WO2008047210A2 - Compounds derived from 1 -ethyl-4,5-diamino-pyrazole and their use for oxidative dyeing of keratin fibres - Google Patents

Compounds derived from 1 -ethyl-4,5-diamino-pyrazole and their use for oxidative dyeing of keratin fibres Download PDF

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WO2008047210A2
WO2008047210A2 PCT/IB2007/003087 IB2007003087W WO2008047210A2 WO 2008047210 A2 WO2008047210 A2 WO 2008047210A2 IB 2007003087 W IB2007003087 W IB 2007003087W WO 2008047210 A2 WO2008047210 A2 WO 2008047210A2
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formula
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diamino
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WO2008047210A3 (en
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Ermano Piergentili
Stefano Manfredini
Silvia Vertuani
Sonia Molesini
Federica Commanducci
Giuliano Nocentini
Sabrina Serafini
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Kemon S.P.A.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C09B55/002—Monoazomethine dyes
    • C09B55/003—Monoazomethine dyes with the -C=N- group attached to an heteroring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C09B55/002—Monoazomethine dyes
    • C09B55/003—Monoazomethine dyes with the -C=N- group attached to an heteroring
    • C09B55/004—Monoazomethine dyes with the -C=N- group attached to an heteroring with the -C=N- group between two heterorings

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

The invention concerns new compounds derived from 1-ethyl-4,5-diamino- pyrazole of formula (I) as dye precursors to be used in compositions with coupling agents for oxidative dyeing of keratin fibres, preferably hair.

Description

COMPOUNDS DERIVED FROM 1-ETHYL-4,5-DIAMINO-PYRAZOLE AND THEIR USE FOR OXIDATIVE DYEING OF KERATIN FIBRES
FIELD OF THE INVENTION
The present invention relates to derivatives of 1-hydroxyethyl-4,5-diamino- pyrazole and 1-aminoethyl-4,5-diamino-pyrazole, as well as relative colouring compositions containing at least one of these compounds as dye precursors for keratin fibres, particularly of human keratin, and more particularly hair.
The colouring compositions of the present invention provide a colour which is more stable to light than known colouring compositions, particularly with regard to red highlights.
STATE OF THE ART
Oxidation dyes are important in hair colouring. Said dyes are formed in situ by the oxidative coupling of some substances used as developers, also known as oxidation bases or dye precursors, with one or more couplers (secondary intermediates or dye precursors) in the presence of an oxidizing agent. The oxidative dyeing process comprises applying to the keratin fibres a mixture of a developer and a coupler with, a hydrogen, peroxide solution as the oxidizing agent, which is left on the fibres for a suitable time and finally removed by rinsing.
An ideal colourant for oxidative dyeing of hair must satisfy particular requirements.
First of all it must be able to develop on the hair the desired colour with sufficient intensity and said colour should remain as resistant as possible to external agents, in particular adverse climate conditions, frequent washing, perspiration and common stressful events to which hair is subjected daily. Finally, hair colourants must be toxicologically and dermatologically safe.
1-hydroxyethyl-4,5~diamino-pyrazole is widely used as a developer in oxidative dyeing of hair, but has the considerable limitation of developing a colour that proves to be unstable when exposed to light.
The main aim of the present invention is therefore to provide a colourant for use on hair that can be easily and successfully used on all hair types with consistent, repeatable and predictable results with regard to the colour.
SUMMARY OF THE INVENTION After thorough research a new family of compounds derived from 1-ethyI-4,5- diamino-pyrazole has been synthesized.
Specifically the present invention concerns a compound derived from 1-ethyl-4,5- diamino-pyrazole of formula (I)
Figure imgf000003_0001
(I) wherein
D is NH2 or N=CH-Z; A is selected from the group consisting of NH2, -N=CH-Z, -NH-CH2-Z,
Figure imgf000003_0002
where Z is a substituent of formula
Figure imgf000003_0003
where R-i, R2, R4 and R5 are the same or different and are selected from the group consisting of H, halogen, hydroxy!, nitro, trifluoromethyl, -SO3H, cyano, amino, (Cr C4) alkylamino, (Ci-C4) hydroxyalkylamino, (Ci-C4) aminoalkylamino, di-(Ci-C4) alkylamino, (C1-C4) hydroxyalkyl, (Ci-C4)alkoxyl, (CrC4) thioalkyl, (Ci-C4) aminoalkyl, carboxy, (C1-C4) alkylcarboxyl, (Ci-C4) alkoxycarbonyl, (Ci-C4) alkylcarboxylate, (Ci-C4) alkylcarboxamide, aminocarbonyl (Ci-C4) alkyl, linear or branched (CrC6) alkyl, phenyl optionally substituted with at least one substituent selected from the group consisting of a halogen atom, (CrC4) alkyl, (CrC4) alkoxyl, nitro, trifluoromethyl, amino, (CrC4) alkylamino; benzyl optionally substituted on the methylene with a group selected from halogen, hydroxyl, amino, carboxy, (CrC4) alkylcarboxyl, (CrC4) alkoxycarbonyl, (C1-C4) alkylcarboxylate, (CrC4) alkylcarboxamide, aminocarbonyl (CrC4) alkyl, linear or branched (Cr C6)alkyl, benzyl optionally substituted on the phenyl with a substituent selected from the group consisting of halogen, (CrC4) alkyl, (CrC4) alkoxyl, nitro, trifluoromethyl, amino, (CrC4) alkylamino, (C5-C6) aryl and (C5-C6) heteroaryl wherein the heteroatom is selected from nitrogen, sulphur and oxygen. X is a nitrogen atom or a carbon atom, said carbon atom being optionally substituted with a substituent R3 selected from the group consisting of halogen, hydroxyl, nitro, trifluoromethyl, -SO3H, cyano, amino, (CrC4) alkylamino, (C1-C4) hydroxyalkylamino, (CrC4) aminoalkylamino, di-(CrC4) alkylamino, (CrC4) hydroxyalkyl, (CrC4) alkoxyl, (CrC4) thioalkyl, (CrC4) aminoalkyl, carboxy, (Cr C4) alkylcarboxyl, (CrC4) alkoxycarbonyl, (CrC4) alkylcarboxylate, (CrC4) alkylcarboxamide, aminocarbonyl (CrC4) alkyl, linear or branched (CrCβ) alkyl, phenyl optionally substituted with at least one substituent selected from the group consisting of a halogen atom, (CrC4) alkyl, (CrC4) alkoxyl, nitro, trifluoromethyl; amino, (C1-C4) alkylamino, benzyl optionally substituted on the methylene with a group selected from halogen, hydroxyl, amino, carboxy, (CrC4) alkylcarboxyl, (Cr C4) alkoxycarbonyl, (CrC4) alkylcarboxylate, (CrC4) alkylcarboxamide, aminocarbonyl (CrC4) alkyl, linear or branched (CrC6) alkyl, benzyl optionally substituted on the phenyl with a substituent selected from a halogen atom, (CrC4) alkyl, (CrC4) alkoxyl, nitro, trifluoromethyl, amino, (CrC4) alkylamino; (C5-C6) aryl and (C5-Cs) heteroaryl wherein the heteroatom is selected from nitrogen, sulphur and oxygen. and wherein
Y is selected from the group consisting of linear or branched (Ci-C6) alkyl; (C5-C6) aryl and (Cs-C6) heteroaryl wherein the heteroatom is selected from nitrogen, sulphur and oxygen; and
E is selected from the group consisting of hydroxyl, NH-B, an azide group and a halogen, where B is selected from the group consisting of H; linear or branched
(Ci-C6) alkyl; phenyl optionally substituted with at least one substituent selected from the group consisting of halogen, (C1-C4) alkyl, (Ci-C4) alkoxyl, nitro, trifluoromethyl, amino; benzyl, optionally substituted on the phenyl with a substituent selected from halogen atom, (CrC4) alkyl, (Ci-C4) alkoxyl, nitro, trifluoromethyl, amino, (C5-C6) aryl and (Cs-C6) heteroaryl wherein the heteroatom is selected from nitrogen, sulphur and oxygen, or E and D together form a saturated nitrogen-containing 5-membered ring; with the proviso that when A has the meaning that comprises Y, then D=NH2 and E=OH, and when A is NH2, E is selected from the group consisting of NH-B, an azide group and halogen.
These compounds act as developers in oxidation dyes and lead to an improvement in colour stability, with good resistance to light, washing, perspiration, rubbing and adverse atmospheric conditions, particularly with regard to red highlights. A combination of these compounds used as precursors together with suitable couplers in the presence of an oxidizing agent is used to produce a wide range of different colours and different tones.
The invention therefore relates to the use of said compounds for colouring keratin fibres and to compositions, mixtures and cosmetic preparations which comprise said compounds as colour precursors.
Preferred compounds and further advantageous aspects of the invention will be evident from the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
The present invention therefore relates to new compounds of formula (I) which are compounds derived from 1-ethyl-4,5-diamino-pyrazo!e. In another aspect, the invention concerns new compounds of formula (IV) which form part of the family of compounds of formula (I) wherein A is selected from the group consisting of NH2, -N=CH-Z, -NH-CH2-Z, D is selected from NH2 and N=CH- Z and E can be an azide group or halogen. Preferably said compound of formula (IV) is selected from the group consisting of:
Figure imgf000006_0001
Figure imgf000006_0002
wherein Z has the aforesaid meaning and E can be an azide group or a halogen, preferably chlorine. Specifically included in the invention are the corresponding reduction derivatives of the imino functions on the compounds of formula (IVb) and (IVc) described above, indicated by formula (IVd).
In another aspect, the invention concerns a compound of formula (I'), being part of the family of compounds of formula (I) wherein E is hydroxyl and A is -N=CH-Z or - NH-CH2-Z and D is NH2 or -N=CH-Z. The invention preferably relates to a compound derived from 1-hydroxyethyl-4,5-diamino-pyrazole substituted in the 4 and/or 5 position of formula (Ia) and (Ib):
Figure imgf000007_0001
and a corresponding reduced derivative of formula (Ic):
Figure imgf000007_0002
wherein:
Z has the above indicated meaning.
A further aspect of the invention concerns new compounds of formula (II), being part of the family of compounds of formula (I) wherein A is selected from NH2, -
N=CH-Z, -NH-CH2-Z, D is NH2 and E is -NH-B, where B has the previously .given meaning. Preferably, said compounds of formula (II) are compounds derived from
1-ethyl-4,5-diamino-pyrazole selected from the group consisting of compounds of formula (Ha) and (lib):
Figure imgf000007_0003
and a reduced derivative of formula (lie):
Figure imgf000008_0001
wherein Z and B have the aforedescribed meaning.
In a still further aspect, the invention concerns compounds of formula (II) which are derived from the intramolecular cyclization of the 4,5-diamino-pyrazole of formula 1 , wherein D and E form a dinitrogen-containing 5-membered ring and A is -N=CH-Z or -NH-CH2-Z. Said 1-ethyl-4,5-diamino-pyrazoIe derivative compounds are selected from the group consisting of compounds of formula (Ilia) and the relative reduction compounds of formula (lllb).
Figure imgf000008_0002
wherein Z has the same meaning as aforedescribed.
A further aspect of the present invention are dimerized derivatives of 1-ethyl-4,5- diamino-pyrazole of formula V, wherein E=OH and D=NH2, selected from compounds of formula (Va) and the respective reduction compounds of formula
(Vb):
Figure imgf000008_0003
where Y can be selected from a linear or branched (Ci-C6) alkyl group; (C5-C6) aryl and (C5-C6) heteroaryl wherein the heteroatom is selected from nitrogen, sulphur and oxygen.
The compounds of the present invention, being bases, can also be used in the form of salts with physiologically compatible acids such as hydrochloric or sulphuric acid and/or, if they contain aromatic OH groups, in the form of salts with organic bases, for example in the form of alkaline phenolates. According to the invention, A can comprise a substituent Z of formula :
Figure imgf000009_0001
Preferably Ri, R2, R4 and R5 are independently selected from hydrogen, hydroxyl, (CrC4) alkoxyl, SO3H, and R3, being present if X=C, is preferably selected from hydrogen, nitro, hydroxyl, (C1-C4) alkoxyl, carboxyl. More preferably, Z is selected from a group consisting of:
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0003
The compounds of formula (Ia) and (Ib) according to the present invention are prepared by reacting 1-hydroxyethyl-4,5-diamino-pyrazole sulphate (1) with a suitable aldehyde (2), wherein X, R-i, R2, R3 and R4 and R5 have the aforesaid meanings, preferably in a molar ratio of between 1 and 4 for the purposes of obtaining imino derivatives of the 1-hydroxyethyl-4,5-diamino-pyrazole of formula (Ia) and (Ib) substituted in positions 4 and/or 5 in accordance with the following scheme:
Figure imgf000011_0001
0) (2)
The reaction is preferably conducted in a mixture consisting of an aqueous sodium hydroxide solution and an organic solvent preferably chosen from methanol, ethanol, acetonitrile and tetrahydrofuran at a temperature of between 20 and
90°C.
The compounds of formula (Va) are prepared in a similar manner using a suitable dialdehyde; i.e. the process comprises the step of reacting the 1-hydroxyethyl-4,5- diamino-pyrazole of formula (1)
Figure imgf000011_0002
with a dialdehyde of formula (5)
Figure imgf000011_0003
(5)
in an aqueous sodium hydroxide solution or in a basic aqueous-alcoholic solution at a temperature in the range from 20 to 9O0C.
The compounds of formula (Ha) of the present invention are prepared starting from the aforedescribed compounds of formula (Ib) by an activation reaction of the hydroxyethyl chain by means of a derivative of p-toluenesulphonic acid. The tosylated intermediate (3) is then reacted with a suitable amine (4) wherein B has the already described meaning. The reaction sequence used can be summarized in the following scheme:
Figure imgf000012_0001
The reaction for forming the intermediate (3) is conducted in an organic solvent, preferably dichloromethane, in the presence of an organic base, such as pyridine, 4-dimethylaminopyridine or triethylamine. 4-toluenesulphonyl chloride is added to the solution at a temperature of 00C. The wished compound of formula (Ha) is prepared by a nucleophiϋc substitution reaction using the appropriate amine in an organic solvent at temperatures of between 50 and 1000C.
The compounds of formula (lib) are prepared from the corresponding compounds of formula (Ha) by acid treatment, preferably with hydrochloric acid or sulphuric acid.
The derivatives^of formula (Ilia); which are also-an aspect- of the-present-invention, are prepared starting from the tosylated intermediate (3) illustrated in the preceding scheme, by intramolecular substitution reaction in a suitable solvent at a temperature between 70 and 12O0C in the presence of a base in accordance with the scheme illustrated below:
Figure imgf000012_0002
The compounds of formula (IVc) of the present invention are prepared from the aforedescribed tosylated intermediate (3) by nucleophilic substitution by suitable reagents such as sodium azide. The compounds (IVa) and (IVb) are prepared by acid treatment of a compound of formula (IVc), preferably with hydrochloric acid.
As an alternative, for preparing the compounds of formula (IVa), (IVb) and (IVc) a process is provided comprising the reaction of 1-hydroxyethyl-4,5-diamino- pyrazole sulphate or of a compound of formula (Ia) or (Ib) according to claim 1 with halogenating agents, preferably thionyl chloride.
The reduction derivatives of formula (Ic), (lie), (lllb), (IVd) and (Vb) can be obtained from the corresponding imino precursor by catalytic hydrogenation, preferably in an alcoholic solvent at room temperature, using 10% Pd supported on carbon as catalyst.
A further aspect of the invention is a composition for keratin fibres in particular human keratin fibres such as hair, comprising, in a medium suitable for colouring, at least one compound of formula (I), (I1), (II), (III), (IV) and/or (V) as developer and at least one known coupler.
The developer, chosen from those described in the present invention, reacts with the known couplers for hair colouring by oxidation to produce a wide range of different colours, nuances and tones.
In addition the colours obtained with the compositions of the present invention are characterized by a good intensity, lustre, excellent colour fastness and good storage stability.
Compounds suitable for use as couplers in accordance with the present invention are selected from the group consisting of:
- phenol, resorcinol and naphthol and relative derivatives,
- metaphenylenediamine,
- heterocyclic derivatives and
- mixtures of the aforesaid components.
Among phenols, resorcinols and naphthols the following can be cited: 1 ,7-dihydroxynaphthalene, resorcinol, 4-chlororesorcinol, 1 -naphthol, 2-methyl-1- naphthol, 1-acetoxy-2-methylnaphthalene, 1 ,5-dihydroxynaphthalene, 2,7- di- hydroxynaphthalene, hydroquinone, 2-methylresorcinol, 1-hydroxy-6- aminonaphthalene-3-sulphonic acid, 2-isopropyl-5-methylphenol, 1 ,5-dihydroxy- 1 ,2,3,4-tetrahydro-naphthalene, 2-chlororesorcinol, 2,3-dihydroxy-1 ,4- naphthoquinone, 1 ,2,3-tri-hydroxybenzene and 1-naphthol-4-sulphuric acid. Among m-phenylenediamines the following can be cited: metaphenylenediamine, 2,4-di-aminophenoxyethanol, N,N-bis-(2-hydroxyethyl)-m-phenylenediamine, 2,6 diamino-toluene, 2-N,N-bis-(hydroxyethyl)-2,4-diaminophenetol] 1 ,3-bis(2,4- diaminophenoxy)-propane, 1-hydroxyethyl~2,4-diaminobenzene, 2-amino-4-(2- hydroxyethylamino)-anisole, 4-(2-aminoethoxy)-1 ,3-diaminobenzene, 2,4- diaminophenoxyacetic acid, 4,6-bis-(2-hydroxyethoxy)-m-phenylenediamine, 2,4- diamino-5-methylphenetol, 2,4-diamino-5-hydroxyethoxy-toluene, 2,4-dimethoxy- 1 ,3-diaminobenzene, 2,6-bis(2-hydroxyethyl)-aminotoluene and 3-(2,4- diaminophenoxy)-1 -propanol.
Among meta-aminophenols the following can be cited: m-aminophenol, 2-hydroxy- (4-carbamoylmethyIamino)-toluene, m-carbamoylmethylaminophenol, 6- hydroxybenzomorpholine, 2-hydroxy-4-aminotoluene, 2-hydroxy-4(2- hydroxyethylamino)-toluene, 4,6-dichloro-m-aminophenol, 2-methyl-m- aminophenol, 2-chloro-6-methyl-m-aminophenol, 4-chIoro-6-methyl-m- aminophenol, N-cyclopentyl-3-aminophenol, 2-(2-hydroxyethoxy)-5-aminophenol, 2-ch!oro-5-trif!uoroethy!aminophenol, N-hydroxyethy!-4-methoxy-6-methy!-m- amino--phenol.-and-5-aminor4-methoxy-2-methylp.heriol.. . . .
Among heterocyclic derivatives the following can be cited: 1-phenyl-3-methyl-5- pyrazolone, 6-methoxy-8-aminoquinoline, 2,6-di-hydroxy-4-methylpyridine, 5- hydroxy-1 ,4-benzodioxane, 3,4-methylene-dioxyphenol, 4-(2-hydroxyethylamino)- 1 ,2-methylene-dioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, 5-chloro-2,3- dihydroxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 3,4-methylendioxyaniline, 2,6-bis(2-hydroxyethoxy)-3,5-diaminopyridine, 5,6-dihydroxy-indole, 7-hydroxy- indole, 5-hydroxy-indole, 2-bromo-4,5-methylendioxyphenol, 6-hydroxy-indole, 2- amino-3-hydroxypyridine, 2-amino-3-hydroxypyridine, 2,6-diaminopyridine, 5-(3,5- diamino-2-piridyloxy)-1 ,3-dihydroxypentane, 3-(3,5-diamino-2-piridyloxy)-2- hydroxypropanol and indole-2,3-dione.
Other compounds suitable as secondary intermediates or couplers to be used in accordance with the present invention include for example: N-(3-dimethy!aminophenyl)-urea, 2,4-diamino-1-fluoro-5-methy!-benzene, 2,4- diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene, 2,4-di[(2-hydroxyethyl)- amino]-1 ,5-dimethoxy-benzene, 2,3-diamino-6-methoxypyridine, 3-amino-6- methoxy-2-(methylamino)-pyridine, 2,6-diamino-3>5-dimethoxypyridine, 1 ,3- diaminobenzene, 2,4-diamino-1 -(2-hydroxyethoxy)-benzene, 2,4-diamino-1 -(3- hydroxypropoxy)-benzene, 2,4-diamino-1-(3-methoxypropoxy)benzene, 2-amino- 1 -(2-hydroxyethoxy)-4-methylamino-benzene, 3-[di-(2-hydroxyethyl) aminojaniline, 4-amino-2-di[(2hydroxyethyIamino]-1 -ethoxybenzene, 5-methy!-2(1 - methylethy!)phenol, 3-[(2-hydroxyethyl)-amino]-aniline, 3-[(2-aminoethyl)-amino]- aniline, 1 ,3-diamino-2,4-dimethoxybenzene, 2,6-bis-(2-hydroxyethyl)-amino- toluene, 4-hydroxy-indole, 3-dimethylaminophenol, 2-amino-6-chloro-4- nitrophenol, 3-diethylaminophenol, 5-amino-2-methylphenol, 4-amino-3- methylphenol, 2-amino-5-methy!phenol, 5-amino-4~fluoro-2-methylphenol, 5- amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichloro-phenol, 5-amino-2,4- dichlorophenol, S-amino^-chloro-δ-methylphenol, 2-[(3-hydroxyphenyl)-amino]- acetamide, 5-[(2-hydroxyethyl)-amino]-2-methylphenol, 3[(2-hydroxyethyl)-amino]- phenol, 3-[(2-methoxyethyl)-amino]-phenol, 5-amino-2-ethylphenol, 2-(4-amino-2- hydroxyphenoxy)-ethanol), δ-^S-hydroxypropyπ-amino^-methylphenol.S-^^- .djhydroxypropyOraminpJ-^-methyJ^henpl, 3-[(2-Jhy_drpxyethyl)-amjnp]-2- methylphenol, 5-amino-4-chloro-2-methylphenol, 1 ,7-dihydroxynaphthalene, 2,3- dihydroxynaphthalene, 2,7- dihydroxynaphthalene, 2-methyl-1-naphthol acetate, 1 ,3-dihydroxybenzene, 1-chloro-2,4-di-hydroxybenzene, 2-chloro-1 ,3-di- hydroxybenzene, 1 ,2-dichloro-3,5-dihydroxy-4-methylbenzene, 1 ,5-dichIoro-2,4- dihydroxybenzene, 1 ,3-dihydroxy-2-methylbenzene, 1 ,3-dihydroxy-2,4- dimethylbenzene, 3,4-methylendioxyphenol, 3,4 methylendioxyaniline, 5[(2- hydroxyethyl) amino]1 ,3-benzodioxol, 6-bromo-1-hydroxy-3,4- methylendioxybenzene, 3,4-diaminobenzoic acid, 3,4-di-hydro-6-hydroxy-1 ,4(2H)- benzoxazine, 6-amino-3,4-dihydro-1 ,4(2H)-benzoxazine, 3-methyl-1-phenyl-5- pyrazolone, 5,6-di-hydroxyindoline, 4-hydroxyindole.
The compounds of the present invention used as developers, and the known couplers, are contained in the colouring composition of the present invention at a total concentration of between 0.01% and 20%, preferably between 0.2% and 6% by weight on the total weight of said composition.
The colouring composition of the present invention can be in the form of an aqueous solution or a mixture of water and organic solvent. However, for the specific application, the hair colourants of the present invention can be incorporated into cosmetic preparations as creams, gels or emulsions, whose composition comprises the aforesaid mixture of oxidation intermediates, together with additives suitable for this type of formulation.
These additives can, for example, comprise antioxidants, such as ascorbic acid, thioglycolic acid, sodium sulphite, as well as also essences, agents able to enhance product penetration, buffers, complexing agents, preservatives, wetting- agents, emulsifiers, thickeners and hair care products.
Additives of conventional use for solutions, creams, emulsions or gels comprise for example solvents such as water, lower aliphatic alcohols such as ethanol, propanol or isopropanol, glycerol, or glycols such as 1 ,2-propylene glycol; wetting- agents or emulsifiers chosen from anionic, cationic, amphoteric or non-ionic surfactant classes such as fatty alcohol sulphates, ethoxylated fatty alcohol sulphates, alkyl sulphonates, alkyl benzene sulphonates, nonylphenol ethoxylates, fatty acid alkanolamides and ethoxylated fatty acid esters; thickeners, such as higher fatty alcohols, starches, cellulose derivatives, petrolatum, paraffin oils and fatty acids; hair care products such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaines.
The aforesaid ingredients are present in those concentrations normally used for their specific purposes.
For example, the organic solvent is preferably present at a concentration between 0.5 and 20% by weight, more preferably between 2 and 10% by weight; effective wetting-agent and emulsifier concentrations are preferably between 0.1 and 30%, preferably between 1 and 15% by weight; effective thickener concentrations are preferably between 0.1 and 30% by weight and the hair care products are preferably used at concentrations between 0.1 and 5% by weight, calculated in each case on the total weight of the formulation.
In a further aspect, the invention concerns a colouring mixture, comprising the colouring composition or the cosmetic colouring preparation of the invention and an oxidizing mixture. Specifically the colouring mixture of the invention is prepared by mixing the colouring composition of the present invention or the relative cosmetic preparations obtained therefrom together with an oxidizing agent at the moment of use.
The oxidizing agent generally used for this type of mixture is principally hydrogen peroxide or an addition compound thereof with urea, melamine, sodium borate or sodium carbonate.
Firstly, an oxidizing composition, generally consisting of an aqueous solution preferably comprising 3-6% by weight of hydrogen peroxide or the aforesaid addition compounds, is mixed with the colouring composition of the present invention or with the cosmetic preparation obtained therefrom. The weight ratio of the colouring composition or the relative cosmetic preparation of the present invention to the oxidizing composition weight is preferably between 5:1 and 1 :3, more preferably between 1 :1 and 1 :2. Advantageously, higher concentrations of oxidizing agent are used mainly when the concentration of dye in the colouring composition is higher or when a stronger bleaching of the hair is required. The colouring mixtures of the present invention can be applied in a neutral or alkaline medium. The pH of the colouring composition or the cosmetic preparation obtained. therefrom js preferably between 7 and 11.5, Independently of whether it is a solution, emulsion, cream or gel, while the pH of the oxidizing composition is between 2 and 6.5. The pH value of the final colouring mixture in accordance with the present invention is affected by the alkali content of the colouring composition and the concentration of acids within the oxidizing composition. Adjusting the pH by base addition is preferably achieved with ammonia, with amines such as 2-amino-2-methyl-1-propanol, tris-(hydroxymethyl)- aminomethane, monoethanolamine, triethanolamine, or with inorganic bases such as sodium hydroxide, potassium hydroxide. Adjusting the pH by acid addition can be achieved with organic or inorganic acids, such as phosphoric acid, acetic acid, lactic acid, ascorbic acid, citric acid or tartaric acid.
The colouring composition of the present invention suitably mixed with the oxidizing agent is applied onto the hair in an amount depending on its thickness, generally being between 50 and 200 grams. The mixture is then left to react on the hair for a sufficient time at a temperature of between 15 and 4O0C, preferably at room temperature, for a time between 10 and 45 minutes, being preferably 30 minutes. Subsequently the mixture is removed from the hair by rinsing. Then the hair is washed with shampoo and dried.
Some non-limiting examples of the invention, of the chemical synthesis of some compounds of formula (I1), (II), (III) and (IV) and of the colouring compositions, as well as the results obtained with the final colouring mixtures containing the colouring compositions of the present invention are given below by way of illustration.
EXAMPLE 1 - Preparation of 1-hvdroxyethyl-4-(4-nitrobenzylidene)-amino-5- amino-pyrazole (compound of formula Ia)
A solution of 2.56 g of p-nitrobenzaldehyde in tetrahydrofuran is added to 4 g of 1- hydroxyethyl-4,5-diamino-pyrazole sulphate dissolved in a 2M aqueous solution of sodium hydroxide. The reaction mixture is heated to 600C and maintained under stirring at said temperature for 6 hours. It is then cooled to 00C and water is added until complete precipitation of a yellow solid. The precipitate is separated by filtration, washed with 20 ml of cold water and left to dry at room temperature.
Yield: 3.82 g of an orange solid. Melting point: 115-118°C.
1 H-NMR (DMSO-d6): δ = 3.67 ppm (m, 2H); 3.95 ppm (t, 2H); 4.94 ppm (t, OH);
5.77 ppm (s, wide, 2H); 7.63 ppm (s, 1 H); 8.04 ppm (d, JHH= 8.8 Hz, 2H); 8.26 ppm (d, JHH= 8.8 Hz, 2H); 8.58 ppm (s, 1H).
EXAMPLE 2 - Preparation of 4-{r5-amino-1-(2-hvdroxyethyl)-1 H-pyrazol-4-ylimino]- methyl)-2-methoxy-phenol (compound of formula Ia)
The compound was obtained by following the procedure indicated in example 1 , starting from 4 g of 1-hydroxyethyl-4,5-diamino-pyrazole sulphate dissolved in a
2M aqueous solution of sodium hydroxide to which 2.54 g of vanillin is added.
The reaction is conducted at 600C for 90 minutes then treated as described in example 1.
Yield: 4.3 g of a yellow solid.
1H-NMR (DMSO-de): δ = 3.66 ppm (m, 2H); 3.76 ppm (s, 3H); 3.95 ppm (t, 2H);
4.91 ppm (t, OH); 5.57 ppm (s, wide, 2H); 6.81 ppm (d, JHH= 8 Hz, 1H); 7.20 ppm
(d, JHH= 8 Hz, 1 H); 7.49 ppm (s, 1H); 7.60 ppm (s, 1H); 8.66 ppm (s, 1H). EXAMPLE 3 - Preparation of 1-hydroxyethyl-4,5-bis-(benzylidene-amino)-pyrazole
(compound of formula Ib)
5 g of 1-hydroxyethyl-4,5-diamino-pyrazole sulphate are dissolved in 20.85 ml of a
2M aqueous solution of sodium hydroxide. 6.75 ml of benzaldehyde and 30 ml of acetonitrile are added to the solution. The mixture is left under stirring for 3 days at 500C. Subsequently it is left to cool at room temperature and the solvents evaporated. The residue is dissolved in 200 ml of dichloromethane and washed twice with 150 ml of water. The organic phase is then separated, dried by means of anhydrous sodium sulphate and evaporated. The solid obtained is washed 5 times with 20 ml of petroleum ether and left to dry at room temperature.
Yield: 6.59 g of a yellow solid. Melting point: 104-1080C.
1 H-NMR (DMSO-d6): δ = 3.77 ppm (m, 2H); 4.30 ppm (t, 2H); 4.87 ppm (t, OH);
7.48-7.59 ppm (m, 6H); 7.84-7.90 ppm (m, 3H); 7.98-8.02 ppm (m, 2H); 8.85 ppm
(s, 1H); 9.29 ppm (s, 1 H).
EXAMPLE 4 - Preparation of 2-(2-benzylamino-ethyl)N4-benzylidene-3,4-diamino-
2H-pyrazole (compound of formula Ha)
Step 1 - Preparation of 2-[4,5-bis-(benzylideneamino)-pyrazol-1-yl]-ethyl-ester of toluene-4-sulphonic acid.
4_g_ ot 1 -hyd.roxyjethyU4., 5rbLsr:(.be.nzyJid.Lne-arjQiQo)rpy.razQle_pιiep_ared,as_dB.sjcribe.d_ in example 2, are dissolved in 70 ml of anhydrous dichloromethane. 3 g of A- dimethylamino-pyridine are added to the solution followed, at a temperature of
0°C, by 4.8 g of 4-toluene-suIphonyl chloride. After 2 hours at 00C, the reaction mixture is brought back to room temperature and left under stirring for 3 days. It is then diluted with 130 ml of dichloromethane and 3 washes are carried out with 100 ml of water. The organic phase is anhydrified by means of anhydrous sodium sulphate and evaporated. The developer 2-[4,5-bis-(benzy!ideneamino)-pyrazol-1- yl]-ethyl-ester of toluene-4-sulphonic acid is crystallized from absolute ethanol.
Yield: 4.51 g of a yellow solid. Melting point 78-80°C.
1 H-NMR (DMSO-d6): δ = 2.24 ppm (s, 3H); 4.45 ppm (m, 4H); 7.22-7.93 (m, 15H);
8.83 ppm (s, 1 H); 9.09 ppm (s, 1 H).
Step 2 - Preparation of 2-(2-benzy!amino-ethyI)-N4-benzylidene-3,4-diamino-2H- pyrazole. 3.57 ml of benzylamine are added to 4 g of 2-[4,5-bis-(benzy]ideneamino)-pyrazol-
1-yl]-ethyl-ester of toIuene-4-sulphonic acid dissolved in 90 ml of anhydrous acetonitrile. The mixture is left under stirring for 24 hours at 600C. It is then left for 30 minutes at 00C during which time a precipitate forms which is removed by filtration. The solution is then evaporated. The product is purified by column chromatography over silica gel using as eluent a 98:2 dichloromethane/methanol mixture.
Yield: 2.26 g of a yellowish-brown solid. Melting point: 73-75°C.
1 H-NMR (DMSO-d6): δ = 2.80 ppm (t, JHH= 12.8 Hz, 2H); 3.70 ppm (s, 2H); 3.97 ppm (t, JHH= 12.8 Hz, 2H); 5.60 ppm (s, wide, 2H); 7.24-7.50 ppm (m, 8H); 7.56 ppm (s, 1H); 7.79-7.84 ppm (m, 2H); 8.49 ppm (s, 1 H).
EXAMPLE 5 - Preparation of 2-(2-benzylamino-ethvO-3,4~diamino-2H-pyrazole trihydrochloride (compound of formula lib)
2-(2-Benzylamino-ethy!)-N4-benzylidene-3,4-diamino-2H-pyrazole is prepared as described in example 4. 4.94 ml of a 37% aqueous solution of hydrochloric acid are added to the crude reaction product derived from step 2 dissolved in 20 ml of acetonitrile. The mixture is left under stirring for 2 hours at room temperature and thereafter for 1 hour at -200C. The precipitate formed is filtered off and washed 6 times with 5 ml of a 90:10 absolute ethanol/methanol mixture and finally with dichloromethane.
Yield: 1.95 g of a pale orange solid. Melting point: decomposes at 2200C.
1 H-NMR (DMSO-d6): δ = 3.24 ppm (t, JHH= 6 Hz, 2H); 4.14 ppm (m, 2H); 4.31 ppm (t, JHH= 6 Hz, 2H); 6.36 ppm (s, wide, 3H)1 7.31 ppm (s, 1H); 7.04-7.44 ppm
(m, 3H); 7.54-7.56 (m, 2H); 9.61 ppm (s, wide, 2H); 10.02 ppm (s, wide, 3H).
EXAMPLE 6 - Preparation of (2.3-dihvdro-1H-imidazoπ ,2-bbyrazol-7-vn- benzylideneamine (compound IHa)
1 g of 2-[4,5-bis-(benzylideneamino)-pyrazol-1-yl]-ethyl-ester of toluene-4- sulphonic acid, prepared as described in example 4 - step 1 , is dissolved in 60 ml of acetonitrile, to which 0.59 ml of triethylamine are added. The mixture is maintained under reflux for 48 hours. It is then left to cool to room temperature and the solvent evaporated. The compound is purified by column chromatography over silica gel using a 98:2 dichloromethane/methanol mixture as the eluent. Yield: 290 mg of a yellowish-brown solid. Melting point: 154-158°C.
1H-NMR (DMSO-d6): δ = 3.89-4.12 ppm (m, 4H); 6.43 ppm (s, wide, 1 H); 7.38-
7.75 ppm (m, 6H); 8.46 ppm (s, 1 H).
EXAMPLE 7 - Preparation of the 2-(2-azido-ethvO-3,4-diamino-2H-pyrazole hydrochloride (compound of formula IVa)
1.3 g of sodium azide are added to 3.16 g of the 2~[4,5-bis-(benzylideneamino)- pyrazol-1-yl]-ethyl-ester of totuene-4-sulphonic acid, prepared as described in example 4 - step 1 , and dissolved in 55 ml of anhydrous dimethylformamide. The mixture is maintained under stirring for 18 hours at 700C. Subsequently the suspended solid is removed by filtration and the solvent is evaporated. The residue is dissolved in 100 ml of dichloromethane and washed twice with 100 ml of water. The organic phase is anhydrified by means of anhydrous sodium sulphate and evaporated. The solid residue is dissolved in 20 ml of acetonitrile to which 1.95 ml of an 37% aqueous hydrochloric acid solution are added. The mixture is left under vigorous stirring for 4 hours then the solid is filtered and washed with 50 ml of acetonitrile.
Yield: 1.25 g of a yellow solid. Melting point: 109-1120C.
I H-NMR (DMSO-d6): δ = 3.63 ppm (t, JHH= 5.6 Hz, 2H); 4.09 ppm (t, JHH= 5.6
-HZ.-2H); .5.02-ppm-(s,-wide,_3H); 7.32-ppm (s, -1H); 9.9£Lppm-(sr.wide,-3H).
IR (KBr): 2101 cm-1 (-N3).
EXAMPLE 8 - Preparation of 2-{5-amino-4-f(4-(r5-amino-1-(2-hvdroxyethvn-1 H— pyrazol-4-ylimino1-methyl}-benzylidene)-amino]-pyrazol-1-yl}-ethanol (compound of formula Va)
1.67 g of terephthalic dialdehyde are added to 6 g of 1-hydroxyethyl-4,5-diamino- pyrazole sulphate dissolved in 25 ml of a 2M aqueous solution of sodium hydroxide. After adding 50 ml of water, the mixture is left under stirring for 1 hour at 650C. The mixture is then brought to O0C and the solid formed is separated by filtration, washed with cold water and dried at 400C.
Yield: 4.52 g of a yellow solid. Melting point: 127-131°C.
1 H-NMR (DMSO-d6): δ = 3.68 ppm (m, 4H); 3.95 ppm (t, 4H); 4.95 ppm (t, 2 OH);
5.50 ppm (s, wide, 4H); 7.58 ppm (s, 2H); 7.85 ppm (s, 4H); 8.51 ppm (s, 2H).
EXAMPLE 9 - Preparation of 1-hvdroxyethyl-4-benzylamino-5-amino-pyrazole (compound Ic)
2 g of 1-hydroxyethyl-4-(4-benzylidene)-amino-5-amino-pyrazole, obtained according to the procedure described in example 1 , are dissolved in 100 ml of methanol and hydrogenated under atmospheric pressure and at room temperature in a H2 saturated environment with 0.2 g of catalyst (10% Pd/C).
After 90 minutes the catalyst is removed by filtration and the solvent evaporated to dryness. The crude product obtained is purified by column chromatography over silica gel (eluent: 9:1 dichloromethanol/methanol).
Yield: 1.53 g of a yellow solid. Melting point: 112-1160C.
1 H-NMR (DMSO~d6): δ = 3.67 ppm (q, 2H); 3.95 ppm (t, 2H); 4.47 ppm (s, 2H);
4.94 ppm (t, OH); 5.77 ppm (s, wide, 2H); 5.98 ppm (s, wide, 1 H); 7.52-7.75 ppm
(m, 6H).
EXAMPLES OF COSMETIC COLOURANT PREPARATIONS
Cosmetic preparations were prepared using the compositions of the invention comprising the coupling agents and the compounds of the invention indicated in
Table 2 and the additives of table 1.
TABLE 1 - Cosmetic colourant preparation
Figure imgf000022_0001
Figure imgf000023_0001
immediately prior to application the aforesaid composition was mixed with twice its weight of a 6% aqueous solution of hydrogen peroxide. The mixture obtained was applied to locks of white yak hair and held in position for 30 minutes at room temperature. The locks were then washed with shampoo, rinsed with water and dried. The resulting shades are listed in table 2 below.
TABLE 2
Figure imgf000023_0002
Figure imgf000024_0001
26 2-amino-6~chloro-4- Yellow-orange nitrophenol
27 6-amino-m-cresol Red-violet
28 4-amino-m-cresol Copper
29 2-amino-3- Mahogany red hydroxypyridine
30 2,6-dihydroxyethylamino- Violet toluene
31 2-{5-amino-4-[(4-{[5-amino-1-(2- resorcinol Mahogany red hydroxyethyl)-1 H-pyrazol-4- ylimino]-methyl}-benzylidene)- amino]-pyrazol-1-yl}-ethanol
(compound of example 8)
-32- 4-a mi nσ-ιτFcreso I" "Copper
33 m-aminophenol Red
34 2-amino~6-chloro-4- Yellow-orange nitrophenol
As can be seen from the table, the compounds of the invention allow oxidation dyes to be obtained in red nuances. The dyes thus applied were evaluated and it was found that said nuances were resistant to external agents, such as climatic conditions.

Claims

CLAIMS 1. A compound derived from 1-ethyl-4,5-diamino-pyτazole of formula (I)
Figure imgf000026_0001
(I) wherein
D is NH2 or N=CH-Z;
A is selected from the group consisting of NH2, -N=CH-Z, -NH-CH2-Z,
Figure imgf000026_0002
where Z is a substituent of formula
Figure imgf000026_0003
where
R-i, R2, R4 and R5 are the same or different and are selected from the group consisting of H, halogen, hydroxy!, nitro, trifluoromethyl, -SO3H, cyano, amino, (Cr C4) alkylamino, (CrC4) hydroxyalkylamino, (Ci-C4) aminoalkylamino, di-(Ci-C4) alkylamino, (Ci-C4) hydroxyalkyl, (C1-C4) alkoxyl, (CrC4) thioalkyl, (CrC4) aminoalkyl, carboxy, (C1-C4) alkylcarboxyl, (C1-C4) alkoxycarbonyl, (CrC4) alkylcarboxylate, (CrC4) alkylcarboxamide, aminocarbonyl (CrC4) alkyl, linear or branched (CrC6) alkyl, phenyl optionally substituted with at least one substituent selected from the group consisting of a halogen atom, (CrC4) alkyl, (CrC4) alkoxyl, nitro, trifluoromethyl, amino, (CrC4) alkylamino; benzyl optionally substituted on the methylene with a group selected from halogen, hydroxyl, amino, carboxy, (CrC4) alkylcarboxyl, (CrC4) alkoxycarbonyl, (CrC4) alkylcarboxylate, (CrC4) alkylcarboxamide, aminocarbonyl (CrC4) alkyl, linear or branched (C1- C6)alkyl, benzyl optionally substituted on the phenyl with a substituent selected from the group consisting of halogen, (CrC4) alkyl, (CrC4) alkoxyl, nitro, trifluoromethyl, amino, (CrC4) alkylamino, (C5-C6) aryl and (C5-C6) heteroaryl wherein the heteroatom is selected from nitrogen, sulphur and oxygen. X is a nitrogen atom or a carbon atom, said carbon atom being optionally substituted with a substituent R3 selected from the group consisting of halogen, hydroxyl, nitro, trifluoromethyl, -SO3H, cyano, amino, (CrC4) alkylamino, (CrC4) hydroxyalkylamino, (CrC4) aminoalkylamino, di-(CrC4) alkylamino, (CrC4) hydroxyalkyl, (CrC4) alkoxyl, (CrC4) thioalkyl, (CrC4) aminoalkyl, carboxy, (Cr C4) alkylcarboxyl, (CrC4) alkoxycarbonyl, (CrC4) alkylcarboxylate, (CrC4) alkylcarboxamide, aminocarbonyl (CrC4) alkyl, linear or branched (CrC6) alkyl, phenyl optionally substituted with at least one substituent selected from the group consisting of a halogen atom, (CrC4) alkyl, (CrC4) alkoxyl, nitro, trifluoromethyl; amino, (CrC4) alkylamino, benzyl optionally substituted on the methylene with a group selected from halogen, hydroxyl, amino, carboxy, (CrC4) alkylcarboxyl, (Cr C4) alkoxycarbonyl, (CrC4) alkylcarboxylate, (C1-C4) alkylcarboxamide, aminocarbonyl (CrC4) alkyl, linear or branched (CrC6) alkyl, benzyl optionally substituted on the phenyl with a substituent selected from a halogen atom, (CrC4) alkyl, (Ci-C4) alkoxyl, nitro, trifluoromethyl, amino, (CrC4) alkylamino; (C5-C6) aryl and (C5-C6) heteroaryl wherein the heteroatom is selected from nitrogen, sulphur and oxygen. and wherein
Y is selected from the group consisting of linear or branched (Ci-C6) alkyl; (C5-C6) aryl and (C5-C6) heteroaryl wherein the heteroatom is selected from nitrogen, sulphur and oxygen; and
E is selected from the group consisting of hydroxyl, NH-B, an azide group and a halogen, where B is selected from the group consisting of H; linear or branched
(Ci-C6) alkyl; phenyl possibly substituted with at least one substituent selected from the group consisting of halogen, (Ci-C4) alkyl, (Ci-C4) alkoxyl, nitro, trifluoromethyl, amino; benzyl, optionally substituted on the phenyl with a substituent selected from halogen atom, (CrC4) alkyl, (Ci-C4) alkoxyl, nitro, trifluoromethyl, amino; (C5-C6) aryl and (C5-C6) heteroaryl wherein the heteroatom is selected from nitrogen, sulphur and oxygen, or E and D together form a saturated nitrogen-containing 5-membered ring; with the proviso that: when A has the meaning that comprises Y, then D=NKb and E=OH, and when A is NH2, E is selected from the group consisting of NH-B, an azide group and halogen.
2. Compound derived from 1-ethyl-4,5-diamino-pyrazole according to claim 1 wherein A is selected from the group consisting of NH2, -N=CH-Z, -NH-CH2-Z,
D is selected from NH2 and N=CH-Z and E can be an azide group or halogen.
3. Compound derived from 1-ethyl-4,5-diamino-pyrazoIe according to claim 2 selected from the group consisting of the compound of formula (IVa), the compound of formula (IVb)1 the compound of formula (IVc) and the compound of formula (IVd):
Figure imgf000028_0001
(IVa) (IVb) (IVc)
Figure imgf000029_0001
(IVd) wherein Z has the meaning given in claim 1 and E is an azide group or halogen.
4. Compound derived from 1-ethyl-4,5-diamino~pyrazole according to claim 1 , wherein
E=OH, said compound being selected from the group consisting of a compound of formula (Ia), a compound of formula (Ib) and a compound of formula (Ic):
Figure imgf000029_0002
Figure imgf000029_0003
where Z has the meaning given in claim 1.
5. Compound derived from 1-ethyl-4,5-diamino-pyrazole according to claim 1 , wherein
E=NH-B,
D=NH2 and
A is selected from the group consisting of NH2, -N=CH-Z, -NH-CH2-Z.
6. Compound derived from 1-ethyl-4,5-diamino-pyrazole according to claim 5, selected from the group consisting of the compound of formula (Ha), the compound of formula (lib) and the compound of formula (lie):
Figure imgf000030_0001
wherein Z and B have the same meaning as given in claim 1.
7. Compound derived from 1-ethyl-4,5-diamino-pyrazole according to claim 1 , wherein D and E form a saturated nitrogen-containing 5-membered cyclic ring, said compound being selected from the group consisting of a compound of formula (Ilia) and a compound of formula (UIb):
Figure imgf000030_0002
wherein Z has the same meaning as given in claim 1.
8. Compound derived from 1-ethy!-4,5-diamino-pyrazo!e according to claim 1 - selected- -from- the-group-Gonsisting-Θf--the~GΘmpΘund-Θf--formula-(Va)— and-a- - compound of formula (Vb)
Figure imgf000030_0003
where Y has the meaning as given in claim 1.
9. Compound derived from 1-ethyl-4,5-diamino-pyrazole according to any one of claims 1 to 7, wherein, in the substituent Z, R1, R2, R4 and R5 are independently selected from hydrogen, hydroxy!, (Ci-C4) alkoxyl, SO3H.
10. Compound derived from 1-ethyl-4,5-diamino-pyrazole according to any one of claims 1 to 7, wherein R3, present if X=C, is preferably selected from hydrogen, nitro, hydroxyl, (Ci-C4) alkoxyl, carboxyl.
11. Compound derived from 1-ethyl-4,5-diamino-pyrazole according to any one of claims 1 to 7 and 8 to 9 wherein Z is selected from the group consisting of:
Figure imgf000031_0001
Figure imgf000031_0002
12. A oxidative-type colouring composition for keratin fibres comprising at least one of the compounds derived from 1-ethyl-4,5-diamino-pyrazo!e according to any one of claims 1 to 11 or a salt thereof with an organic or inorganic acid and at least one coupling agent in a suitable colouring medium.
13. Composition according to claim 12 wherein said keratin fibres are hair.
14. Colouring composition according to claims 12 or 13 wherein said at least one coupling agent is selected from the group consisting of
- phenol, resorcinol and naphthol and relative derivatives,
- metaphenylenediamine,
- heterocyclic derivatives and - mixtures of the aforesaid components.
15. Colouring composition according to any one of claims 12-14 wherein said composition comprises one or more of the compounds derived from 1-ethyl-4,5- diamino-pyrazole and the coupling agent at a total concentration in the range from 0.01 % to 20% by weight on the total weight of said composition.
16. Colouring composition according to claim 15 wherein said composition comprises one or more of the compounds derived from 1-ethyl-4,5-diamino- pyrazole at a total concentration in the range from 0.2% to 6% by weight on the total weight of said composition.
17. Colouring composition according to any one of claims 12-16 wherein said suitable colouring medium is an aqueous medium.
18. Colouring composition according to claim 17 wherein said suitable aqueous medium essentially consists of water.
19. Colouring composition according to claim 17 wherein said aqueous medium comprises an organic solvent.
20. Composition according to claim 19 wherein said organic solvent is selected from the group consisting of alcohol, glycols and glycerol.
21. Use of a compound derived from 1-ethyl-4,5-diamino-pyrazole according to any one of claims 1 to 11 for oxidative-type colouring of keratin fibres.
22. A cosmetic preparation comprising a colouring composition according to any one of claims 12 to 20 and at least one cosmetic additive.
23. Cosmetic preparation according to claim 22 wherein said cosmetic preparation is in the form of a suspension, cream, gel or emulsion.
24. Preparation according to claim 22 or claim 23 wherein the at least one cosmetic additive is selected from the group consisting of alcohols, antioxidants, essences, agents able to enhance product penetration, buffers, complexing agents, preservatives, wetting-agents, emulsifiers, thickeners, surfactants and hair care products.
25. A colouring mixture comprising a colouring composition according to any one of claims 12-20 or a cosmetic preparation according to any one of claims 22-24, and an oxidizing composition.
26. Mixture according to claim 25 wherein said colouring composition or said cosmetic preparation and said oxidizing composition are in a weight ratio in the range from 5:1 to 1 :3.
27. Mixture according to claim 26 wherein said weight ratio is in the range from 1:1 to 1 :2.
28. Mixture according to any one of claims 25-27 wherein said oxidizing composition is an aqueous solution containing from 3% to 6% by weight of hydrogen peroxide or one of its addition compounds with urea, melamine, sodium borate or sodium carbonate.
29. Process for dyeing keratin fibres comprising the following steps:
1) applying an effective amount of the mixture according to any one of claims 25 to 28
2) allowing the mixture to react for a time period ranging from 10 to 45 minutes, at a temperature in the range from 15 to 4O0C
3) rinsing, washing and drying the aforesaid keratin fibres.
30. Process according to claim 29 wherein the keratin fibres are hair.
31. Process for preparing a compound of formula (Ia) and formula (Ib) according to claim 4 comprises the reaction of 1-hydroxyethyl-4,5-diamino-pyrazole sulphate (1)
Figure imgf000033_0001
with the aldehyde of formula (2)
(2)
Figure imgf000033_0002
wherein R1, R2, R3 and R5 have the meanings as given in claim 1 , in an aqueous sodium hydroxide solution or in a basic aqueous-alcoholic solution at a temperature in the range from 20 to 90°C.
32. Process according to claim 31 wherein when a basic aqueous-alcoholic solution is used, the alcohol is selected from the group consisting of methanol, ethanol and isopropanol.
33. Process for preparing the compound of formula (Va) according to claim 8, comprising the step of reacting the 1-hydroxyethyl-4,5-diamino-pyrazole sulphate of formula (1)
with a dialdehyde of formula (5)
Figure imgf000034_0002
(5) in an aqueous sodium hydroxide solution or in a basic aqueous-alcoholic solution at a temperature in the range from 20 to 90°C.
34. Process for preparing a compound of formula (Ha) according to claim 6 comprising the following steps:
- reacting a compound of formula (Ib) with 4-toluenesulphonyl chloride in an organic solvent in the presence of an organic base at a temperature from 0-250C and
- reacting the intermediate (3) obtained with an amine (4) in an organic solvent at a temperature between 50 and 1000C.
Figure imgf000035_0001
wherein Z and B have the meanings indicated in claim 1.
35. Process according to claim 34 wherein said organic solvent is selected from dichloromethane and acetonitrile and said organic base is selected from pyridine, 4-dimethylaminopyridine and triethylamine.
36. Process for preparing a compound of formula (lib) according to claim 6 comprising the step of acid treating a compound of formula (Ha).
37. Process for preparing a compound of formula (Ilia) according to claim 7 comprising an intramolecular substitution reaction of an intermediate (3),
Figure imgf000035_0002
wherein Z has the meaning given in claim 1 , in an organic solvent at a temperature from 70 to 12O0C in the presence of a base.
38. Process for preparing the compound of formula (IVc) according to claim 3 comprising the reaction of an intermediate (3)
Figure imgf000036_0001
(3) with a nucleophilic reagent in an organic solvent at 7O0C.
39. Process according to claim 38 wherein said nucleophilic reagent is sodium azide and said organic solvent is dimethylformamide.
40. Process for preparing a compound of formula (IVb) and of formula (IVa) according to claim 3 comprising the step of acid treating a compound of formula (IVc).
41. Process for preparing a compound of formula (IVa), (IVb) and (IVc) according to claim 3 comprising the reaction of 1-hydroxyethyl-4,5-diamino-pyrazole sulphate, or of a compound of formula (Ia) or (Ib) according to claim 1 , with halogenating agents, preferably thionyl chloride.
42. Process for preparing the compounds of formula (IVd), (Ic), (lie), (IHb) and (Vb) according to claims 3, 4, 6, 7 and 8, respectively, comprising the catalytic hydFogenatiΘn-of~the-cor-respondingHmino-precursor-of-formαla"(1Vb")r(IVσ)r(la")7 (Ib), (Ha), (Ilia) and (Va) according to claims 3, 4, 6, 7 and 8.
43. Process according to claim 42 wherein said catalytic hydrogenation is carried out in an alcoholic solvent at room temperature in the presence of a 10% Pd/C catalyst.
PCT/IB2007/003087 2006-10-17 2007-10-17 Compounds derived from 1 -ethyl-4,5-diamino-pyrazole and their use for oxidative dyeing of keratin fibres WO2008047210A2 (en)

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US9060953B2 (en) 2012-02-16 2015-06-23 The Procter & Gamble Company 1-hexyl-1H-pyrazole-4,5-diamine hemisulfate, and its use in dyeing compositions
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