U.S. patent application number 09/843842 was filed with the patent office on 2001-09-13 for compositions for dyeing keratinous fibres, containing 3-aminopyrazolo[1,5-a]pyrimidines, method of dyeing, and novel 3-aminopyrazolo[1,5-a]pyrimidines.
This patent application is currently assigned to L'Oreal S.A.. Invention is credited to Fadli, Aziz, Lagrange, Alain, Terranova, Eric.
Application Number | 20010020310 09/843842 |
Document ID | / |
Family ID | 9514119 |
Filed Date | 2001-09-13 |
United States Patent
Application |
20010020310 |
Kind Code |
A1 |
Terranova, Eric ; et
al. |
September 13, 2001 |
Compositions for dyeing keratinous fibres, containing
3-aminopyrazolo[1,5-a]pyrimidines, method of dyeing, and novel
3-aminopyrazolo[1,5-a]pyrimidines
Abstract
The invention relates to novel compositions for the oxidation
dyeing of keratinous fibres, comprising at least one
3-aminopyrazolo[1,5-a]-pyrimid- ine, to the method of dyeing which
employs this composition, to novel
3-aminopyrazolo[1,5-a]pyrimidines and to the process for their
preparation.
Inventors: |
Terranova, Eric; (Bois
Colombes, FR) ; Fadli, Aziz; (Chelles, FR) ;
Lagrange, Alain; (Coupvray, FR) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT &
DUNNER LLP
1300 I STREET, NW
WASHINGTON
DC
20005
US
|
Assignee: |
L'Oreal S.A.
|
Family ID: |
9514119 |
Appl. No.: |
09/843842 |
Filed: |
April 30, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09843842 |
Apr 30, 2001 |
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09204559 |
Dec 3, 1998 |
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6248137 |
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Current U.S.
Class: |
8/405 ; 8/406;
8/409 |
Current CPC
Class: |
C07D 487/04 20130101;
A61K 8/4953 20130101; A61Q 5/10 20130101 |
Class at
Publication: |
8/405 ; 8/406;
8/409 |
International
Class: |
A61K 007/13 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 3, 1997 |
FR |
97 15244 |
Claims
What is claimed is:
1. A composition for the oxidation dyeing of keratinous fibres
wherein said composition comprises, in a medium suitable for
dyeing, at least one 3-aminopyrazolo[1,5-a]pyrimidine chosen from
compounds of formula (I) and acid and base addition salts thereof:
9in which R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are identical or
different and represent a hydrogen atom, a halogen atom, a
C.sub.1--C.sub.4 alkyl radical, a C.sub.1--C.sub.4 trifluoroalkyl
radical, a C.sub.1--C.sub.4 alkoxy radical, an aryl radical, a
C.sub.1--C.sub.4 monohydroxyalkyl radical, a C.sub.2--C.sub.4
polyhydroxyalkyl radical, a C.sub.1--C.sub.4 (C.sub.1--C.sub.4
alkoxy)alkyl radical, a C.sub.1--C.sub.4 aminoalkyl radical, a
C.sub.1--C.sub.4 (C.sub.1--C.sub.4 alkyl)aminoalkyl radical, a
C.sub.1--C.sub.4 di(C.sub.1--C.sub.4 alkyl)aminoalkyl radical, a
C.sub.1--C.sub.4 monohydroxy (C.sub.1--C.sub.4 alkyl)aminoalkyl
radical or a C.sub.1--C.sub.4 di[hydroxy(C.sub.1--C.sub.4
alkyl)]aminoalkyl radical.
2. The composition of claim 1 wherein said keratinous fibers are
human keratinous fibers.
3. The composition of claim 2 wherein said human keratinous fibers
are hair.
4. The composition of claim 1, wherein said at least one
3-aminopyrazolo[1,5-a]-pyrimidine is chosen from:
pyrazolo[1,5-a]pyrimidi- n-3-ylamine;
5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;
5-methylpyrazolo[1,5-a]pyrimi- din-3-ylamine;
7-methoxypyrazolo[1,5-a]pyrimidin-3-ylamine;
5-methoxypyrazolo[1,5-a]pyrimidin-3-ylamine;
7-methoxy-5-methylpyrazolo[1- ,5-a]pyrimidin-3-ylamine;
2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidin-3-yl- amine;
2-methoxy-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine;
5,7-di-trifluoromethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
2,6-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
2-chloro-5,7-dimethylpyra- zolo[1,5-a]pyrimidin-3-ylamine; 7-methyl
2-tert-butyl-5- trifluoromethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine;
and the acid and base addition salts thereof.
5. The composition of claim 1, wherein said at least one
3-aminopyrazolo[1,5-a]-pyrimidine is chosen from:
pyrazolo[1,5-a]pyrimidi- n-3-ylamine;
5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
2-methoxy-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
5,7-di-trifluoromethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;
5-methylpyrazolo[1,5-a]pyrimi- din-3-ylamine; and acid and base
addition salts thereof.
6. The composition of claim 1, wherein said at least one,
3-aminopyrazolo[1,5-a]-pyrimidine represents from 0.0005 to 12% by
weight relative to the total weight of the dyeing composition.
7. The composition of claim 6, wherein said at least one
3-aminopyrazolo[1,5-a]-pyrimidine represents from 0.005 to 6% by
weight relative to the total weight of the dyeing composition.
8. The composition of claim 1, wherein said medium suitable for
dyeing comprises water, a water/alcohol mixture or a mixture of
water and at least one organic solvent chosen from C.sub.1--C.sub.4
lower alkanols, glycerol, glycols and glycol ethers, aromatic
alcohols, and mixtures thereof.
9. The composition of claim 8, wherein said at least one organic
solvent is present in proportion ranging from 1 to 40% by weight
approximately relative to the total weight of the dye
composition.
10. The composition of claim 9, wherein said at least one organic
solvent is present in proportions ranging from 5 to 30%.
11. The composition of claim 1, where said composition has a pH
ranging from 3 to 12.
12. The composition of claim 11, wherein said composition has a pH
ranging from 5 to 11.
13. The composition of claim 1, wherein said composition contains
at least one coupler.
14. The composition of claim 13, wherein said at least one coupler
is chosen from meta-phenylenediamines, meta-aminophenols,
meta-diphenols and heterocyclic couplers.
15. The composition of claim 14, wherein said at least one coupler
is chosen from 2-methyl-5-aminophenol,
5-N-(.beta.-hydroxyethyl)amino-2-meth- ylphenol, 3-aminophenol,
1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenze- ne,
4-chloro-1,3-dihydroxy-benzene,
2,4-diamino-1-(.beta.-hydroxyethoxy)be- nzene,
2-amino-4-(.beta.-hydroxyethylamino)-1 -methoxybenzene,
1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol,
.alpha.-naphthol, 6-hydroxyindole, 4-hydroxyindole,
4-hydroxy-N-methylindole, 6-hydroxyindoline,
2,6-dihydroxy4-methylpyridin- e, 1 H-3-methylpyrazol-5-one,
1-phenyl-3-methylpyrazol-5-one, and the addition salts thereof.
16. The composition of claim 13, wherein said at least one coupler
represents from 0.0001 to 10% by weight relative to the total
weight of the dyeing composition.
17. The composition of claim 16, where said at least one coupler
represents from 0.005 to 5% by weight relative to the total weight
of the dyeing composition.
18. The composition of claim 1, wherein said composition
additionally contains at least one additional oxidation base.
19. The composition of claim 18, wherein said additional oxidation
base is chosen from para-phenylenediamines,
bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols
and heterocyclic bases which are different from the
3-aminopyrazolo[1,5-a]pyrimidines of formula (I).
20. The composition of claim 19, wherein said
para-phenylenediamines are chosen from para-phenylenediamine,
para-tolylenediamine, 2-chloro-para-phenylenediamine,
2,3-dimethyl-para-phenylene-diamine,
2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine,
2,5-dimethyl-para-phenylenediamine,
N,N-dimethyl-para-phenylenediamine,
N,N-diethyl-para-phenylenediamine,
N,N-dipropyl-para-phenylenediamine,
4-amino-N,N-diethyl-3-methylaniline,
N,N-bis(.beta.-hydroxyethyl)-para-ph- enylenediamine,
4-N,N-bis(.beta.-hydroxyethyl)amino-2-methylaniline,
4-N,N-bis(.beta.-hydroxyethyl)amino-2-chloroaniline,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-fluoro-para-phenylenediami- ne,
2-isopropyl-para-phenylenediamine,
N-(.beta.-hydroxypropyl)-para-pheny- lenediamine,
2-hydroxymethyl-para-phenylenediamine,
N,N-dimethyl-3-methyl-para-phenylenediamine,
N,N-(ethyl,.beta.-hydroxyeth- yl)-para-phenylenediamine,
N-(.beta.,.gamma.-dihydroxypropyl)-para-phenyle- nediamine,
N-(4'-aminophenyl)-para-phenylenediamine,
N-phenyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-para-phenylenedi- amine,
2-.beta.-acetylaminoethyloxy-para-phenylenediamine,
N-(.beta.-methoxyethyl)-para-phenylenediamine and the acid addition
salts thereof.
21. The composition of claim 20, wherein said para-phenyldiamines
are chosen from para-phenylenediamine, para-tolylenediamine,
2-isopropyl-para-phenylenediamine,
2-.beta.-hydroxyethyl-para-phenylenedi- amine,
2-.beta.-hydroxyethyloxy-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
N,N-bis(.beta.-hydroxyethyl)-para-phe- nylenediamine,
2-chloro-para-phenylenediamine, 2-.beta.-acetylaminoethylox-
y-para-phenylenediamine, and the acid addition salts thereof.
22. The composition of claim 19, wherein said
bisphenylalkylenediamines are chosen from
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,-
3-diaminopropanol, N,N'-bis(.beta.-hydroxyethyl)-N,N
'-bis(4'-aminophenyl)ethylenediamine,
N,N'-bis(4-aminophenyl)-tetramethyl- enediamine,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetrameth-
ylenediamine, N,N '-bis(4-methylaminophenyl)tetramethylenediamine,
N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)-ethylenediamine,
1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the acid addition
salts thereof.
23. The composition of claim 19, wherein said para-aminophenols are
chosen from para-aminophenol, 4-amino-3-methylphenol,
4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,
4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,
4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,
4-amino-2-(.beta.-hydroxyethylaminomethyl)ph- enol,
4-amino-2-fluorophenol, and the acid addition salts thereof.
24. The composition claim 19, wherein said ortho-aminophenols are
chosen from 2-aminophenol, 2-amino-5-methylphenol,
2-amino-6-methylphenol, 5-acetamido-2-aminophenol, and the acid
addition salts thereof.
25. The composition of claim 19, where said other heterocyclic
bases are chosen from pyridine derivatives, pyrimidine derivatives
and pyrazole derivatives.
26. The composition of claim 18, wherein said at least one
additional oxidation base represents from 0.0005 to 12% by weight
of the total weight of the dyeing composition.
27. The composition of claim 26, wherein said at least one
additional oxidation base represents from 0.005 to 6% by weight of
the total weight of the dyeing composition.
28. The composition of claim 1, wherein said acid addition salts
are chosen from hydrochlorides, hydrobromides, sulphates, citrates,
succinates, tartrates, lactates and acetates.
29. The composition of claim 1, wherein said base addition salts
are chosen from sodium hydroxide solution, potassium hydroxide
solution, aqueous ammonia, and amines.
30. The composition of claim 1, wherein said composition
additionally contains at least one direct dye.
31. The composition of claim 30, wherein said at least one direct
dye is chosen from the nitro derivatives of benzene.
32. The composition of claim 1, wherein said composition
additionally contains at least one adjuvant chosen from anionic,
cationic, nonionic, amphoteric and zwitterionic surfactants,
anionic, cationic, nonionic, amphoteric and zwitterionic polymers,
organic and inorganic thickeners, antioxidants, penetration agents,
sequestrants, fragrances, buffers, dispersants, conditioners, film
forming agents, ceramides, preserving agents and opacifiers.
33. The composition of claim 32, wherein said conditioners are
chosen from modified and unmodified, volatile and nonvolatile
silicones.
34. A method for dyeing keratinous fibres, comprising the steps of
contacting said fibres for a time sufficient to achieve color
development, with a dye composition of claim 1 or a salt
thereof.
35. The method of claim 34 wherein said keratinous fibers are human
keratin fibers.
36. The method of claim 35 wherein said human keratinous fibers are
hair.
37. The method of claim 34, wherein said dye composition is mixed
at the time of use with an oxidizing composition comprising, in a
medium suitable for dyeing, at least one oxidizing agent present in
an amount sufficient for color development.
38. The method of claim 34, wherein said dye composition
additionally contains at least one oxidation catalyst.
39. The method of claim 37, wherein said at least one oxidizing
agent is chosen from hydrogen peroxide, urea peroxide, alkali metal
bromates, persalts, and enzymes.
40. The method of claim 39, wherein said persalts are chosen from
perborates and persulphates.
41. The method of claim 39, wherein said enzymes are chosen from
peroxidases and oxidoreductases with 2 unpaired electrons.
42. The method of claim 37, wherein said oxidizing composition is
added simultaneously, sequentially, or separately at the time the
dye composition is employed.
43. The method of claim 34, wherein said time ranges from 3 to 50
minutes.
44. The method of claim 43, wherein said time ranges from 5 to 30
minuts.
45. The method of claim 37, wherein said oxidizing composition has
a pH ranging from 3 to 12.
46. The method of claim 45, wherein said oxidizing composition has
a pH ranging from 5 to 11.
47. The method of claim 37, wherein said oxidizing composition
additionally contains at least one adjuvant chosen from anionic,
cationic, nonionic, amphoteric and zwitterionic surfactants,
anionic, cationic, nonionic, amphoteric and zwitterionic polymers,
organic and inorganic thickeners, antioxidants, penetration agents,
sequestrants, fragrances, buffers, dispersants, conditioners, film
forming agents, ceramides, preserving agents and opacifiers.
48. The method of claim 34, wherein said color development occurs
at an acidic, neutral or alkaline pH.
49. The composition of claim 1, wherein said composition further
comprises an oxidizing composition comprising, in a medium suitable
for dyeing, at least one oxidizing agent present in an amount
sufficient for color development of said keratinous fibers.
50. The composition of claim 49, wherein said oxidizing agent is
chosen from hydrogen peroxide, urea peroxide, alkali metal
bromates, persalts, and enzymes.
51. The composition of claim 50, wherein said persalts are chosen
from perborates and persulphates.
52. The composition of claim 50, wherein said enzymes are chosen
from peroxidases and oxidoreductases with 2 unpaired electrons.
53. The composition of claim 49, wherein said oxidizing composition
has a pH ranging from 3 to 12.
54. The composition of claim 53, wherein said oxidizing composition
has a pH ranging from 5 to 11.
55. The composition of claim 49, wherein said oxidizing composition
additionally contains at least one adjuvant chosen from anionic,
cationic, nonionic, amphoteric and zwitterionic surfactants,
anionic, cationic, nonionic, amphoteric and zwitterionic polymers,
organic and inorganic thickeners, antioxidants, penetration agents,
sequestrants, fragrances, buffers, dispersants, conditioners, film
forming agents, ceramides, preserving agents and opacifiers.
56. The composition of claim 1, wherein said composition contains
at least one oxidation catalyst.
57. The composition of claim 1, said composition being in the form
of a liquid, a cream, a gel or any other form suitable for dyeing
keratinous fibers.
58. A method of making at least one
3-aminopyrazolo[1,5-a]pyrimidine chosen from compounds of formula
(I) or an acid or base addition salt thereof: 10in which R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 are identical or different and
represent a hydrogen atom, a halogen atom, a C.sub.1--C.sub.4 alkyl
radical, a C.sub.1--C.sub.4 trifluoroalkyl radical, a
C.sub.1--C.sub.4 alkoxy radical, an aryl radical, a
C.sub.1--C.sub.4 monohydroxyalkyl radical, a C.sub.2--C.sub.4
polyhydroxyalkyl radical, a C.sub.1--C.sub.4 (C.sub.1--C.sub.4
alkoxy)alkyl radical, a C.sub.1--C.sub.4 aminoalkyl radical, a
C.sub.1--C.sub.4 (C.sub.1--C.sub.4 alkyl)aminoalkyl radical, a
C.sub.1--C.sub.4 di(C.sub.1--C.sub.4 alkyl)aminoalkyl radical, a
C.sub.1--C.sub.4 monohydroxy (C.sub.1--C.sub.4 alkyl)aminoalkyl
radical or a C.sub.1--C.sub.4 di[hydroxy(C.sub.1--C.sub.4
alkyl)]aminoalkyl radical comprising the steps of: (a) carrying out
a cyclocondensation reaction between a 3(5)-amino-4-nitropyrazole
derivative and a .beta.-keto ester, or a .beta.-diketone or a
.beta.-keto aldehyde to form a nitro derivative
pyrazolo[1,5-a]pyrimidine; and (b) reducing the nitro derivative of
(a) to give a 3-amino-pyrazolo[1 ,5-a]pyrimidine of formula (I) or
(c) nitrating the nitro derivative of (a) followed by reducing to
give the 3-amino-pyrazolo.
59. A multi-compartment dyeing device or kit for dyeing keratin
fibers, comprising at least two compartments, wherein a first
compartment contains a dyeing composition according to claim 1 and
a second compartment contains an oxidizing composition.
60. A 3-Aminopyrazolo[1,5-a]pyrimidine chosen from:
pyrazolo[1,5-a]pyrimidin-3-ylamine;
5,6,7-trimethylpyrazolo[1,5-a]pyrimid- in-3-ylamine;
7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;
5-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;
7-methoxypyrazolo[1,5-a]pyrim- idin-3-ylamine;
5-methoxypyrazolo[1,5-a]pyramid-3-ylamine;
7-methoxy-5-methylpyrazolo[1,5-a]pyrimidin-3 -ylamine;
2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine;
5,7-di-trifluoromethylpyrazolo[1,5-a]pyrimidin-3-ylamine; and the
acid and base addition salts thereof.
Description
[0001] The invention relates to novel compositions for the
oxidation dyeing of keratinous fibres, comprising at least one
3-aminopyrazolo[1,5-a]-pyrimidine as an oxidation base, the method
of dyeing which employs this composition, novel
3-amino-pyrazolo[1,5-a]pyrim- idines, and the process for their
preparation.
[0002] It is well known to dye keratinous fibres, and in particular
human hair, using dyeing compositions comprising oxidation dye
precursors, such as ortho- or para-phenylenediamines and ortho- or
para-aminophenols, and heterocyclic compounds, such as
diaminopyrazole derivatives, which are generally referred to as
oxidation bases. The oxidation dye precursors, or oxidation bases,
are colourless or lightly coloured compounds which, when combined
with oxidizing products, are able to give rise to coloured
compounds and dyes by a process of oxidative condensation. These
compounds have the common feature of possessing one amino group and
one hydroxyl group or two amino groups, which give them their
oxidation-base character.
[0003] It is also known that the shades obtained with these
oxidation bases can be varied by combining them with couplers or
coloration modifiers, the latter being chosen in particular from
aromatic meta-diamines, meta-aminophenols, meta-diphenols and
certain heterocyclic compounds.
[0004] The diversity of molecules employed as oxidation bases and
couplers makes it possible to obtain a wide range of colours.
[0005] The "permanent" coloration obtained by these oxidation dyes
should optimally meet, certain conditions. Hence it should have no
toxicological effects, should allow shades of the desired intensity
to be obtained, and should have good resistance to external agents
(light, inclement weather, washing, permanent-waving, perspiration
and friction).
[0006] The dyes should also allow white hairs to be covered and,
finally, they should be as unselective as possible--in other words,
they should allow the smallest possible differences in coloration
to be produced over the entire length of a single keratinous fibre,
which may vary in condition of sensitization or damage from its tip
to its root.
[0007] Patent application DE 4 029 324 proposes the use of certain
2-hydroxypyrazolo[1,5-a]pyrimidines, which may be substituted by
C.sub.1--C.sub.4 alkyl radicals in positions 4, 5 and/or 6, as
couplers for the oxidation dyeing of keratinous fibres.
[0008] Patent application DE 4 133 957 also proposes the use of
certain pyrazolo-[1,5-a]pyrimidine derivatives, belonging to the
class of the tetrahydropyrazolo[1,5-a]pyrimidines, as oxidation dye
precursors for the oxidation dyeing of keratinous fibres.
[0009] The inventors have now made the unexpected and surprising
discovery that a new class of 3-aminopyrazolo[1,5-a]pyrimidines of
formula (I) defined below, some of which are themselves novel, are
suitable for use as an oxidation base. These compounds contain only
a single amino group that makes it possible to obtain dyeing
compositions which lead to colorations which are strong and have
good resistance to external agents (light, inclement weather,
washing, permanent-waving, perspiration and friction). Finally,
these compounds can be easy to synthesize.
[0010] These discoveries form the basis of the present
invention.
[0011] The invention therefore provides a composition for the
oxidation dyeing of keratinous fibres, and in particular human
keratinous fibres such as hair, that comprises, in a medium
suitable for dyeing, at least one 3-aminopyrazolo[1,5-a]pyrimidine
chosen from compounds of formula (I) below and acid and base
addition salts thereof, as oxidation base: 1
[0012] in which
[0013] R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are identical or
different and represent a hydrogen atom, a halogen atom, a
C.sub.1--C.sub.4 alkyl radical, a C.sub.1--C.sub.4 trifluoroalkyl
radical, a C.sub.1--C.sub.4 alkoxy radical, an aryl radical, a
C.sub.1--C.sub.4 monohydroxyalkyl radical, a C.sub.2--C.sub.4
polyhydroxyalkyl radical, a C.sub.1--C.sub.4 (C.sub.1--C.sub.4
alkoxy)alkyl radical, a C.sub.1--C.sub.4 aminoalkyl radical, a
C.sub.1--C.sub.4 (C.sub.1--C.sub.4 alkyl)aminoalkyl radical, a
C.sub.1--C.sub.4 di(C.sub.1--C.sub.4 alkyl)aminoalkyl radical, a
C.sub.1--C.sub.4 monohydroxy (C.sub.1--C.sub.4 alkyl)aminoalkyl
radical or a C.sub.1--C.sub.4 di[hydroxy(C.sub.1--C.sub.4
alkyl)]aminoalkyl radical. Among the
3-aminopyrazolo[1,5-a]pyrimidines of formula (I) which can be used
as an oxidation base in the compositions in accordance with the
invention generally preferred 3-aminopyrazolo [1,5-a]pyrimidines
are:
[0014] pyrazolo[1 ,5-a]pyrimidin-3-ylamine;
[0015] 5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0016] 5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0017] 7-methylrpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0018] 5-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0019] 7-methoxypyrazolo[1,5-a]pyrimidin-3-ylamine;
[0020] 5-methoxypyrazolo[1,5-a]pyrimidin-3-ylamine;
[0021] 7-methoxy-5-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0022] 2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidin-3 -ylamine;
[0023]
2-methoxy-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0024] 5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0025]
5,7-di-trifluoromethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0026] 2,6-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0027] 2-chloro-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0028]
7-methyl-2-tert-butyl-5-trifluoromethylpyrazolo-[1,5-a]pyrimidin-3--
ylamine; and the acid or base addition salts thereof.
[0029] Among the 3-aminopyrazolo[1,5-a]pyrimidines of formula (I)
which can be used as an oxidation base in the compositions in
accordance with the invention particularly preferred
3-aminopyrazolo [1,5-a]pyrimidines are:
[0030] pyrazolo[1,5-a]pyrimidin-3-ylamine;
[0031] 5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0032] 5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0033] 2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0034] 2-methoxy
5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0035]
5,7-di-trifluoromethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0036] 7-methyl pyrazolo[1,5-a]pyrimidin-3-ylamine;
[0037] 5-methyl pyrazolo[1,5-a]pyrimidin-3- ylamine;
[0038] and the acid or base addition salts thereof.
[0039] The great majority of the 3-aminopyrazolo[1,5-a]pyrimidines
of formula (1) are compounds which are known in the pharmaceutical
field and are described, in particular, in patent applications
EP-A-0 433 854 and EP-A-0 433 855.
[0040] The 3-aminopyrazolo[1,5-a]pyrimidine or -pyrimidines of
formula (I) above makes or make up preferably from 0.0005 to 12% by
weight approximately relative to the total weight of the dyeing
composition and, more preferably, from 0.005 to 6% by weight,
approximately, of the total weight.
[0041] A medium (or vehicle) suitable for dyeing is, for example,
water, water/alcohol mixtures, and a mixture of water and at least
one organic solvent to dissolve any compounds which are not
sufficiently water soluble. Preferred organic solvents are, for
example, C.sub.1--C.sub.4 lower alkanols, such as ethanol and
isopropanol; glycerol; glycols and glycol ethers such as
2-butoxyethanol, propylene glycol, propylene glycol monomethyl
ether and diethylene glycol monoethyl and monomethyl ether, and
aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar
products and mixtures thereof.
[0042] The solvents can be present in proportions preferably
ranging from 1 to 40% by weight approximately relative to the total
weight of the dyeing composition, and even more preferably from 5
to 30% by weight approximately.
[0043] The pH of the dyeing composition in accordance with the
invention generally ranges from 3 to 12, approximately, and
preferably approximately from 5 to 11. It can be adjusted to the
desired value by means of acidifying or basifying agents commonly
used in the dyeing of keratinous fibres, or by using conventional
buffer systems.
[0044] Preferred acidifying agents include, for example, mineral
acids or organic acids, such as hydrochloric acid, orthophosphoric
acid, sulphuric acid, carboxylic acids such as acetic acid,
tartaric acid, citric acid and lactic acid, and sulphonic
acids.
[0045] Preferred basifying agents include, for example, of aqueous
ammonia, alkali metal carbonates, alkanolamines such as mono-, di-
and triethanolamines and derivatives thereof, sodium hydroxide,
potassium hydroxide, and the compounds of the following formula
(II): 2
[0046] in which W is a propylene residue optionally substituted by
a hydroxyl radical or a C.sub.1--C.sub.4 alkyl radical; R.sub.5,
R.sub.6, R.sub.7 and R.sub.8, which may be identical or different,
represent a hydrogen atom, a C.sub.1--C.sub.4 alkyl radical or a
C.sub.1--C.sub.4 hydroxyalkyl radical.
[0047] In a preferred embodiment, the oxidation dyeing composition
in accordance with the invention additionally includes at least one
coupler in order to modify or enrich with glints the shades
obtained by employing the compounds of formula (I).
[0048] The couplers which can be used in the oxidation dyeing
compositions in accordance with the invention may be chosen from
the couplers used conventionally in oxidation dyeing, among which
generally preferred couplers are: meta-phenylenediamines,
meta-aminophenols, meta-diphenols and heterocyclic couplers.
[0049] More particularly preferred couplers are chosen from
2-methyl-5-aminophenol,
5-N-(.beta.-hydroxyethyl)amino-2-methylphenol, 3-aminophenol,
1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,
4-chloro-1,3-dihydroxy-benzene,
2,4-diamino-1-(.beta.-hydroxyethoxy)benze- ne,
2-amino-4-(.beta.-hydroxyethylamino)-1-methoxybenzene,
1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol,
.alpha.-naphthol, 6- hydroxyindole, 4-hydroxyindole,
4-hydroxy-N-methylindole, 6-hydroxyindoline,
2,6-dihydroxy-4-methylpyridi- ne, 1H-3-methylpyrazol-5-one,
1-phenyl-3-methylpyrazol-5-one, and the addition salts thereof.
[0050] When present, the coupler(s) preferably represent(s) from
0.0001 to 10% by weight approximately relative to the total weight
of the dyeing composition, and even more preferably from 0.005 to
5% by weight approximately relative to this weight.
[0051] The dyeing composition in accordance with the invention may
additionally comprise, as well as the above-defined dyes, at least
one additional oxidation base chosen from the oxidation bases which
are conventionally employed in oxidation dyeing, among which
preferred oxidation bases are: para-phenylenediamines,
bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols
and heterocyclic bases which are different from the
3-aminopyrazolo[1,5-a]-pyrimidines of formula (I) that are employed
in accordance with the invention.
[0052] Among the para-phenylenediamines, preferred
para-phenylenediamines are: para-phenylenediamine,
para-tolylenediamine, 2-chloro-para-phenylene- diamine,
2,3-dimethyl-para-phenylene-diamine, 2,6-dimethyl-para-phenylened-
iamine, 2,6-diethyl-para-phenylenediamine,
2,5-dimethyl-para-phenylenediam- ine,
N,N-dimethyl-para-phenylenediamine,
N,N-diethyl-para-phenylenediamine- ,
N,N-dipropyl-para-phenylenediamine,
4-amino-N,N-diethyl-3-methylaniline,
N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
4-N,N-bis(.beta.-hydroxyethyl)amino-2-methylaniline,
4-N,N-bis(.beta.-hydroxyethyl)amino-2-chloroaniline,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-fluoro-para-phenylenediami- ne,
2-isopropyl-para-phenylenediamine,
N-(.beta.-hydroxypropyl)-para-pheny- lenediamine,
2-hydroxymethyl-para-phenylenediamine,
N,N-dimethyl-3-methyl-para-phenylenediamine,
N,N-(ethyl,.beta.-hydroxyeth- yl)-para-phenylenediamine,
N-(.beta.,.gamma.-dihydroxypropyl)-para-phenyle- nediamine,
N-(4'-aminophenyl)-para-phenylenediamine,
N-phenyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-para-phenylenedi- amine,
2-.beta.-acetylaminoethyloxy-para-phenylenediamine,
N-(.beta.-methoxyethyl)-para-phenylenediamine and the acid addition
salts thereof.
[0053] Among the abovementioned para-phenylenediamines more
preferred para-phenylenediamines are: para-phenylenediamine,
para-tolyienediamine, 2-isopropyl-para-phenylenediamine,
2-.beta.-hydroxyethyl-para-phenylenedi- amine,
2-.beta.-hydroxyethyloxy-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
N,N-bis(.beta.-hydroxyethyl)-para-phe- nylenediamine,
2-chloro-para-phenylenediamine, 2-.beta.-acetylaminoethylox-
y-para-phenylenediamine, and the acid addition salts thereof.
[0054] Among the bisphenylalkylenediamines preferred
bisphenylalkylenediamines are:
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'--
aminophenyl)-1,3-diaminopropanol,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4-
'-aminophenyl)ethylenediamine,
N,N'-bis(4-aminophenyl)-tetramethylenediami- ne, N,N
'-bis(.beta.-hydroxyethyl)-N,N '-bis(4-aminophenyl)tetramethylened-
iamine, N,N'-bis(4-methylaminophenyl)tetramethylenediamine,
N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)-ethylenediamine,
1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the acid addition
salts thereof.
[0055] Among the para-aminophenols, preferred para-aminophenols
are: para-aminophenol, 4-amino-3-methylphenol,
4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,
4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,
4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,
4-amino-2-(.beta.-hydroxyethylaminomethyl)ph- enol,
4-amino-2-fluorophenol, and the acid addition salts thereof.
[0056] Among the ortho-aminophenols, preferred ortho-aminophenols
are: 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol,
5-acetamido-2-aminophenol, and the acid addition salts thereof.
[0057] Among the heterocyclic bases, preferred heterocyclic bases
are: pyridine derivatives, pyrimidine derivatives and pyrazole
derivatives.
[0058] When used, the additional oxidation base(s) preferably
represent(s) from 0.0005 to 12% by weight approximately relative to
the total weight of the dyeing composition and, more preferably
from 0.005 to 6% by weight approximately relative to this
weight.
[0059] In general terms, the acid addition salts used within the
scope of the dyeing compositions of the invention (compounds of
formula (I), additional oxidation bases and couplers) are chosen in
particular from hydrochlorides, hydrobromides, sulphates, citrates,
succinates, tartrates, lactates and acetates.
[0060] The base addition salts used within the scope of the dyeing
compositions of the invention (compounds of formula (I), additional
oxidation bases and couplers) are chosen from sodium hydroxide
solution, potassium hydroxide solution, aqueous ammonia, or
amines.
[0061] The dyeing composition in accordance with the invention can
additionally comprise one or more direct dyes which can be chosen
in particular from the nitrated dyes of the benzene series.
[0062] The dyeing composition in accordance with the invention can
also contain various adjuvants used conventionally in hair dyeing
compositions, such as anionic, cationic, nonionic, amphoteric or
zwitterionic surfactants or mixtures thereof, anionic, cationic,
nonionic, amphoteric or zwitterionic polymers or mixtures thereof,
organic or inorganic thickeners, antioxidants, penetration agents,
sequestrants, fragrances, buffers, dispersants, conditioners such
as, for example, modified or unmodified, volatile or nonvolatile
silicones, film formers, ceramides, preservatives and
opacifiers.
[0063] The person skilled in the art can select the optional
complementary compound(s) such that the advantageous properties
intrinsically associated with the dyeing composition in accordance
with the invention are not, or not substantially, adversely
affected by the additions envisaged.
[0064] The dyeing composition according to the invention may be in
various forms, such as in the form of liquids, creams, gels or any
other form which is suitable for dyeing keratinous fibres, and in
particular human hair.
[0065] The invention also provides a process for dyeing keratinous
fibres, and in particular human keratinous fibres such as hair
using the dyeing composition as defined above.
[0066] According to this process, at least one dyeing composition
as defined above is applied to the fibres for a period which is
sufficient to develop the desired coloration either in air or with
the aid of an oxidizing agent. The dyeing composition can
optionally include oxidation catalysts in order to accelerate the
process of oxidation.
[0067] According to one embodiment of the process of the invention,
the dyeing of the fibres can be carried out without the addition of
an oxidizing agent, solely by contact with the oxygen in the
air.
[0068] According to another embodiment of the process of the
invention at least one dyeing composition as defined above is
applied to the fibres, the colour being developed at an acidic,
neutral or alkaline pH with the aid of an oxidizing agent which is
added right at the time when the dyeing composition is employed or
which is present in an oxidizing composition which is applied
simultaneously or sequentially and separately.
[0069] According to this embodiment of the dyeing process of the
invention, the above-described dyeing composition is preferably
mixed at the time of use with an oxidizing composition comprising,
in a medium suitable for dyeing, at least one oxidizing agent which
is present in an amount sufficient for color development. The
resulting mixture is subsequently applied to the keratinous fibres
and left to act for approximately 3 to 50 minutes, preferably for
approximately 5 to 30 minutes, after which the fibres are rinsed,
optionally washed with shampoo, rinsed again and dried.
[0070] The oxidizing agent present in the oxidizing composition as
defined above can be chosen from the oxidizing agents
conventionally used for the oxidation dyeing of keratinous fibres,
among which preferred oxidizing agents are: hydrogen peroxide, urea
peroxide, alkali metal bromates, and persalts, such as perborates
and persulphates, and enzymes, such as peroxidases and
oxidoreductases with 2 unpaired electrons. It is particularly
preferred to use hydrogen peroxide.
[0071] The pH of the oxidizing composition comprising the oxidizing
agent as defined above is such that, after it has been mixed with
the dyeing composition, the pH of the resulting composition applied
to the keratinous fibres preferably ranges from approximately 3 to
12, and more preferably, from 5 to 11. The pH can be adjusted to
the desired value by means of acidifying or basifying agents which
are commonly employed in the dyeing of keratinous fibres and are as
defined above.
[0072] The oxidizing composition as defined above can also contain
various adjuvants which are conventionally employed in hair-dyeing
compositions and are as defined above.
[0073] The composition which is ultimately applied to the
keratinous fibres can be in various forms, such as in the form of
liquids, creams or gels or in any other form suitable for dyeing
keratinous fibres, and in particular human hair.
[0074] Another aspect of the invention is a multi-compartment
dyeing device or "kit" or any other multi-compartment packaging
system a first compartment of which contains the dyeing composition
as defined above and a second compartment of which contains the
oxidizing composition as defined above. These devices may be
equipped with a means for delivering the desired mixture onto the
hair, such as the devices described in patent FR-2 586 913 the
disclosure of which is specifically incorporated by reference
herein.
[0075] Certain compounds of formula (I) which are used as an
oxidation base within the scope of the present invention are novel
and, to that extent, are further provided by the invention.
[0076] These novel 3-aminopyrazolo[1,5-a]pyrimidines are:
[0077] pyrazolo[1,5-a]pyrimidin-3-ylamine;
[0078] 5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0079] 7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0080] 5-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0081] 7-methoxypyrazolo[1,5-a]pyrimidin-3-ylamine;
[0082] 5-methoxypyrazolo[1,5-a]pyrimidin-3-ylamine;
[0083] 7-methoxy-5-methyl pyrazolo[1,5-a]pyrimidin-3-ylamine;
[0084] 2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0085] 5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine;
[0086] 5,7-ditrifluoromethylpyrazolo[1,5-a]pyrimidin-3-ylamine; and
the acid or base addition salts thereof.
[0087] These novel 3-aminopyrazolo[1,5-a]pyrimidines can be
prepared by methods which are known and are described in the
literature.
[0088] For example, a cyclocondensation reaction is carried out
between a 3(5)-amino-4-nitropyrazole derivative and a .beta.-keto
ester, a .beta.-diketone or a .beta.-keto aldehyde in order to form
the pyrazolo[1,5-a]pyrimidine structure. This reaction is carried
out in a manner according to the methods described in the following
references:
[0089] EP-A-628559 BEIERSDORF-LILLY
[0090] G. Muhmel, R. Hanke, E. Breitmaier, Synthesis, 673,
1982.
[0091] The resulting nitro derivative is subsequently reduced to
give the expected 3-amino-pyrazolo[1,5-a]pyrimidine in accordance
with known processes (R. Hemmer, W. Lurken in Houben-Weyl,
"Methoden der Organischen Chemie" [Methods of Organic Chemistry],
Vol. E16d, p. 815 ff.). Preference is given to the use of metals
such as palladium (Pd), platinum (Pt) or nickel (Ni) in the
presence of a hydrogen donor such as ammonium formate, formic acid
or else cyclohexene in place of hydrogen (S. Ram, R. E.
Ehrenkaufer, Synthesis, 91, 1988). It is also possible to use
metals such as zinc (Zn), tin (Sn) or iron (Fe) in an acidic medium
such as aqueous hydrochloric acid or aqueous acetic acid,
optionally with addition of an organic solvent such as methanol,
ethanol or tetrahydrofuran.
[0092] Alternatively, it is possible to carry out a
cyclocondensation reaction between a 3(5)-aminopyrazole derivative
and a .beta.-keto ester, a .beta.-diketone or a .beta.-keto
aldehyde in order to form the pyrazolo[1,5-a]pyrimidine structure.
This reaction is carried out in a manner according to the methods
described in the following references:
[0093] R. H. Springer, M. B. Scholten, D. E. O'Brien, T. Novinson,
J. P. Miller, R. K. Robins, J. Med. Chem., 25, 235, 1982.
[0094] T. Novinson, R. K. Robins, T. R. Matthews, J. Med. Chem.,
20, 386, 1977.
[0095] K. Nagahara, H. Kawano, S. Sasaoka, C. Ukawa, T. Hirama, A.
Takada, J. Heterocyclic Chemistry, 239, 1994.
[0096] It is also possible to carry out a nitration reaction of
this pyrazolo[1,5-a]pyrimidine structure by well-known methods. By
way of example, reference is made to the following document:
[0097] K. Senga, T. Novinson, R. H. Springer, R. P. Rao, D. E.
O'Brien, R. K. Robins, H. R. Wilson, J. Med. Chem., 18(3), 312,
1975.
[0098] The nitro derivative is subsequently reduced as above to
give the expected 3-aminopyrazolo-[1,5-a]pyrimidine.
[0099] The 3-aminopyrazolo[1,5-a]pyrimidines of formula (I) and the
addition salts thereof, as defined above, can likewise be used as
an oxidation base in and for the preparation of compositions
intended for photography or chemical imaging.
[0100] The following examples serve to illustrate the invention
without, however, limiting its scope.
SYNTHESIS EXAMPLES
Example 1
Synthesis of pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride
[0101] 3
[0102] a) Preparation of 3-nitropyrazole[1,5-a]pyrimidine
[0103] 44 g of malonaldehyde bisdiethyl acetal, 300 cc of acetic
acid and 30 g of 4-nitro-2H-pyrazol-3-ylamine hydrochloride
(prepared according to H. Dorn and H. Dilcher, Liebigs Ann. Chem.,
707, 141, 1967) were introduced into a 500 ml three-necked
round-bottomed flask fitted with a magnetic stirrer, a condenser
and a thermometer. The medium was refluxed for 5 hours and then
approximately 100 cc of acetic acid were evaporated off. The solid
was filtered off and washed with diisopropyl ether. Drying under
vacuum and over phosphoric anhydride at 40.degree. C. yielded 27.7
g of 3-nitropyrazolo[1,5-a]pyrimidine (yield=92.5%).
[0104] .sup.1H NMR (DMSO-d.sub.6; 200 MHz): 3.34 (s; 1H); 7.51
(dxd; J1=4.3 Hz and J2=6.9 Hz; 1H); 9.04 (dxd; J1=4.3 Hz and J3=1.2
Hz; 1H); 9.09 (s; 1H); 9.44 (dxd; J2=6.9 Hz and J3=1.2 Hz; 1H)
[0105] b) Preparation of pyrazolo[1,5-a]pyrimidin-3-ylamine
hydrochloride
[0106] 100 cc of ethanol, 12 cc of water, 3.3 g of ammonium
chloride and 10 g of 3-nitropyrazolo[1,5-a]-pyrimidine obtained
above in the preceding step were introduced into a 250 ml
three-necked round-bottomed flask fitted with a magnetic stirrer, a
condenser and a thermometer. The medium was then refluxed. The
heating was withdrawn, and 16 g of zinc powder were added in small
portions in order to maintain the reflux. When this addition was
complete, the mixture was heated at reflux for 3 hours. The zinc
salts were filtered off hot. The filtrate was cooled until
crystallization took place. The crystalline product was filtered
off and dissolved in 100 cc of absolute ethanol. After bubbling
gaseous hydrochloric acid through the ethanolic solution, the
hydrochloride was precipitated by addition of 1 liter of
diisopropyl ether. Drying under vacuum and over phosphoric
anhydride yielded 6 g of pyrazolo[1,5-a]-pyrimidin-3-ylamine
hydrochloride (red solid) (yield=57.5%).
[0107] .sup.1H NMR (D.sub.2O; 200 MHz): 7.18 (dxd; J.sub.1=4.2 Hz
and J.sub.2=7.1 Hz; 1H); 8.33 (s; 1H); 8.65 (dxd; J.sub.1=4.2 Hz
and J.sub.3=1.6 Hz; 1H); 8.90 (dxd; J.sub.2=7.1 Hz and J.sub.3=1.6
Hz; 1H)
Example 2
Synthesis of 5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine
hydrochloride
[0108] 4
[0109] a) Preparation of 5,6,7-trimethyl-3-nitropyrazole-[1,
5-a]pyrimidine
[0110] 80 cc of acetic acid, 8.2 g of 4-nitro-2H-pyrazol-3-ylamine
hydrochloride (prepared according to H. Dorn and H. Dilcher,
Liebigs Ann. Chem., 707, 141, 1967) and 7.2 g of
3-methylpentane-2,4-dione were introduced into a 100 ml
three-necked round-bottomed flask fitted with a magnetic stirrer, a
condenser and a thermometer. The medium was refluxed for 3 hours.
The medium was filtered at room temperature and the solid was
washed with diisopropyl ether. This yielded 9.4 g of crude product.
3.5 g of this product was recrystallized in 23 cc of absolute
ethanol. Drying under vacuum and over phosphoric anhydride yielded
3.1 g of 5,6,7-trimethyl-3-nitropyrazolo[1,5-a]pyrimidine
(yield=80%).
[0111] .sup.1H NMR (DMSO-d.sub.6; 200 MHz): 2.31 (s; 3H); 2.62 (s;
3H); 2.75 (s; 3H); 8.89 (s; 1H)
[0112] b) Preparation of
5,6,7-trimethylpyrazolo[1,5-a]-pyrimidin-3-ylamin- e
hydrochloride
[0113] 90 cc of ethanol, 10 cc of water, 1.5 g of ammonium chloride
and 6.18 g of 5,6,7-trimethyl-3-nitropyrazolo[1,5-a]pyrimidine
obtained above in the preceding step were introduced into a 250 ml
three-necked round-bottomed flask fitted with a magnetic stirrer, a
condenser and a thermometer. The medium was then refluxed. The
heating was withdrawn, and 7.8 g of zinc powder were added in small
portions in order to maintain the reflux. When this addition was
complete, the mixture was heated at reflux for 1 hour. The
zinciferous sludges were filtered off hot. The filtrate was
concentrated to a tenth of its volume, and the product which
crystallized was filtered off. This product was washed with
petroleum ether. Drying under vacuum and over phosphoric anhydride
yielded 4.9 g of 5,6,7-trimethylpyrazolo[1,5-a]pyrimidine
hydrochloride (yield=82%).
[0114] .sup.1H NMR (DMSO-d.sub.6; 200 MHz): 2.27 (s; 3H); 2.55 (s;
3H); 2.70 (s; 3H); 8.22 (s; 1H); 10.61 (broad s; 3H)
Example 3
Synthesis of 7-methylpyrazolo[1,5-a]-pyrimidin-3-ylamine
hydrochloride
[0115] 5
[0116] a) Preparation of
7-methyl-3-nitropyrazolo[5-a]-pyrimidine
[0117] This compound was obtained by following the protocol
described in the first step of Example 2. All quantities were
multiplied by four and the 3-methylpentane-2,4-dione was replaced
by 1.1 molar equivalent of acetylacetaldehyde dimethyl acetal. At
the end of the reaction, the green solution was concentrated and
poured onto ice. The greenish solid which precipitated was filtered
off and washed with diisopropyl ether and petroleum ether. Drying
under vacuum and over phosphoric anhydride at 40.degree. C. yielded
26 g of crude 7-methyl-3-nitropyrazolo[1,5-a]pyrimi- dine
(Yield=73%).
[0118] .sup.1H NMR (DMSO-d.sub.6; 200 MHz): 2.82 (s; 3H); 7.46 (d;
J=4.5 Hz, 1H); 8.90 (d; J=4.5 Hz; 1H); 9.09 (s; 1H)
[0119] b) Preparation of 7-methylpyrazolo[1,
5-a]pyrimidin-3-ylamine hydrochloride
[0120] 19.3 g of 7-methyl-3-nitropyrazolo[1,5-a]-pyrimidine, 500 cc
of methanol and 2.2 g of 5% palladium on charcoal with a water
content of 50% were introduced into a 1 liter hydrogenation
reactor. The medium was heated to about 60.degree. C. and 7.7 bars
of hydrogen were introduced. Following complete reduction, the
reactor was cooled and the catalyst was filtered off. A stream of
gaseous hydrochloric acid was passed through the filtrate, and the
hydrochloride which precipitated was filtered off. Drying under
vacuum and over phosphoric anhydride yielded 14.6 g of
7-methyl-pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride
(yield=72%).
[0121] .sup.1H NMR (DMSO-d.sub.6; 200 MHz): 2.75 (s; 3H); 7.17 (d;
J=3.4 Hz, 1H); 8.40 (s; 1H); 8.75 (d; J=4.2 Hz; 1H); 10.77 (broad
s; 3H)
Example 4
Synthesis of 2,5,6,7-tetramethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine
hydrochloride
[0122] 6
[0123] a) Preparation of
2,5,6,7-tetramethylpyrazolo-[1,5-a]pyrimidine
[0124] 12.6 g of 3-methyl-2,4-pentanedione, 30 cc of acetic acid
and 9.6 9 of 3-amino-5-methylpyrazole were introduced into a 100 ml
three-necked round-bottomed flask fitted with a magnetic stirrer, a
condenser and a thermometer. The medium was refluxed for 1 hour.
The acetic acid was evaporated off and the product was taken up in
50 cc of petroleum ether. The solid was filtered off and washed
with petroleum ether. Drying under vacuum and over phosphoric
anhydride yielded 15 g of
2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidine (yield=85.7%).
[0125] .sup.1H NMR (DMSO-d.sub.6; 200 MHz): 2.06 (s; 3H); 2.25 (s;
3H); 2.31 (s; 3H); 2.50 (s; 3H); 6.13 (s; 1H)
[0126] b) Preparation of 2,5,6,7-tetramethyl-3-nitropyrazolor[1
.5-a]pyrimidine
[0127] 50 cc of 98% sulphuric acid, in which 12.25 g of
2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidine obtained above in the
preceding step had been dissolved, were introduced into a 100 ml
three-necked round-bottomed flask fitted with a magnetic stirrer, a
condenser, a dropping funnel and a thermometer. At about 0.degree.
C., 4.4 g of 100% nitric acid diluted in 2.5 cc of 98% sulphuric
acid were added dropwise. At the end of the addition, stirring was
continued at 0.degree. C. for 1 hour and then the medium was poured
onto 200 g of ice. The pH was brought to using 20% aqueous ammonia.
The precipitate was filtered off. It was washed with water and with
ethanol and with diisopropyl ether. Drying under vacuum and over
phosphoric anhydride yielded 11 g of
2,5,6,7-tetramethyl-3-nitropyrazolo[1,5-a]pyrimidine
(yield=71.4%).
[0128] .sup.1H NMR (DMSO-d6; 200 MHz): 2.33 (s; 3H); 2.63 (s; 3H);
2.67 (s; 3H); 2.75 (s; 3H)
[0129] c) Preparation of
2,5,6,7-tetramethylpyrazolo-[1,5-a]pyrimidin-3-yl- amine
hydrochloride
[0130] 2.2 g of
2,5,6,7-tetramethyl-3-nitropyrazolo[1,5-a]pyrimidine, 40 cc of
ethanol and 1 g of ammonium chloride were introduced into a 100 ml
three-necked round-bottomed flask fitted with a magnetic stirrer, a
condenser and a thermometer. The medium was brought to reflux, and
2.5 g of zinc powder were added in small portions in order to
maintain the reflux. After 0.5 hour of refluxing, the zinciferous
sludges were filtered. The filtrate was concentrated until it
crystallized. The crystals were filtered off. Drying under vacuum
and over phosphoric anhydride yielded 2 g of
2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidin-3-yl- amine
hydrochloride (yield=88.2%).
[0131] .sup.1H NMR (DMSO-d.sub.6; 200 MHz): 2.24 (s; 3H); 2.35 (s;
3H); 2.49 (s; 3H); 2.62 (s; 3H); 6.34 (broad s; 3H)
Example 5
Synthesis of 5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine
hydrochloride
[0132] 7
[0133] a) Preparation of
5.7-di-tert-butyl-3-nitropyrazolor[1,5-a]pyrimidi- ne
[0134] 36.85 g of 2,2,6,6-tetramethyl-3,5-heptanedione, 200 cc of
acetic acid and 32.91 g of 4-nitro-2H-pyrazol-3-ylamine
hydrochloride (prepared in accordance with H. Dorn and H. Dilcher,
Liebigs Ann. Chem., 707, 141, 1967) were introduced into a 500 ml
three-necked flask fitted with a condenser, a thermometer and a
magnetic bar. The mixture was refluxed for 8.5 hours. The solution
was poured, hot, onto ice. The yellow solid which precipitated was
filtered off. It was recrystallized from an acetic acid/water
mixture. Drying under vacuum and over phosphoric anhydride yielded
25.4 g of 5,7-di-tert-butyl-3-nitropyrazolo[1,5-a]pyrimidine
(yield=46%).
[0135] .sup.1H NMR (DMSO-d.sub.6; 200 MHz): 1.40 (s; 9H); 1.57 (s;
9H); 7.26 (s; 1H); 8.98 (s; 1H);
[0136] b) Preparation of
5,7-di-tert-butylpyrazolo[1,5-a]-pyrimidin-3-ylam- ine
hydrochloride
[0137] 8 g of 5,7-di-tert-butyl-3-nitropyrazolo-[1,5-a]pyrimidine,
350 cc of ethanol and 2 g of 5% palladium on charcoal with a water
content of 50% were introduced into a 1 liter hydrogenation
reactor. The medium was brought to 65.degree. C., and 10.6 bars of
hydrogen pressure were introduced. After 1.5 hours, the catalyst
was filtered off, with the filtrate running into 5 M hydrochloric
ethanol. This filtrate was treated with vegetable black. Filtration
to remove the carbon black, evaporation of the ethanol, drying
under vacuum and over phosphoric anhydride yielded 4.5 g of
5,7-di-tert-butylpyrazolo[1,5-a]pyrimdin-3-ylamine hydrochloride
(yield=54.9%).
[0138] .sup.1'H NMR (DMSO-d.sub.6; 200 MHz): 1.40 (s; 9H); 1.58 (s;
9H); 7.02 (s; 1H); 8.35 (s; 1H); 10.55 (broad s; 3H)
Example 6
Synthesis of
5,7-di-trifluoromethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine
hydrochloride
[0139] 8
[0140] a) Preparation of
5,7-di-trifluoromethyl-3-nitropyrazolo[1,5-a]pyri- midine
[0141] 31.2 g of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, 125 cc of
acetic acid and 24.7 g of 4-nitro-2H-pyrazol-3-ylamine
hydrochloride (prepared in accordance with H. Dorn and H. Dilcher,
Liebigs Ann. Chem., 707, 141, 1967) were introduced into a 500 ml
three-necked flask fitted with a condenser, a thermometer and a
magnetic bar. The mixture was refluxed for 8.5 hours. The solution
was poured, hot, onto ice. The yellow solid which precipitated was
filtered off. It was washed with petroleum ether. Drying under
vacuum and over phosphoric anhydride yielded 31.9 g of
5,7-di-trifluoromethyl-3-nitropyrazolo[1,5-a]pyrimidine
(yield=71%).
[0142] .sup.1H NMR (DMSO-d.sub.6; 200 MHz): 8.67 (s; 1H); 9.54 (s;
1H);
b) Preparation of
5,7-di-trifluoromethylpyrazolo-[1,5-a]pyrimidin-3-ylamin- e
hydrochloride
[0143] 3 g of
5,7-di-trifluoromethyl-3-nitro-pyrazolo[1,5-a]pyrimidine, 100 cc of
ethanol and 0.4 g of 5% palladium on charcoal with a water content
of 50% were introduced into a 250 cc hydrogenation reactor. 4.2
bars of hydrogen pressure were introduced. After 1 hour and 40
minutes, the catalyst was filtered off, with the filtrate running
into 5 M hydrochloric ethanol. The ethanol was evaporated to yield
2 g of crude
5,7-di-trifluoromethylpyrazolo[1,5-a]pyrimidin-3-ylamine
hydrochloride. 1.6 g of this crude product was recrystallized from
7 cc of hydrochloric ethanol. Drying under vacuum and over
phosphoric anhydride yielded 1 g of
5,7-di-trifluoromethylpyrazolo[1,5-a]pyrimidin-3-ylamine
hydrochloride (yield 32.6%).
[0144] .sup.1H NMR (DMSO-d.sub.6; 200 MHz): 8.23 (s; 1H); 8.72 (s;
1H); 9.54 (broad s; 3H)
APPLICATION EXAMPLES
Examples 1 to 4
DYEING IN AN ALKALINE MEDIUM
[0145] The following dyeing compositions in accordance with the
invention were prepared (contents in grams):
1 COMPOSITION 1 2 3 4 Pyrazolo[1,5-a]pyrimidin-3-ylamine 0.51 -- --
-- hydrochloride (oxidation base of formula (I))
2,5,6,7-Tetramethylpyrazolo- - -- 0.68 -- --
[1,5-a]pyrimidin-3-ylamine hydrochloride (oxidation base of formula
(I)) 5,7-Dimethylpyrazolo[1,5-a]-pyrimi- din-3- -- -- 0.60 --
ylamine hydrochloride (oxidation base of formula (I))
5,6,7-Trimethylpyrazolo[1,5-a]-pyrimidin- -- -- -- 0.64 3-ylamine
hydrochloride (oxidation base of formula (I))
2-Methyl-5-aminophenol (coupler) 0.37 0.37 0.37 0.37 Common dye
vehicle No. 1 (*) (*) (*) (*) demineralized water q.s. 100 g 100 g
100 g 100 g (*)Common dye vehicle No. 1: 96.degree. Ethyl alcohol
18 g Sodium metabisulphite in 35% aqueous solution 0.68 g
Pentasodium salt of diethylenetriaminepentaacetic acid 1.1 g 20%
Aqueous ammonia 10.0 g Demineralized water q.s. 100 g
[0146] Each of the above dyeing compositions was mixed at the time
of use with an equal weight of a 20-volume (6% by weight) solution
of hydrogen peroxide with a pH of 3.
[0147] The mixture obtained was applied to locks of natural grey
hair containing 90% white hairs for 30 minutes. The locks were
subsequently rinsed, washed with a standard shampoo, rinsed again
and then dried.
[0148] The shades obtained are given in the following table:
2 EXAMPLE Resulting shade 1 Coppery orange 2 Coppery orange 3 Very
light orange-yellow 4 Light orange-yellow
Examples 5 to 7
DYEING IN AN ALKALINE MEDIUM
[0149] The following dyeing compositions in accordance with the
invention were prepared (contents in grams):
3 COMPOSITION 5 6 7 7-Methylpyrazolo[1,5-a]-- pyrimidin-3-ylamine
0.55 -- -- hydrochloride (oxidation base of formula (I))
5,7-Di-tert-butylpyrazolo[1,5-a]-pyrimidin-3- -- 0.85 -- ylamine
hydrochloride (oxidation base of formula (I)) 2-Methoxy
5,7-dimethylpyrazolo[1,5-a]-pyrimidin- -- -- 0.69 3-ylamine
hydrochloride (oxidation base of formula (I))
2-Methyl-5-aminophenol (coupler) 0.37 0.37 0.37 Common dye vehicle
No. 2 (**) (**) (**) Demineralized water q.s. 100 g 100 g 100 g
(**)Common dye vehicle No. 2: 96.degree. Ethyl alcohol 20 g Sodium
metabisulphite 0.23 g Sequestrant q.s. 20% Aqueous ammonia 10.0 g
Demineralized water q.s. 100 g
[0150] Each of the above dyeing compositions was mixed at the time
of use with an equal weight of a 20-volume (6% by weight) solution
of hydrogen peroxide with a pH of 3.
[0151] The mixture obtained was applied to locks of natural grey
hair containing 90% white hairs for 30 minutes. The locks were
subsequently rinsed, washed with a standard shampoo, rinsed again
and then dried.
[0152] The shades obtained are given in the following table:
4 EXAMPLE Resulting shade 5 Coppery 6 Yellow 7 Coppery gold
Example 8
DYEING IN AN ALKALINE MEDIUM
[0153] The following dyeing composition was prepared:
5 5,7-Di-trifluoromethylpyrazolo[1,5-a]- 0.92 g pyrimidin-3-ylamine
hydrochloride (oxidation base of formula (I))
2-Methyl-5-aminophenol (coupler) 0.37 g Benzyl alcohol 2 g
Polyethylene glycol containing 6 mol of 3 g ethylene oxide
96.degree. Ethanol 18 g C.sub.8-C.sub.10-Alkyl polyglucoside in
aqueous 6 g solution containing 60% of active substance, buffered
with ammonium citrate, sold under the name ORAMIX CG110 .RTM. by
the company SEPPIC Aqueous ammonia containing 20% NH.sub.3 10 g
Sodium metabisulphite 0.23 g Sequestrant q.s. Demineralized water
q.s. 100 g
[0154] The above composition was mixed at the time of use with an
equal weight of a 20-volume (6% by weight) solution of hydrogen
peroxide with a pH of 3.
[0155] The mixture obtained was applied to locks of natural grey
hair containing 90% white hairs for 30 minutes. The locks were
subsequently rinsed, washed with a standard shampoo, rinsed again
and then dried.
[0156] The locks of hair had been dyed in a reddish copper
shade.
* * * * *