (Ib), and their addition salts: ##STR00041## wherein: R.sub.1 is chosen from: a halogen atom; and saturated and unsaturated C.sub.1 C.sub.8 aliphatic and alicyclic hydrocarbon-based chains, wherein at least one carbon atom is optionally replaced with at least one entity chosen from oxygen, nitrogen, silicon, sulphur, and SO.sub.2 groups; and wherein R.sub.1 does not comprise peroxide bonds or diazo, nitro or nitroso radicals; n ranges from 0 to 4, wherein, when n is greater than 1, each R.sub.1 may be identical or different; R.sub.2 and R'.sub.2, which may be identical or different, are chosen from: saturated and unsaturated alkyl radicals, wherein saturated and unsaturated alkyl radicals may be optionally be substituted with at least one radical chosen from carboxyls, alkylcarbonyls, alkoxycarbonyls, carbamoyls, monoalkylcarbamoyls and dialkylcarbamoyls, and saturated and unsaturated heterocyclic radicals comprising 4, 5, 6 or 7 atoms, wherein at least one hetero atomis chosen from nitrogen, oxygen, and sulphur; and --CH.sub.2R radicals, wherein R is chosen from saturated and unsaturated alkyl radicals, substituted with at least one radical chosen from hydroxyls, alkoxys, thiols, halogens, aminos, monoalkylaminos, dialkylaminos and amino radicals with the amine substituted with a radical chosen from alkylcarbonyls, carbamyls and alkylsulphonyls; aryl radicals; and benzyl radicals; R.sub.3 is chosen from: a hydrogen atom; optionally unsaturated alkyl radicals; hydroxyl radicals; hydroxyalkyl radicals; alkoxy radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; amino radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; alkyl radicals substituted with at least one hydroxy radical and at least one amino radical; monoalkylamino radicals; dialkylamino radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; R.sub.4 is chosen from: saturated and unsaturated alkyl radicals; hydroxyalkyl radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; hydroxy radicals aminoalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; m ranges from 0 to 4, wherein when m is greater than 1, each R.sub.4 may be identical or different; and X.sup.- is a counterion.

24. At least one para-Phenylenediamine derivative chosen from formula (Ia), formula (Ib), and their addition salts: ##STR00042## wherein: R.sub.1 is chosen from: a halogen atom; and saturated and unsaturated C.sub.1 C.sub.8 aliphatic and alicyclic hydrocarbon-based chains, wherein at least one carbon atom is optionally replaced with at least one entity chosen from oxygen, nitrogen, silicon, sulphur, and SO.sub.2 groups; and wherein R.sub.1 does not comprise peroxide bonds or diazo, nitro or nitroso radicals; n ranges from 0 to 4, wherein, when n is greater than 1, each R.sub.1 may be identical or different; R.sub.2 and R'.sub.2, which may be identical or different, are chosen from: saturated and unsaturated alkyl radicals, wherein saturated and unsaturated alkyl radicals may be optionally be substituted with at least one radical chosen from carboxyls, alkylcarbonyls, alkoxycarbonyls, carbamoyls, monoalkylcarbamoyls and dialkylcarbamoyls, and saturated and unsaturated heterocyclic radicals comprising 4, 5, 6 or 7 atoms, wherein at least one hetero atom is chosen from nitrogen, oxygen, and sulphur; and --CH.sub.2R radicals, wherein R is chosen from saturated and unsaturated alkyl radicals, substituted with at least one radical chosen from hydroxyls, alkoxys, thiols, halogens, aminos, monoalkylaminos, dialkylaminos and amino radicals with the amine substituted with a radical chosen from alkylcarbonyls, carbamyls and alkylsulphonyls; aryl radicals; and benzyl radicals; R.sub.3 is chosen from: a hydrogen atom; optionally unsaturated alkyl radicals; hydroxyl radicals; hydroxyalkyl radicals; alkoxy radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; amino radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; alkyl radicals substituted with at least one hydroxy radical and at least one amino radical; monoalkylamino radicals; dialkylamino radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; R.sub.4 is chosen from: saturated and unsaturated alkyl radicals; hydroxyalkyl radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; hydroxy radicals aminoalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; m ranges from 0 to 4, wherein when m is greater than 1, each R.sub.4 may be identical or different; and X.sup.- is a counterion; wherein the at least one para-phenylenediamine derivative is not substituted with a diazacyclohexane ring wherein n is equal to 0, m is equal to 0 and R.sub.2 and R'.sub.2 are methyl radicals.

25. At least one para-Nitroaniline derivative chosen from formula (IIa), (IIb), and their addition salts: ##STR00043## wherein: R.sub.1 is chosen from: a halogen atom; and saturated and unsaturated C.sub.1 C.sub.8 aliphatic and alicyclic hydrocarbon-based chains, wherein at least one carbon atom is optionally replaced with at least one entity chosen from oxygen, nitrogen, silicon, sulphur, and SO.sub.2 groups; and wherein R.sub.1 does not comprise peroxide bonds or diazo, nitro or nitroso radicals; n ranges from 0 to 4, wherein, when n is greater than 1, each R.sub.1 may be identical or different; R.sub.2 and R'.sub.2, which may be identical or different, are chosen from: saturated and unsaturated alkyl radicals, wherein saturated and unsaturated alkyl radicals may be optionally be substituted with at least one radical chosen from carboxyls, alkylcarbonyls, alkoxycarbonyls, carbamoyls, monoalkylcarbamoyls and dialkylcarbamoyls, and saturated and unsaturated heterocyclic radicals comprising 4, 5, 6 or 7 atoms, wherein at least one hetero atom is chosen from nitrogen, oxygen, and sulphur; and --CH.sub.2R radicals, wherein R is chosen from saturated and unsaturated alkyl radicals, substituted with at least one radical chosen from hydroxyls, alkoxys, thiols, halogens, aminos, monoalkylaminos, dialkylaminos and amino radicals with the amine substituted with a radical chosen from alkylcarbonyls, carbamyls and alkylsulphonyls; aryl radicals; and benzyl radicals; R.sub.3 is chosen from: a hydrogen atom; optionally unsaturated alkyl radicals; hydroxyl radicals; hydroxyalkyl radicals; alkoxy radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; amino radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; alkyl radicals substituted with at least one hydroxy radical and at least one amino radical; monoalkylamino radicals; dialkylamino radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; R.sub.4 is chosen from: saturated and unsaturated alkyl radicals; hydroxyalkyl radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; hydroxy radicals aminoalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; m ranges from 0 to 4, wherein when m is greater than 1, each R.sub.4 may be identical or different; and X.sup.- is a counterion wherein the at least one paraphenylenediamine is not 4-(4-nitrophenyl)-1,1-dimethylpiperazin-1-ium.

26. A composition for dyeing keratin fibres, comprising, in a cosmetic medium that is suitable for dyeing, (a) at least one para-phenylenediamine derivative chosen from formula (Ia), formula (Ib), and their addition salts: ##STR00044## wherein: R.sub.1 is chosen from: a halogen atom; and saturated and unsaturated C.sub.1 C.sub.8aliphatic and alicyclic hydrocarbon-based chains, wherein at least one carbon atom is optionally replaced with at least one entity chosen from oxygen, nitrogen, silicon,sulphur, and SO.sub.2 groups; and wherein R.sub.1 does not comprise peroxide bonds or diazo, nitro or nitroso radicals; n ranges from 0 to 4, wherein, when n is greater than 1, each R.sub.1 may be identical or different; R.sub.2 and R'.sub.2, which may be identical or different, are chosen from: saturated and unsaturated alkyl radicals, wherein saturated and unsaturated alkyl radicals may optionally be substituted with at least one radical chosen from carboxyls, alkylcarbonyls, alkoxycarbonyls, carbamoyls, monoalkylcarbamoyls and dialkylcarbamoyls, and saturated and unsaturated heterocyclic radicals comprising 4, 5, 6 or 7 atoms, wherein at least one hetero atomis chosen from nitrogen, oxygen, and sulphur; and --CH.sub.2R radicals, wherein R is chosen from saturated and unsaturated alkyl radicals, substituted with at least one radical chosen from hydroxyls, alkoxys, thiols, halogens, aminos, monoalkylaminos, dialkylaminos and amino radicals with the amine substituted with a radical chosen from alkylcarbonyls, carbamyls and alkylsulphonyls; aryl radicals; and benzyl radicals; R.sub.3is chosen from: a hydrogen atom; optionally unsaturated alkyl radicals; hydroxyl radicals; hydroxyalkyl radicals; alkoxy radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; amino radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; alkyl radicals substituted with at least one hydroxy radical and at least one amino radical; monoalkylamino radicals; dialkylamino radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; R.sub.4is chosen from: saturated and unsaturated alkyl radicals; hydroxyalkyl radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; hydroxy radicals aminoalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; m ranges from 0 to 4, wherein when m is greater than 1, each R.sub.4 may be identical or different; and X.sup.- is a counterion and (b) at least one adjuvant chosen from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic polymers and mixtures thereof, inorganic and organic thickeners, antioxidants, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, packaging agents, film-forming agents, ceramides, preserving agents and opacifiers.

27. A composition for dyeing keratin fibres, comprising, in a cosmetic medium that is suitable for dyeing, (a) at least one para-phenylenediamine derivative chosen from formula (Ia), formula (Ib), and their addition salts: ##STR00045## wherein: R.sub.1 is chosen from: a halogen atom; and saturated and unsaturated C.sub.1 C.sub.8 aliphatic and alicyclic hydrocarbon-based chains, wherein at least one carbon atom is optionally replaced with at least one entity chosen from oxygen, nitrogen, silicon,sulphur, and SO.sub.2 groups; and wherein R.sub.1 does not comprise peroxide bonds or diazo, nitro or nitroso radicals; n ranges from 0 to 4, wherein, when n is greater than 1, each R.sub.1 may be identical or different; R.sub.2 and R'.sub.2, which may be identical or different, are chosen from: saturated and unsaturated alkyl radicals, wherein saturated and unsaturated alkyl radicals may optionally be substituted with at least one radical chosen from carboxyls, alkylcarbonyls, alkoxycarbonyls, carbamoyls, monoalkylcarbamoyls and dialkylcarbamoyls, and saturated and unsaturated heterocyclic radicals comprising 4, 5, 6 or 7 atoms, wherein at least one hetero atomis chosen from nitrogen, oxygen, and sulphur; and --CH.sub.2R radicals, wherein R is chosen from saturated and unsaturated alkyl radicals, substituted with at least one radical chosen from hydroxyls, alkoxys, thiols, halogens, aminos, monoalkylaminos, dialkylaminos and amino radicals with the amine substituted with a radical chosen from alkylcarbonyls, carbamyls and alkylsulphonyls; aryl radicals; and benzyl radicals; R.sub.3is chosen from: a hydrogen atom; optionally unsaturated alkyl radicals; hydroxyl radicals; hydroxyalkyl radicals; alkoxy radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; amino radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; alkyl radicals substituted with at least one hydroxy radical and at least one amino radical; monoalkylamino radicals; dialkylamino radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; R.sub.4is chosen from: saturated and unsaturated alkyl radicals; hydroxyalkyl radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; hydroxy radicals aminoalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; m ranges from 0 to 4, wherein when m is greater than 1, each R.sub.4 may be identical or different; and X.sup.- is a counterion and (b) at least one adjuvant chosen from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic polymers and mixtures thereof.

28. A composition for dyeing keratin fibres, comprising, in a cosmetic medium that is suitable for dyeing, at least one para-phenylenediamine derivative chosen from formula (Ia), formula (Ib), and their addition salts: ##STR00046## wherein: R.sub.1 is chosen from: a halogen atom; and saturated and unsaturated C.sub.1 C.sub.8 aliphatic and alicyclic hydrocarbon-based chains, wherein at least one carbon atom is optionally replaced with at least one entity chosen from oxygen, nitrogen, silicon,sulphur, and SO.sub.2 groups; and wherein R.sub.1 does not comprise peroxide bonds or diazo, nitro or nitroso radicals; n ranges from 0 to 4, wherein, when n is greater than 1, each R.sub.1 may be identical or different; R.sub.2 and R'.sub.2, which may be identical or different, are chosen from: saturated and unsaturated alkyl radicals, wherein saturated and unsaturated alkyl radicals may optionally be substituted with at least one radical chosen from carboxyls, alkylcarbonyls, alkoxycarbonyls, carbamoyls, monoalkylcarbamoyls and dialkylcarbamoyls, and saturated and unsaturated heterocyclic radicals comprising 4, 5, 6 or 7 atoms, wherein at least one hetero atomis chosen from nitrogen, oxygen, and sulphur; and --CH.sub.2R radicals, wherein R is chosen from saturated and unsaturated alkyl radicals, substituted with at least one radical chosen from hydroxyls, alkoxys, thiols, halogens, aminos, monoalkylaminos, dialkylaminos and amino radicals with the amine substituted with a radical chosen from alkylcarbonyls, carbamyls and alkylsulphonyls; aryl radicals; and benzyl radicals; R.sub.3is chosen from: a hydrogen atom; optionally unsaturated alkyl radicals; hydroxyl radicals; hydroxyalkyl radicals; alkoxy radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; amino radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; alkyl radicals substituted with at least one hydroxy radical and at least one amino radical; monoalkylamino radicals; dialkylamino radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; R.sub.4is chosen from: saturated and unsaturated alkyl radicals; hydroxyalkyl radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; hydroxy radicals aminoalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; m ranges from 0 to 4, wherein when m is greater than 1, each R.sub.4 may be identical or different; and X.sup.- is a counterion wherein the para-phenylenediamine derivative is not substituted with a diazacyclohexane ring wherein n is equal to 0, m is equal to 0 and R.sub.2 and R'.sub.2 are methyl radicals.

Description

In one embodiment, the disclosure relates to a composition for dyeing keratin fibres, for example, human keratin fibres such as the hair, comprising as an oxidation base at least one para-phenylenediamine derivative substituted with a diazacyclohexane or diazacycloheptane ring, the nitrogen in position 4 of which is a quaternary ammonium.

It is known practice to dye keratin fibres, for example, human keratin fibres such as the hair with dye compositions comprising oxidation dye precursors, generally known as oxidation bases, for example, ortho- or para-phenylenediamines; ortho- or para-aminophenols; heterocyclic compounds such as diaminopyrazole derivatives; pyrazolo[1,5-a]pyrimidine derivatives; pyrimidine derivatives; pyridine derivatives; 5,6-dihydroxyindole derivatives and 5,6-dihydroxyindoline derivatives. Oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds that, when combined with oxidizing products, can give rise to coloured compounds or dyes 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 meta-phenylenediamines, meta-aminophenols, meta-hydroxyphenols and certain heterocyclic compounds such as, for example, pyrazolo[1,5-b]-1,2,4-triazole derivatives, pyrazolo[3,2-c]-1,2,4-triazole derivatives, pyrazolo[1,5-a]pyrimidine derivatives, pyridine derivatives, pyrazol-5-one derivatives, indoline derivatives and indole derivatives.

The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.

In one embodiment, the "permanent" coloration obtained with these oxidation dyes may moreover satisfy a certain number of requirements. It may have no toxicological drawbacks, it may allow shades to be obtained in the desired intensity, and it may show good resistance to external agents such as light, bad weather, washing, permanent-waving, perspiration and rubbing.

The dyes may also allow white hairs to be covered and, finally, they may be as unselective as possible, i.e. they may produce the smallest possible colour differences along the same length of keratin fibre, which may in fact be differently sensitized (i.e. damaged) between its end and its root. They may also show good chemical stability in the formulations, and may have a good toxicological profile.

In the field of hair dyeing, para-phenylenediamine and para-tolylenediamine are oxidation bases that are widely used. They can give varied shades with oxidation couplers.

However, for some embodiments, it is desirable to discover novel oxidation bases that have a better toxicological profile than para-phenylenediamine and para-tolylenediamine, while at the same time giving the hair excellent properties in terms of colour intensity, variety of shades, colour uniformity and fastness with respect to external agents.

It is already known practice to use 1,4-diazacycloheptane derivatives for the oxidation dyeing of keratin fibres. For example, U.S. Pat. No. 6,165,230 describes a dye composition comprising 1,4-diazacycloheptane derivatives substituted on the two nitrogen atoms of the ring with a 4'-aminobenzene group.

It has already been proposed, for example, in patents FR 9 709 027 and FR 9 709 028, to use para-pheylenediamine derivatives comprising a cationic group.

In some embodiments, however, these compounds may not make it possible to give a coloration that is equivalent in quality to that obtained with para-phenylenediamine or with para-tolylenediamine due to the lack of intensity and colour uniformity.

Thus, it is still desirable for some uses to discover novel oxidation bases that have both a good toxicological profile and properties such that the dye compositions containing them are able to give the hair excellent properties in terms of colour intensity, variety of shades, colour uniformity and fastness with respect to the various external attacking factors to which the hair may be subjected.

One of the objectives of the present disclosure is to develop novel dye compositions that may not have the drawbacks of the oxidation bases of the prior art, by providing novel dye compositions for dyeing keratin fibres, which do not degrade the keratin fibres, while at the same time being capable of generating intense colorations in varied shades, which are relatively unselective, resistant and have a good toxicological profile.

This objective may be achieved by the present disclosure, one non-limiting embodiment of which is a composition for dyeing keratin fibres, for example, human keratin fibres such as the hair, comprising, in a cosmetic medium that is suitable for dyeing, at least one para-phenylenediamine derivative of formula (I), as used herein formula (I) refers to formula (Ia), formula (Ib), and their addition salts:

##STR00001## wherein: R.sub.1 is chosen from: a halogen atom; and saturated and unsaturated C.sub.1 C.sub.8 aliphatic and alicyclic hydrocarbon-based chains, wherein at least one carbon atom is optionally replaced with at least one entity chosen from oxygen, nitrogen, silicon, sulphur, and SO.sub.2 groups; and wherein R.sub.1 does not comprise peroxide bonds or diazo, nitro or nitroso radicals; n ranges from 0 to 4, wherein, when n is greater than 1, each R.sub.1 may be identical or different; R.sub.2 and R'.sub.2, which may be identical or different, are chosen from: saturated and unsaturated alkyl radicals, wherein saturated and unsaturated alkyl radicals may be optionally be substituted with at least one radical chosen from carboxyls, alkylcarbonyls, alkoxycarbonyls, carbamoyls, monoalkylcarbamoyls and dialkylcarbamoyls, and saturated and unsaturated heterocyclic radicals comprising 4, 5, 6 or 7 atoms, wherein at least one hetero atom is chosen from nitrogen, oxygen, and sulphur; and --CH.sub.2R radicals, wherein R is chosen from saturated and unsaturated alkyl radicals, substituted with at least one radical chosen from hydroxyls, alkoxys, thiols, halogens, aminos, monoalkylaminos, dialkylaminos and amino radicals with the amine substituted with a radical chosen from alkylcarbonyls, carbamyls and alkylsulphonyls; aryl radicals; and benzyl radicals; R.sub.3 is chosen from: a hydrogen atom; optionally unsaturated alkyl radicals; hydroxyl radicals; hydroxyalkyl radicals; alkoxy radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; amino radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; alkyl radicals substituted with at least one hydroxy radical and at least one amino radical; monoalkylamino radicals; dialkylamino radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; R.sub.4 is chosen from: saturated and unsaturated alkyl radicals; hydroxyalkyl radicals; alkoxyalkyl radicals; alkylcarbonyl radicals; hydroxyalkoxyalkyl radicals; aminoalkyl radicals, wherein the amine is optionally monosubstituted or disubstituted with a radical chosen from alkyl radicals, acetyl radicals and hydroxyalkyl radicals; hydroxy radicals aminoalkyl radicals; carboxyl radicals; carboxyalkyl radicals; carbamoyl radicals; carbamoylalkyl radicals; alkoxycarbonyl radicals; monoalkylaminocarbonyl radicals; dialkylaminocarbonyl radicals; monoalkylaminocarbonylalkyl radicals; and dialkylaminocarbonylalkyl radicals; m ranges from 0 to 4, wherein when m is greater than 1, each R.sub.4 may be identical or different; and X.sup.- is a counterion.

The present disclosure makes it possible, for example, to obtain at least one of chromatic, strong, relatively unselective and fast dyeing of keratin fibres.

Another subject of the disclosure is a process for dyeing keratin fibres using the composition disclosed herein.

Other non-limiting embodiments of the disclosure are novel para-phenylenediamine derivatives substituted with at least one ring chosen from diazacyclohexane and diazacycloheptane, the nitrogen in position 4 of which is a quaternary ammonium.

Another non-limiting embodiment of the invention is a para-nitroaniline derivative substituted with at least one ring chosen from diazacyclohexane and diazacycloheptane, the nitrogen in position 4 of which is a quaternary ammonium, allowing the synthesis of the derivatives of formula (I) described above.

The compounds of formula (I) are para-phenylenediamines wherein one amine is included in a ring chosen from the 1,4-diazacycloheptane type, known in the literature as 1,4-diazepane; and the 1,4-diazacyclohexane type, known in the literature as 1,4-piperazine.

In the above definitions, the alkyl radicals are linear or branched and, unless otherwise mentioned, comprise from 1 to 10 carbon atoms, for example, from 1 to 6 carbon atoms. An alkoxy radical is an alkyl-O-radical, the alkyl radical being as defined above.

The expression "unsaturated alkyl radical" means an alkyl ranging from 2 to 10 carbon atoms comprising at least one double and/or triple bonds. A substituted alkyl radical is a monosubstituted or polysubstituted alkyl. For example, a hydroxyalkyl or an aminoalkyl is an alkyl that may be substituted with at least one hydroxyl or amino group, respectively.

In formula (I), the radical R.sub.1 may be chosen, for example, from chlorine atoms, methyl radicals, ethyl radicals, isopropyl radicals, vinyl radicals, allyl radicals, methoxymethyl radicals, hydroxymethyl radicals, 1-carboxymethyl radicals, 1-aminomethyl radicals, 2-carboxyethyl radicals, 2-hydroxyethyl radicals, 3-hydroxypropyl radicals, 1,2-dihydroxyethyl radicals, 1-hydroxy-2-aminoethyl radicals, 1-amino-2-hydroxyethyl radicals, 1,2-diaminoethyl radicals, methoxy radicals, ethoxy radicals, allyloxy radicals, and 2-hydroxyethyloxy radicals.

According to one non-limiting embodiment of the invention, n is equal to 0 or R.sub.1 is chosen from alkyl radicals, hydroxyalkyl radicals, aminoalkyl radicals, alkoxy radicals, and hydroxyalkoxy radicals. In the latter case, when n is not equal to 0, the radical R.sub.1 may, for example, be chosen from methyl radicals, hydroxymethyl radicals, 2-hydroxyethyl radicals, 1,2-dihydroxyethyl radicals, methoxy radicals, isopropyloxy radicals, and 2-hydroxyethoxy radicals, for instance, methyl radicals, hydroxymethyl radicals, and 1,2-dihydroxyethyl radicals.

According to one non-limiting embodiment of the invention, the oxidation bases of formula (I) are such that n is equal to 0 or 1.

According to another non-limiting embodiment of the disclosure, the radical R.sub.2 is chosen from an alkyl radical; an alkyl radical substituted with a saturated or unsaturated heterocyclic radical comprising 4, 5, 6 or 7 atoms, at least one hetero atom of which is chosen from nitrogen, oxygen, sulphur, and --CH.sub.2R radicals, wherein R is an alkyl radical substituted with at least one hydroxyl radical. A substituted alkyl radical, as used in this disclosure, may be saturated or unsaturated. In this case, the radical R.sub.2, for example, may be chosen from a 2-hydroxyethyl radical, a 2,3-dihydroxypropyl radical, a 3-(1-pyrrolidinyl)propyl radical, and a methyl radical. For example, the radical R.sub.2 may be chosen from a 2-hydroxyethyl radical and a methyl radical.

According to one non-limiting embodiment of the disclosure, the radical R'.sub.2 is chosen from alkyl radicals and --CH.sub.2R radicals, wherein R is an alkyl radical substituted with at least one radical chosen from hydroxyls, aminos, monoalkylaminos and dialkylaminos. In this case, the radical R'.sub.2 may be, for example, chosen from a methyl radical, an ethyl radical, and a 2-hydroxyethyl radical.

According to one non-limiting embodiment of the disclosure, the radical R.sub.3 is chosen from a hydrogen atom, alkyl radicals, hydroxyalkyl radicals, aminoalkyl radicals, carboxyl radicals, carbamoyl radicals, hydroxyl radicals, alkoxy radicals, amino radicals, monoalkylamino radicals, and dialkylamino radicals. In this case, the radical R.sub.3 may be chosen from, for example, a hydrogen atom, a hydroxyl radical, a carboxyl radical, a carbamoyl radical, an amino radical, a hydroxymethyl radical, and an aminomethyl radical. For instance, the radical R.sub.3 is a hydrogen atom.

According to one non-limiting embodiment of the disclosure, m is equal to 0 or R.sub.4 is chosen from alkyl radicals, hydroxyalkyl radicals, aminoalkyl radicals, carboxyl radicals, carbamoyl radicals, monoalkylcarbamoyl radicals, and dialkylcarbamoyl radicals. For example, m is equal to 0 or 1.

The compounds of formula (I) may optionally be salified with strong mineral acids, for instance, HCl, HBr and H.sub.2SO.sub.4, or organic acids, for instance acetic acid, lactic acid, tartaric acid, citric acid and succinic acid.

The counterion (X.sup.-) disclosed herein may be chosen from halide ions such as chloride, bromide, fluoride and iodide ions; hydroxide ions; hydrogen sulphate ions; and C.sub.1 C.sub.6 alkyl sulphate ions such as methyl sulphate and ethyl sulphate.

Examples of the derivatives of formula (I) that may be mentioned include the compounds given in the table below.

TABLE-US-00001 Formula Nomenclature ##STR00002## 4-(4-aminophenyl)-1-ethyl-1-methylpiperazin-1-iumchloride ##STR00003## 4-(4-aminophenyl)-1,1-dimethylpiperazin-1-iumchloride ##STR00004## 4-(4-aminophenyl)-1,1-dimethyl[1,4]diazepam-1-ium chloride ##STR00005## 4-(4-aminophenyl)-1,1-bis-(2-hydroxyethyl)-[1,4]diazepam-1-iumchloride ##STR00006## 4-(4-aminophenyl)-6-hydroxy-1,1-dimethyl[1,4]-diazepan-1-ium chloride ##STR00007## 4-(4-aminophenyl)-1-(2-methoxyethyl)-1-methyl-piperazin-1-ium chloride ##STR00008## 4-(4-aminophenyl)-1-(2-hydroxyethyl)-1-methyl[1,4]-diazepan-1-ium chloride ##STR00009## 4-(4-aminophenyl)-1,2-dimethyl-1-m-tolylpiperazin-1-ium chloride ##STR00010## 4-(4-aminophenyl)-1-(2-hydroxyethyl)-1-methyl-piperazin-1-ium chloride ##STR00011## 4-(4-aminophenyl)-1,1-bis-(2-hydroxyethyl)piperazin-1-ium chloride ##STR00012## 4-(4-aminophenyl)-1,2-dimethyl-1-m-tolylpiperazin-1-ium chloride ##STR00013## 4-(4-aminophenyl)-1-ethyl-1-(2-hydroxyethyl)-piperazin-1-ium chloride ##STR00014## 4-(4-aminophenyl)-1-(2-hydroxyethyl)-1-ethyl[1,4]-diazepan-1-ium chloride ##STR00015## 4-(4-aminophenyl)-1-methyl-1-(3-pyrrolidin-1-ylpropyl)[1,4]diazepam-1-iu- m chloride ##STR00016## 4-(4-aminophenyl)-1-methyl-1-(3-pyrrolidin-1-ylpropyl)piperazin-1-iumchl- oride ##STR00017## 4-(4-aminophenyl)-1-carbamoylmethyl-1-methylpiperazin-1-iumchloride ##STR00018## 4-(4-amino-3-methylphenyl)-1-ethyl-1-methylpiperazin-1-ium chloride ##STR00019## 4-(4-amino-3-methyl-phenyl)-1,1-dimethyl-piperazin-1-ium chloride ##STR00020## 4-(4-amino-3-methylphenyl)-1,1-dimethyl[1,4]diazepam-1-ium chloride ##STR00021## 4-(4-amino-3-methyl-phenyl)-1,1-bis-(2-hydroxyethyl)[1,4]-diazepam-1-ium chloride ##STR00022## 4-(4-amino-3-methylphenyl)-6-hydroxy-1,1-dimethyl[1,4]diazepam-1-ium chloride ##STR00023## 4-(4-amino-3-methyl-phenyl)-1-(2-methoxyethyl)-1-methylpiperazin-1-iumch- loride ##STR00024## 4-(4-amino-3-methylphenyl)-1-(2-hydroxyethyl)-1-methyl-[1,4]diazepam-1-i- umchloride ##STR00025## 4-(4-amino-3-methyl-phenyl)-1,2-dimethyl-1-m-tolylpiperazin-1-iumchlorid- e ##STR00026## 4-(4-amino-3-methylphenyl)-1-(2-hydroxyethyl)-1-methylpiperazin-1-iumchl- oride ##STR00027## 4-(4-amino-3-methyl-phenyl)-1,1-bis-(2-hydroxyethyl)piperazin-1-ium chloride ##STR00028## 4-(4-amino-3-methylphenyl)-1,2-dimethyl-1-m-tolylpiperazin-1-ium chloride ##STR00029## 4-(4-amino-3-methyl-phenyl)-1-ethyl-1-(2-hydroxyethyl)piperazin-1-ium chloride ##STR00030## 4-(4-amino-3-methylphenyl)-1-(2-hydroxyethyl)1-ethyl[1,4]diazepam-1-iumc- hloride ##STR00031## 4-(4-amino-3-methyl-phenyl)-1-methyl-1-(3-pyrrolidin-1-ylpropyl)-[1,4]di- azepam-1-iumchloride ##STR00032## 4-(4-amino-3-methylphenyl)-1-methyl-1-(3-pyrrolidin-1-ylpropyl)piperazin- -1-iumchloride ##STR00033## 4-(4-amino-3-amino-phenyl)-1-carbamoyl-methyl-1-methylpiperazin1-ium chloride

Among these compounds, the derivatives of formula (I) may be, for example, 4-(4-aminophenyl)-1,1-dimethyl[1,4]diazepam-1-ium chloride, 4-(4-aminophenyl)-1,1-dimethylpiperazin-1-ium chloride