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United States Patent |
7,294,151 |
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Pasquier , et al. |
November 13, 2007 |
Means and method for dyeing keratin fibres
Abstract
The agent for coloring keratin fibers is based on oxidative dye precursors and contains: (a) at least one hydrazone derivative of formula (I) or a physiologically compatible salt thereof, (b) at least one coupler or a physiologically compatible salt thereof, and (c) a persulfate salt as oxidant. A multicomponent kit for coloring keratin fibers and a method of coloring keratin fibers using the agent are also provided ##STR00001##
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Inventors: |
Pasquier; Ce (Marly, CH), Kiener; Caroline (Marly, CH), Braun; Hans-Juergen (Ueberstorf, CH) |
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Assignee: |
Wella AG (Darmstadt, DE) |
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Appl. No.: |
10/529,979 |
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Filed: |
January 30, 2004 |
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PCT Filed: |
January 30, 2004 |
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PCT No.: |
PCT/EP2004/000815 |
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371(c)(1),(2),(4) Date: |
March 24, 2005 |
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PCT Pub. No.: |
WO20/04/078151 |
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PCT Pub. Date: |
September 16, 2004 |
Claims
What is claimed is:
1. A fiber-coloring agent (A), containing a) at least one hydrazone
derivative of formula (I), or a physiologically compatible salt thereof:
##STR00005## in which X denotes oxygen, sulfur, or N--R4; Y denotes C--R5 or
nitrogen, and Z denotes C--R6 or nitrogen; provided that a heterocyclic part of
the derivative of the formula (I) contains at the most three heteroatoms; in
which R1 and R4 are equal or different and, independently of each other, each
denote a saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group, a
(C.sub.1-C.sub.12)-alkyl group substituted with a halogen atom, a hydroxy-(C.sub.1-C.sub.12)-alkyl
group, an amino-(C.sub.1 -C.sub.12)-alkyl group, a (C.sub.1-C.sub.12)-alkylsulfonic
acid group, a formyl group, a C(O)-(C.sub.1-C.sub.12)-alkyl group, a
C(O)-phenyl group, a C(O)NH--(C.sub.1-C.sub.12)-alkyl group, a C(O)NH-phenyl
group, a substituted or unsubstituted phenyl group, or a benzyl group; R2 and
R3 are equal or different and, independently of each other, each denote a
saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group; R5 and R6 are equal or
different and, independently of each other, each denote hydrogen, a halogen
atom, a saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group, a
(C.sub.1-C.sub.12)-alkyl group substituted with a halogen atom, a
(C.sub.1-C.sub.12)-hydroxyalkyl group, a (C.sub.1-C.sub.12)-alkoxy group, a cyano
group, a nitro group, an amino group, a (C.sub.1-C.sub.12)-alkylamino group, a
(C.sub.1-C.sub.12)-dialkylamino group, a carboxylic acid group, a
C(O)O-(C.sub.1-C.sub.12)-alkyl group, a substituted or unsubstituted
C(O)O-phenyl group, a substituted or unsubstituted phenyl group, or a naphthyl
group; and with the proviso that, if Y and Z denote said C--R3 and said C--R4,
then R5 and R6 together with a remainder of the formula (I) form a heterocyclic
or carbocyclic, saturated or unsaturated, substituted or unsubstituted ring
system; (b) at least one coupler, or a physiologically compatible salt thereof;
and (c) a persulfate salt as oxidant.
2. The agent as defined in claim 1, in which X denotes said sulfur, Y and Z
denote said C--R5 and said C--R6 respectively, and R2 and R3 each denote a
methyl group.
3. The agent as defined in claim 1 in which the at least one hydrazone
derivative of the formula (I) is selected from the group consisting of 3-methyl-2(3H)-thiazolone-(1-methylethylidene)hyd
razone, 3,4-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-tert.-butyl-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-methyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hyd razone, 3-methyl-4-(4-tolyl)-2(3H)-thiazolone-(1-methylethylidene)hyd
razone, 4-(4-methoxy)-phenyl-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydraz-
one, 4-(3-hydroxyphenyl )-3-methyl-2(3H )-thiazolone-(1-methylethylidene)hyd razone,
4-(4-ethoxyphenyl )-3-methyl-2(3H )-thiazolone-(1-methylethylidene)hydrazone,
4-(4-bromophenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone- ,
4-(3-bromophenyl)-3-methyl-2(3H )-thiazolone-(1-methylethylidene)hydrazone,
4-(4-chlorophenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazon- e,
4-(3-chlorophenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hyd razone,
3-methyl-4-(4-nitrophenyl)-2(3H)-thiazolone-(1-methylethylidene)h- ydrazone,
3-methyl-4-(3-nitrophenyl)-2(3H)-thiazolone-(1-methylethylidene)- hydrazone, 4-[(1,1-biphenyl]-4-yl)-3-methyl-2(3H)-thiazolone-(1-methylethy-
lidene)hydrazone, ethyl 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-4-thiazolecarboxyl-
ate, 3,4,5-trimethyl-2(3H)-thiazolone-(1-methylethylidene)hyd razone,
3,4-dimethyl-5-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3,5-dimethyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-methyl-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
5-ethyl-3-methyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-(4-bromophenyl)-3-methyl-5-phenyl-2(3H)-thiazolone-(1-methylethylidene)- -hydrazone,
3-methyl-5-phenyl-4-(4-tolyl)-2(3 H )-thiazolone-(1-methylethylidene)hyd razone,
5-(4-chlorophenyl )-4-phenyl-3-methyl-2(3H )-thiazolone-(1-methylethylidene)-hydrazone,
5-(4-chlorophenyl)-4-(4-methoxyphenyl)-3-methyl-2(3H )-thiazolone-(1-methyl-ethylidene)hydrazone,
ethyl 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3,4-dimethyl-4-thiazole carboxylate,
4-amino-2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-5-thiazole carbonitrile,
3-ethyl-4 ,5-dimethyl-2(3H )-thiazolone-(1-methylethylidene)hydrazone, ethyl
2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-ethyl-4-methylthiazole carboxylate,
5-methyl-3-(1-methylethyl)-4-phenyl-2(3 H )-thiazolone-(1-methylethylidene)-hydrazone,
4,5-dimethyl-3-(1-methylethyl)-2(3H)-thiazolone-(1-methylethylidene)hydra-
zone, 3-(1-methylethyl)-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)- hydrazone,
4-methyl-3-propyl-2(3H)-thiazolone-(1-methylethylidene)hydrazon- e, 4,5-dimethyl-3-propyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4,5-diphenyl-3-propyl-2(3H)-thiazolone-(1-methylethylidene)hyd razone,
3-butyl-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-butyl-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4,5-dimethyl-3-(2-methylpropyl)-2(3H)-thiazolone-(1-methylethylidene)hydr- azone,
3-(2-methylpropyl)-4,5-diphenyl-2(3H)-thiazolone-(1-methylethyliden- e)hydrazone,
3-allyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, 3-allyl-4-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-allyl-4-tert-butyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-allyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-aIIyi-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-allyl-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-hydroxyethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-hydroxyethyl-4-methyl-2(3H )-thiazolone-(1-methylethylidene)hyd razone,
3-hydroxyethyl-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hyd razone,
3-aminoethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-aminoethyl-4-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-aminoethyl-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, 3,4-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-methyl-3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-p-biphenylyl-3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hyd razone,
4-(4-methoxy)phenyl-3-phenyl-2(3H)-thiazolone-(I -methylethylidene)hyd razone,
4-tert.butyl-3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydraz- one,
4,5-dimethyl-3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
5-methyl-3,4-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, 3,4,5-triphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4,5-dimethyl-3-(phenylmethyl)-2(3H)-thiazolone-(1-methylethylidene)hydraz- one,
4-phenyl-3-(phenylmethyl)-2(3H)-thiazolone-(1-methylethylidene)hydraz- one,
5-methyl-4-phenyl-3-(phenyl methyl)-2(3 H )-thiazolone-(1-methylethylidene)-hydrazone,
3-methyl-4 ,5 ,6 ,7-tetrahydro-2(3H )-benzothiazole-(1-methylethylidene)hyd razone,
3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone, 3,6-dimethyl-2(3H
)-benzothiazole-(1-methylethylidene)hydrazone, 6-chloro-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
7-chloro-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
6-hydroxy-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
5-methoxy-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
7-methoxy-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
5,6-dimethoxy-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
5-ethoxy-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
6-ethoxy-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
3-methyl-5-nitro-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
3-methyl-6-nitro-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
5-acetamido-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
6-acetamido-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hyd razone,
5-anilino-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hyd razone,
6-anilino-3-methyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-6-benzothiazole
carboxylic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-4-benzothiazole
sulfonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-5-benzothiazole
sulfonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-6-benzothiazole
sulfonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-7-benzothiazole
sulfonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-N,N-3-trimethyl-6-benzothia-
zole sulfonamide [(2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-6-benzothiazole)-
oxy]acetic hydrazide, 3-ethyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
6-ethoxy-3-ethyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone,
3-propyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone, 3-butyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone
and 3-hexyl-2(3H)-benzothiazole-(1-methylethylidene)hydrazone.
4. The agent as defined in claim 1, in which said at least one coupler is
selected from the group consisting of N-(3-dimethylaminophenyl)urea,
2,6-diamino-pyridine, 2-amino-4-[(2-hydroxyethyl)-amino]-anisole,
2,4-diamino-1-fluoro-5-methyl-benzene, 2,4-diamino-1-methoxy-5-methylbenzene,
2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methyl
benzene, 2 ,4-d i[(2-hydroxy-ethyl)amino]-1,5-dimethoxy-benzene,
2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)-pyridine,
2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine,
1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxy-ethoxy)-benzene, 1,3-diamino-4-(2,3-dihydroxypropoxy)benzene,
1,3-diamino-4-(3-hydroxypropoxy)-benzene,
1,3-diamino-4-(2-methoxyethoxy)-benzene,
2,4-diamino-1,5-di(2-hydroxy-ethoxy)-benzene,
1-(2-aminoethoxy)-2,4-diamino-benzene,
2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene, 2,4-diamino-phenoxyacetic
acid, 3-[di(2-hydroxyethyl)amino]-aniline,
4-amino-2-di[(2-hydroxy-ethyl)amino]-1-ethoxybenzene,
5-methyl-2-(1-methyl-ethyl)phenol, 3-[(2-hydroxy-ethyl)amino]aniline,
3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)-propane, di(2,4-diaminophenoxy)methane,
1,3-diamino-2,4-dimethoxybenzene, 2,6-bis-(2-hydroxyethyl)aminotoluene,
4-hydroxyindole, 3-dimethylaminophenol, 3-diethylaminophenol,
5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol,
5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methyl phenol,
3-amino-2,4-dichlorophenyl, 5-amino-2,4-dichlorophenyl, 3-amino-2-methylphenol,
3-amino-2-chloro-6-methylphenol, 3-aminophenol, 2-[(3-hydroxy-phenyl)amino]-acetamide,
5-[(2-hydroxyethyl )amino]-4-methoxy-2-methylphenol,
5-[(2-hydroxyethyl)amino]-2-methylphenol, 3-[(2-hydroxyethyl)amino]-phenol,
3-[(2-methoxyethyl)amino]-phenol, 5-amino-2-ethyl phenol,
5-amino-2-methoxy-phenol, 2-(4-amino-2-hydroxy-phenoxy)ethanol,
5-[(3-hydroxypropyl)amino]-2-methylphenol, 3-[(2,3-dihydroxy-propyl)amino]-2-methylphenol,
3-[(2-hydroxyethyl)-amino]-2-methylphenol, 2-amino-3-hydroxypyridine,
2,6-dihydroxy-3,4-dimethyl-pyridine, 5-amino-4-chloro-2-methyl-phenol,
1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxy-naphthalene,
2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-methyl-1-naphthol
acetate, 1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,
2-chloro-1,3-dihydroxy-benzene, 1,2-dichloro-3,5-dihydroxy-4-methylbenzene,
1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,
3,4-methylenedioxyphenol, 3,4-methylenedoxyaniline, 5-[(2-hydroxyethyl
)amino]-1,3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylene-dioxybenzene,
3,4-diaminobenzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,
6-amino-3,4-dihydro-1 ,4(2H)benzoxazine, 3-methyl-1-phenyl-5-pyrazoline,
5,6-dihydroxyindole, 5,6-dihydroxyindole, 5-hydroxyindole, 6-hydroxyindole,
7-hydroxyindole and 2,3-indolinedione.
5. The agent as defined in claim 1, in which said persulfate salt is selected
from the group consisting of potassium persulfate, sodium persulfate and
ammonium persulfate.
6. The agent as defined in claim 1, containing said at least one hydrazone
derivative of the formula (I), said at least one coupler and said persulfate
salt in a total amount from 0.01 to 10 weight percent.
7. The agent as defined in claim 1, containing from 0.01 to 10 weight percent
of at least one physiologically harmless direct dye, and in which
said at least one physiologically harmless direct dye is selected
from the group consisting of cationic dyes, anionic dyes, disperse dyes, nitro
dyes, azo dyes, quinone dyes and triphenylmethane dyes.
8. The agent as defined in claim 1, having a pH from 6 to 10.
9. The agent as defined in claim 1, consisting of a hair
colorant.
10. A two-component kit, consisting of a dye carrier composition
(A1) and another dye carrier composition (A2), in
which said dye carrier composition (A1) contains at
least one hydrazone derivative of formula (I), or a physiologically compatible
salt thereof: ##STR00006## in which X denotes oxygen, sulfur, or N--R4; Y
denotes C--R5 or nitrogen, and Z denotes C--R6 or nitrogen; provided that a
heterocyclic part of the derivative of the formula (I) contains at the most
three heteroatoms; in which R1 and R4 are equal or different and, independently
of each other, each denote a saturated or unsaturated (C.sub.1-C.sub.12)-alkyl
group, a (C.sub.1-C.sub.12)-alkyl group substituted with a halogen atom, a hydroxy-(C.sub.1-C.sub.12)-alkyl
group, an amino-(C.sub.1-C.sub.12)-alkyl group, a (C.sub.1-C.sub.12)-alkylsulfonic
acid group, a formyl group, a C(O)--(C.sub.1-C.sub.12)-alkyl group, a
C(O)-phenyl group, a C(O)NH--(C.sub.1-C.sub.12)-alkyl group, a C(O)NH-phenyl
group, a substituted or unsubstituted phenyl group, or a benzyl group; R2 and
R3 are equal or different and, independently of each other, each denote a
saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group; R5 and R6 are equal or
different and, independently of each other, each denote hydrogen, a halogen
atom, a saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group, a
(C.sub.1-C.sub.12)-alkyl group substituted with a halogen atom, a
(C.sub.1-C.sub.12)-hydroxyalkyl group, a (C.sub.1-C.sub.12)-alkoxy group, a cyano
group, a nitro group, an amino group, a (C.sub.1-C.sub.12)-alkylamino group, a
(C.sub.1-C.sub.12)-dialkylamino group, a carboxylic acid group, a
C(O)O--(C.sub.1-C.sub.12)-alkyl group, a substituted or unsubstituted
C(O)O-phenyl group, a substituted or unsubstituted phenyl group, or a naphthyl
group; and with the proviso that, if Y and Z denote C--R3 and C--R4, then R5
and R6 together with a remainder of the formula (I) form a heterocyclic or carbocyclic,
saturated or unsaturated, substituted or unsubstituted ring system; and in
which said another dye carrier composition (A2)
contains at least one coupler, a persulfate salt, and optionally a pH-adjusting
agent.
11. A two-component kit comprising a first component and a second component, in
which said first component consists of a powder containing at least one
coupler, at least one hydrazone derivative of formula I, a persulfate salt, and
optionally at least one powdered cosmetic additive, provided that the at least
one hydrazone derivative of the formula (I), the at least one coupler and the persulfate
salt are in solid form, ##STR00007## in which X denotes oxygen, sulfur, or
N--R4; Y denotes C--R5 or nitrogen, and Z denotes C--R6 or nitrogen; provided
that a heterocyclic part of the derivative of the formula (I) contains at the
most three heteroatoms; in which R1 and R4 are equal or different and,
independently of each other, each denote a saturated or unsaturated
(C.sub.1C.sub.12)-alkyl group, a (C.sub.1-C.sub.12)-alkyl group substituted
with a halogen atom, a hydroxy-(C.sub.1-C.sub.12)-alkyl group, an
amino-(C.sub.1-C.sub.12)-alkyl group, a (C.sub.1-C.sub.12)-alkylsulfonic acid
group, a formyl group, a C(O)--(C.sub.1-C.sub.12)-alkyl group, a C(O)-phenyl
group, a C(O)NH--(C.sub.1-C.sub.12)-alkyl group, a C(O)NH-phenyl group, a
substituted or unsubstituted phenyl group, or a benzyl group; R2 and R3 are
equal or different and, independently of each other, each denote a saturated or
unsaturated (C.sub.1-C.sub.12)-alkyl group; R5 and R6 are equal or different
and, independently of each other, each denote hydrogen, a halogen atom, a
saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group, a
(C.sub.1-C.sub.12)-alkyl group substituted with a halogen atom, a
(C.sub.1-C.sub.12)-hydroxyalkyl group, a (C.sub.1-C.sub.12)-alkoxy group, a cyano
group, a nitro group, an amino group, a (C.sub.1-C.sub.12)-alkylamino group, a
(C.sub.1-C.sub.12)-dialkylamino group, a carboxylic acid group, a
C(O)O--(C.sub.1-C.sub.12)-alkyl group, a substituted or unsubstituted
C(O)O-phenyl group, a substituted or unsubstituted phenyl group, or a naphthyl
group; and with the proviso that, if Y and Z denote C--R3 and C--R4, then R5
and R6 together with a remainder of the formula (I) form a heterocyclic or carbocyclic,
saturated or unsaturated, substituted or unsubstituted ring system; and in
which said second component consists of water or a liquid cosmetic preparation
optionally containing a pH-adjusting agent.
12. A method of coloring hair, said method comprising the steps
of: a) providing a colorant of the hair, said colorant containing
a persulfate salt as oxidant; at least one coupler, or a physiologically
compatible salt thereof; and at least one hydrazone derivative of formula (I),
or a physiologically compatible salt thereof: ##STR00008## in which X denotes
oxygen, sulfur, or N--R4; Y denotes C--R5 or nitrogen, and Z denotes C--R6 or
nitrogen; provided that a heterocyclic part of the derivative of the formula
(I) contains at the most three heteroatoms; in which R1 and R4 are equal or
different and, independently of each other, each denote a saturated or
unsaturated (C.sub.1 C.sub.12)-alkyl group, a (C.sub.1-C.sub.12)-alkyl group
substituted with a halogen atom, a hydroxy-(C.sub.1-C.sub.12)-alkyl group, an
amino-(C.sub.1-C.sub.12)-alkyl group, a (C.sub.1-C.sub.12)-alkylsulfonic acid
group, a formyl group, a C(O)--(C.sub.1-C.sub.12)-alkyl group, a C(O)-phenyl
group, a C(O)NH--(C.sub.1-C.sub.12)-alkyl group, a C(O)NH-phenyl group, a
substituted or unsubstituted phenyl group, or a benzyl group; R2 and R3 are
equal or different and, independently of each other, each denote a saturated or
unsaturated (C.sub.1-C.sub.12)-alkyl group; R5 and R6 are equal or different
and, independently of each other, each denote hydrogen, a halogen atom, a
saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group, a
(C.sub.1-C.sub.12)-alkyl group substituted with a halogen atom, a
(C.sub.1-C.sub.12)-hydroxylalkyl group, a (C.sub.1-C.sub.12)-alkoxy group, a cyano
group, a nitro group, an amino group, a (C.sub.1-C.sub.12)-alkylamino group, a
(C.sub.1-C.sub.12)-dialkylamino group, a carboxylic acid group , a
C(O)O-(C.sub.1-C.sub.12)-alkyl group, a substituted or unsubstituted
C(O)O-phenyl group, a substituted or unsubstituted phenyl group, or a naphthyl
group; and with the proviso that, if Y and Z denote C--R3 and C--R4, then R5
and R6 together with a remainder of the formula (I) form a heterocyclic or carbocyclic,
saturated or unsaturated, substituted or unsubstituted ring system; b) applying
said colorant to the hair; c) allowing said colorant to remain on
the hair for an exposure time of 5 to 60 minutes at a temperature
from 20 to 50.degree. C. after the applying; and then d) rinsing the hair
with water, optionally washing the hair with a shampoo and then
drying the hair.
13. A method of coloring hair, said method comprising the steps
of: a) providing a two-component kit for coloring the hair, said
two-component kit consisting of a dye carrier composition
(A1) and another dye carrier composition (A2), in
which said dye carrier composition (A1) contains at
least one hydrazone derivative of formula (I), or a physiologically compatible
salt thereof: ##STR00009## in which X denotes oxygen, sulfur, or N--R4; Y
denotes C--R5 or nitrogen, and Z denotes C--R6 or nitrogen; provided that a
heterocyclic part of the derivative of the formula (I) contains at the most
three heteroatoms; in which R1 and R4 are equal or different and, independently
of each other, each denote a saturated or unsaturated (C.sub.1-C.sub.12)-alkyl
group, a (C.sub.1-C.sub.12)-alkyl group substituted with a halogen atom, a hydroxy-(C.sub.1-C.sub.12)-alkyl
group, an amino-(C.sub.1-C.sub.12)-alkyl group, a (C.sub.1-C.sub.12)-alkylsulfonic
acid group, a formyl group, a C(O)--(C.sub.1-C.sub.12)-alkyl group, a
C(O)-phenyl group, a C(O)NH--(C.sub.1-C.sub.12)-alkyl group, a C(O)NH-phenyl
group, a substituted or unsubstituted phenyl group, or a benzyl group; R2 and
R3 are equal or different and, independently of each other, each denote a
saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group; R5 and R6 are equal or
different and, independently of each other, each denote hydrogen, a halogen
atom, a saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group, a
(C.sub.1-C.sub.12)-alkyl group substituted with a halogen atom, a
(C.sub.1-C.sub.12)-hydroxyalkyl group, a (C.sub.1-C.sub.12)-alkoxy group, a cyano
group, a nitro group, an amino group, a (C.sub.1-C.sub.12)-alkylamino group, a
(C.sub.1-C.sub.12)-dialkylamino group, a carboxylic acid group, a
C(O)O-(C.sub.1-C.sub.12)-alkyl group, a substituted or unsubstituted
C(O)O-phenyl group, a substituted or unsubstituted phenyl group, or a naphthyl
group; and with the proviso that, if Y and Z denote C--R3 and C--R4, then R5
and R6 together with a remainder of the formula (I) form a heterocyclic or carbocyclic,
saturated or unsaturated, substituted or unsubstituted ring system; and in
which said another dye carrier composition (A2)
contains at least one coupler, a persulfate salt, and optionally a pH-adjusting
agent; b) immediately prior to application to the hair, preparing
a ready-to-apply colorant mixture (A) by mixing said another dye
carrier composition (A2) with said dye carrier composition
(A1) and optionally with an alkalinizing agent or an acid; and then c) applying
said ready-to-apply colorant mixture (A) to the hair; d) after
the applying of step c), allowing the ready-to-apply colorant mixture (A) to
remain on the hair for an exposure time of 5 to 60 minutes at a
temperature from 20 to 50.degree. C.; and then e) rinsing the hair
with water, optionally washing the hair with a shampoo and then
drying the hair.
Description
CROSS-REFERENCE
This is the U.S. National Stage of PCT/EP04/000815, filed on Jan. 30, 2004, in
Europe, which, in turn, is based on DE 103 09 521.7, which was filed in Germany
on Mar. 5, 2003. The foregoing German Patent Application discloses
substantially the same invention as described herein below and provides the
basis for a claim of priority of invention for the invention described herein
below under 35 U.S.C. 119 (a) to (d).
BACKGROUND OF THE INVENTION
The present invention has for an object an agent for coloring keratin fibers,
for example silk, wool or hair and particularly human hair, based on oxidation
dye precursors and which contains at least one heterocyclic hydrazone
derivative of formula (I) and at least one persulfate salt as oxidant, and
furthermore a multicomponent kit and a method for coloring keratin fibers by
use of said agent.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an agent, kit and a method
for coloring keratin fibers that satisfies the requirements for colorant
systems better than the known conventional colorant systems.
Hair colorants are divided mainly into the group of oxidative colorants or that
of tinting agents, depending on the color of the hair to be dyed and on the end
result desired. Oxidative colorants are eminently suited for covering large
gray areas for which, when the proportion of gray hair is 50%, the oxidative
colorants used are usually referred to as oxidative tinting agents, whereas the
oxidative colorants used when the proportion of gray hair is greater than 50%
or for "brightening" are usually referred to as oxidative dyes Direct
dyes are contained mainly in non-oxidative colorants (known as tinting
colorants). Some direct dyes, for example nitro dyes, can, because of their
small [molecular] size, penetrate into the hair and dye the hair directly, at
least in the outer regions. Such tinting agents are very gentle to the hair and
as a rule withstand 6 to 8 hair washes, Direct dyes are often also used in
oxidative colorants to create certain shades or for color intensification. The
colorant systems known to date, however, do not meet the requirements placed on
colorants in every respect, particularly in terms of luster and coloration
intensity.
Surprisingly, we have now found that certain heterocyclic hydrazone derivatives
give with conventional couplers, for example aromatic compounds containing
hydroxyl and/or amino groups, in the presence of persuffate salts, intense
colorations in the yellow to blue color range. The novel colorants gives
particularly brilliant and intense colorations showing very high resistance to
perspiration.
According to the present invention the agent for coloring keratin fibers (A),
for example wool, silk or hair and particularly human hair, contains a) at
least one hydrazone derivative of formula (I) or a physiologically compatible
salt thereof:
##STR00002## wherein X denotes oxygen, sulfur or N--R4; Y denotes C--R5 or
nitrogen and Z denotes C--R6 or nitrogen; provided that the heterocyclic part
of the compound of formula (I) contains at the most three heteroatoms; R1 and
R4 can be equal or different and independently of each other stand for a
saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group, a
(C.sub.1-C.sub.12)-alkyl group substituted with a halogen atom (F, Cl, Br, I),
a hydroxy-(C.sub.1-C.sub.12)-alkyl group, an amino-(C.sub.1-C.sub.12)-alkyl
group, a (C.sub.1-C.sub.12)-alkylsulfonic acid group, a formyl group, a
C(O)--(C.sub.1-C.sub.12)-alkyl group, a substituted or unsubstituted
C(O)-phenyl group, a C(O)NH--(C.sub.1-C.sub.12)-alkyl group, a C(O)NH-phenyl
group, a substituted or unsubstituted phenyl group or a benzyl group; R2 and R3
can be equal or different and independently of each other denote a saturated or
unsaturated (C.sub.1-C.sub.12)-alkyl group; R5 and R6 can be equal or different
and independently of each other stand for hydrogen, a halogen atom (F, Cl, Br,
I), a saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group, a
(C.sub.1-C.sub.12)-alkyl group substituted with a halogen atom (F, Cl, Br, I),
a (C.sub.1-C.sub.12)-hydroxyalkyl group, a (C.sub.1-C.sub.12)-alkoxy group, a cyano
group, a nitro group, an amino group, a (C.sub.1-C.sub.12)-alkylamino group, a
(C.sub.1-C.sub.12)-dialkylamino group, a carboxylic acid group, a
C(O)O--(C.sub.1-C.sub.12)-alkyl group, a substituted or unsubstituted
C(O)O-phenyl group, a substituted or unsubstituted phenyl group or a naphthyl
group; and when Y and Z denote C--R3 and C--R4, then R5 and R6 together with
the remainder of the molecule form a heterocyclic or carbocyclic, saturated or
unsaturated, substituted or unsubstituted ring system; (b) at least one coupler
or a physiologically compatible salt thereof, and (c) a persulfate salt as
oxidant.
Preferred are hydrazone derivatives of formula (I) or the physiologically
compatible salts thereof wherein X stands for sulfur, Y and Z denote C--R5 and
C--R6, and R2 and R3 denote a methyl group, and particularly preferred are the hydrazone
derivatives of formula (I) or the physiologically compatible salts thereof
wherein X stands for sulfur, R2 and R3 denote a methyl group, R1 denotes a
saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group, a hydroxy-(C.sub.1-C.sub.12)-alkyl
group, an amino-(C.sub.1-C.sub.12)-alkyl group or a substituted or unsubstituted
phenyl group, and R5 and R6 independently of each other denote hydrogen, a
saturated or unsaturated (C.sub.1-C.sub.12)-alkyl group, a cyano group, a nitro
group, an amino group, a (C.sub.1-C.sub.12)-alkylamino group, a
(C.sub.1-C.sub.12)-dialkylamino group, a C(O)O--(C.sub.1-C.sub.12)-alkyl group
or a substituted or unsubstituted phenyl group or a naphthyl group, or R5 and
R6 together with the remainder of the molecule form a carbocyclic, unsaturated,
substituted or unsubstituted ring system.
The following compounds may be mentioned as examples of compounds of formula
(I): 3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3,4-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-methyl-4-tert.butyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-methyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-methyl-4-(4-tolyl)-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-(4-methoxy)phenyl-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazo- ne,
4-(3-hydroxyphenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydr- azone,
4-(4-ethoxyphenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hy- drazone,
4-(4-bromophenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)h- ydrazone,
4-(3-bromophenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)- hydrazone,
4-(4-chlorophenyl)-3-methyl-2(3H)-thiazolone-(1-methylethyliden- e)hydrazone,
4-(3-chlorophenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazon- e,
3-methyl-4-(4-nitrophenyl)-2(3H)-thiazolone-(1-methylethylidene)hydrazo- ne,
3-methyl-4-(3-nitrophenyl)-2(3H)-thiazolone-(1-methylethylidene)hydraz- one,
4-([1,1'-biphenyl]-4-yl)-3-methyl-2(3H)-thiazolone-(1-methylethyliden- e)hydrazone,
3-methyl-4-(2-naphthalenyl)-2(3H)-thiazolone-(1-methylethylidene)hydrazon- e,
ethyl 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-4-thiazole- carboxylate,
3,4,5-trimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3,4-dimethyl-5-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3,5-dimethyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-methyl-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
5-ethyl-3-methyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-(4-bromophenyl)-3-methyl-5-phenyl-2(3H)-thiazolone-(1-methylethylidene)- hydrazone,
3-methyl-5-phenyl-4-(4-tolyl)-2(3H)-thiazolone-(1-methylethylid- ene)hydrazone,
5-(4-chlorophenyl)-4-phenyl-3-methyl-2(3H)-thiazolone-(1-methylethylidene- )hydrazone,
5-(4-chlorophenyl)-4-(4-methoxyphenyl)-3-methyl-2(3H)-thiazolone-(1-methy- lethylidene)hydrazone,
ethyl 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3,4-dimethyl-4-thiazololeca-
rboxylate, 4-amino-2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl--
5-thiazolecarbonitrile, 3-ethyl-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
ethyl 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-ethyl-4-methylthiaz- olecarboxylate,
5-methyl-3-(1-methylethyl)-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)- hydrazone,
4,5-dimethyl-3-(1-methylethyl)-2(3H)-thiazolone-(1-methylethyli- dene)hydrazone,
3-(1-methylethyl)-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydra-
zone, 3-(1-methylethyl)-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)- hydrazone,
4-methyl-3-propyl-2(3H)-thiazolone-(1-methylethylidene)hydrazon- e,
4,5-dimethyl-3-propyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4,5-diphenyl-3-propyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-butyl-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-butyl-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4,5-dimethyl-3-(2-methylpropyl)-2(3H)-thiazolone-(1-methylethylidene)hydr- azone,
3-(2-methylpropyl)-4,5diphenyl-2(3H)-thiazolone-(1-methylethylidene- )hydrazone,
3-hydroxyethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-hydroxyethyl-4-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-hydroxyethyl-4,5-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-aminoethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, 3-aminoethyl-4-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-aminoethyl-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-allyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, 3-allyl-4-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-allyl-4-tert.butyl-2(3H)-thiazolone(1-methylethylidene)hydrazone,
3-allyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-allyl-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-allyl-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, 3,4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-methyl-3-phenyl-2(3H)-thiazolon-(1-methylethylidene)hydrazone,
4-p-biphenylyl-3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-(4-methoxy)phenyl-3phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazon- e,
4-tert.butyl-3phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, ethyl
2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-phenyl-4-thiazoloac- etoacetate,
4,5-dimethyl-3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
5-methyl-3,4-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3,4,5-triphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4,5-dimethyl-3-(phenylmethyl)-2(3H)-thiazolone-(1-methylethylidene)hydraz- one,
4-phenyl-3-(phenylmethyl)-2(3H)-thiazolone-(1-methylethylidene)hydraz- one,
5-methyl-4-phenyl-3-(phenylmethyl)-2(3H)-thiazolone-(1-methylethylide- ne)hydrazone,
ethyl 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-[(phenylamino)carbonyl]-4-
-methyl-thiazolecarboxylate, 3-methyl-4,5,6,7-tetrahydro-2(3H)-benzothiazolone-(1-methylethylidene)hyd-
razone, 3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-chloro-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone, 7-chloro-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-hydroxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
5-methoxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
7-methoxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
5,6-dimethoxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazon- e,
5-ethoxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-ethoxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone, 3-methyl-5-nitro-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
3-methyl-6-nitro-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
5-acetamido-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-acetamido-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
5-anilino-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-anilino-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-6-benzothazolecarb- oxylic
acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-4-benzothiazolesul-
fonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-5-benzothiazolesul-
fonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-6-benzothiazolesul-
fonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-7-benzothiazolesul-
fonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-N,N,3-trimethyl-6-benzothia-
zole-sulfonamide, [(2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-6-benzothiazolyl-
)oxy]acetic hydrazide,
3-methylnaphthol[2,3-d]thiazol-2(3H)-one-(1-methylethylidene)hydrazone,
3-ethyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-ethoxy-3-ethyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
3-propyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone, 3-butyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
3-hexyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
3-hydroxyethyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
3-aminoethyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
3-(4-methylbenzyl)-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-(2-hydroxyethyl)-6-benzot- hiazole-carboxylic
acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-6-methoxy-3(2H)-benzothiazo-
lepro-panesulfonic acid, 6-hexadecyloxy-2-[(1-methylethylidene)hydrazono]-3(2H)-benzothiazolepropa-
nesulfonic acid, ethyl 2-keto-3-benzothiazolineacetate-(1-methylethylidene)hydrazone,
3-acetyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
2-[(1-methylethylidene)hydrazono]-3(2H)-benzothiazolecarboxaldehyde,
3-methyl-2(3H)-oxazolone-(1-methylethylidene)hydrazone, 3-phenyl-2(3H)-oxazolone-(1-methylethylidene)hydrazone,
3-methyl-2(3H)-benzoxazolone-(1-methylethylidene)hydrazone, 3-phenyl-2(3H)-benzoxazolone-(1-methylethylidene)hydrazone,
1,3-dimethyl-4-imidazoline-2-one-(1-methylethylidene)hydrazone,
1,3-diethyl-4-imidazoline-2-one-(1-methylethylidene)hydrazone,
1,3-dihydroxyethyl-4-imidazoline-2-one-(1-methylethylidene)hydrazone,
1,3-diaminoethyl-4-imidazoline-2-one-(1-methylethylidene)hydrazone,
1,3-dimethyl-4-methoxy-4-imidazoline-2-one-(1-methylethylidene)hydrazone,
1,3,4-trimethyl-4-imidazoline-2-one-(1-methylethylidene)hydrazone,
1,3-dimethyl-4-phenyl-4-imidazoline-2-one-(1-methylethylidene)hydrazone,
4-carboxy-1,3-dimethyl-4-imidazoline-2-one-(1-methylethylidene)hydrazone,
4-amino-1,3-dimethyl-4-imidazoline-2-one-(1-methylethylidene)hydrazone,
1,3-dimethyl-4-dimethylamino-4-imidazoline-2-one-(1-methylethylidene)hydr- azone,
1,3-dimethyl-2-benzimidazolinone-(1-methylethylidene)hydrazone,
1,3-diethyl-2-benzimidazolinone-(1-methylethylidene)hydrazone,
1,3-dihydroxyethyl-2-benzimidazolinone-(1-methylethylidene)hydrazone,
1,3-diaminoethyl-2-benzimidazolinone-(1-methylethylidene)hydrazone,
1,3,5-trimethyl-2-benzimidazolinone-(1-methylethylidene)hydrazone,
5-methoxy-1,3-dimethyl-2-benzimidazolinone-(1-methylethylidene)hydrazone,
5-bromo-1,3-dimethyl-2-benzimidazolinone-(1-methylethylidene)hydrazone,
4,6-dibromo-1,3-dimethyl-2-benzimidazolinone-(1-methylethylidene)hydrazon- e,
5-chloro-1,3-dimethyl-2-benzimidazolinone-(1-methylethylidene)hydrazone- ,
1,3-dimethyl-5-nitro-2-benzimidazolinone-(1-methylethylidene)hydrazone,
1,3-dimethyl-6-nitro-2-benzimidazolinone-(1-methylethylidene)hydrazone,
1,4-dimethyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylidene)hydrazone- ,
1,4-dihydroxyethyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylidene)hy- drazone,
1,4-diaminoethyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylide- ne)hydrazone,
1,3,4-trimethyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylidene)hydraz- one,
1,4-dimethyl-3-phenyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylid- ene)hydrazone,
1,4-dimethyl-3-methoxy-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylidene- )hydrazone,
1,4-dimethyl-3-dimethylamino-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethy- lidene)hydrazone,
4-carboxy-1,4-dimethyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylidene- )hydrazone,
4-amino-1,4-dimethyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylidene)h- ydrazone,
4-butyl-1-methyl-3-phenyl-.DELTA.2-1,3,4-triazolin-5-one-(1-meth- ylethylidene)hydrazone,
4-methyl-.DELTA.2-1,3,4-thiadiazolin-5-one-(1-methylethylidene)hydrazone,
4-hydroxyethyl-.DELTA.2-1,3,4-thiadiazolin-5-one-(1-methylethylidene)hydr- azone,
4-aminoethyl-.DELTA.2-1,3,4-thiadiazolin-5-one-(1-methylethylidene)- hydrazone,
4-methyl-2-phenyl-.DELTA.2-1,3,4-thiadiazolin-5-one-(1-methylet- hylidene)hydrazone,
2-methoxy-4-methyl-.DELTA.2-1,3,4-thiadiazolin-5-one-(1-methylethylidene)- hydrazone,
2-anilino-4-methyl-.DELTA.2-1,3,4-thiadiazolin-5-one-(1-methyle- thylidene)hydrazone,
2-amino-4-methyl-.DELTA.2-1,3,4-thiadiazolin-5-one-(1-methylethylidene)hy- drazone,
2-dimethylamino-4-methyl-.DELTA.2-1,3,4-thiadiazolin-5-one-(1-met- hylethylidene)hydrazone,
4-methyl-2-(methylthio)-.DELTA.2-1,3,4-thiadiazolin-5-one-(1-methylethyli- dene)hydrazone,
4-(5-[(1-methylethylidene)hydrazono]-4,5-dihydro-4-methyl-.DELTA.2-1,3,4--
thiadiazol-2-yl)benzenesulfonyl fluoride,
4-methyl-.DELTA.2-1,2,4-thiadiazolin-5-one-(1-methylethylidene)hydrazone,
4-hydroxyethyl-.DELTA.2-1,2,4-thiadiazolin-5-one-(1-methylethylidene)hydr- azone,
4-aminoethyl-.DELTA.2-1,2,4-thiadiazolin-5-one-(1-methylethylidene)- hydrazone,
4-methyl-3-phenyl-.DELTA.2-1,2,4-thiadiazolin-5-one-(1-methylet- hylidene)hydrazone,
3-methoxy-4-methyl-.DELTA.2-1,2,4-thiadiazolin-5-one-(1-methylethylidene)- hydrazone,
3-amino-4-methyl-.DELTA.2-1,2,4-thiadiazolin-5-one-(1-methyleth- ylidene)hydrazone,
3-dimethylamino-4-methyl-.DELTA.2-1,2,4-thiadiazolin-5-one-(1-methylethyl- idene)hydrazone,
3-carboxy-4-methyl-.DELTA.2-1,2,4-thiadiazolin-5-one-(1-methylethylidene)- hydrazone,
1,4-dimethyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylidene- )hydrazone,
1,4-dihydroxyethyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylidene)hyd- razone,
1,4-aminoethyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylidene)- hydrazone,
1,3,4-trimethyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylid- ene)hydrazone,
1,4-dimethyl-3-phenyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylidene)- hydrazone,
and 4-methyl-3-phenyl-.DELTA.2-1,2,4-triazolin-5-one-(1-methylethylidene)hydr- azone.
Particularly preferred) are the following compounds of formula (I):
3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, 3,4-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-tert.butyl-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-methyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-methyl-4-(4-tolyl)-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-(4-methoxy)phenyl-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazo- ne,
4-(3-hydroxyphenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydr- azone,
4-(4-ethoxyphenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hy- drazone,
4-(4-bromophenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)h- ydrazone,
4-(3-bromophenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)- hydrazone,
4-(4chlorophenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene- )hydrazone,
4-(3chlorophenyl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone- ,
3-methyl-4-(4-nitrophenyl)-2(3H)-thiazolone-(1-methylethylidene)hydrazon- e,
3-methyl-4-(3-nitrophenyl)-2(3H)-thiazolone-(1-methylethylidene)hydrazo- ne,
4-[(1,1'-biphenyl]-4-yl)-3-methyl-2(3H)-thiazolone-(1-methylethylidene- )hydrazone,
ethyl 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-4-thiazolecarboxyl-
ate, 3,4,5-trimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3,4-dimethyl-5-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3,5-dimethyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-methyl-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
5-ethyl-3-methyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-(4-bromophenyl)-3-methyl-5-phenyl-2(3H)-thiazolone-(1-methylethylidene)- hydrazone,
3-methyl-5-phenyl-4-(4-tolyl)-2(3H)-thiazolone-(1-methylethylid- ene)hydrazone,
5-(4-chlorophenyl)-4-phenyl-3-methyl-2(3H)-thiazolone-(1-methylethylidene- )hydrazone,
5-(4-chlorophenyl)-4-(4-methoxyphenyl)-3-methyl-2(3H)-thiazolone-(1-methy- lethylidene)hydrazone,
ethyl 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3,4-dimethyl-4-thiazolecar--
boxylate, 4-amino-2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-5- -thiazolecarbonitrile,
3-ethyl-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, ethyl
2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-ethyl-4-methylthiaz- olecarboxylate,
5-methyl-3-(1-methylethyl)-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)- hydrazone,
4,5-dimethyl-3-(1-methylethyl)-2(3H)-thiazolone-(1-methylethyli- dene)hydrazone,
3-(1-methylethyl)-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydra-
zone, 4-methyl-3-propyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4,5-dimethyl-3-propyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4,5-diphenyl-3-propyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-butyl-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-butyl-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4,4-dimethyl-3-(2-methylpropyl)-2(3H)-thiazolone-(1-methylethylidene)hydr- azone,
3-(2-methylpropyl)-4,5-diphenyl-2(3H)-thiazolone-(1-methylethyliden- e)hydrazone,
3-allyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, 3-allyl-4-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-allyl-4-tert.butyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, 3-allyl-4-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-allyl-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-allyl-4,5-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-hydroxyethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-hydroxyethyl-4-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-hydroxyethyl-4,5-dimethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazon- e,
3-aminoethyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-aminoethyl-4-methyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3-aminoethyl-4,5-dimethyl-2(3H)-thiazolone-1-methylethylidene)hydrazone,
3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone, 3,4-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-methyl-3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-p-biphenylyl-3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4-(4-methoxy)phenyl-3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazo- ne,
4-tert.butyl-3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4,5-dimethyl-3-phenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
5-methyl-3,4-diphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
3,4,5-triphenyl-2(3H)-thiazolone-(1-methylethylidene)hydrazone,
4,5-dimethyl-3-(phenylmethyl)-2(3H)-thiazolone-(1-methylethylidene)hydraz- one,
4-phenyl-3-(phenylmethyl)-2(3H)-thiazolone-(1-methylethylidene)hydraz- one,
5-methyl-4-phenyl-3-(phenylmethyl)-2(3H)-thiazolone-(1-methylethylide- ne)hydrazone,
3-methyl-4,5,6,7-tetrahydro-2(3H)-benzothiazolone-(1-methylethylidene)hyd- razone,
3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
3,6-dimethyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-chloro-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
7-chloro-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-hydroxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
5-methoxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
7-methoxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
5,6-dimethoxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazon- e,
5-ethoxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-ethoxy-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
3-methyl-5-nitro-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
3-methyl-6-nitro-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
5-acetamido-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-acetamido-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
5-anilino-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-anilino-3-methyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-6-benzothiazolecar- boxylic
acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-4-benzothiazolesul-
fonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-5-benzothiazolesul-
fonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-6-benzothiazolesul-
fonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-7-benzothiazolesul-
fonic acid, 2-[(1-methylethylidene)hydrazono]-2,3-dihydro-N,N-3-trimethyl-6-benzothia-
zolesulfonamide, [(2-[(1-methylethylidene)hydrazono]-2,3-dihydro-3-methyl-4-benzothiazolyl-
)oxy]acetic hydrazide, 3-ethyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
6-ethoxy-3-ethyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone,
3-propyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone, 3-butyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone
and 3-hexyl-2(3H)-benzothiazolone-(1-methylethylidene)hydrazone.
The compounds of formula (I) can be prepared by methods of synthesis known from
the literature, for example by the method described in Research Disclosure
October 1978, pages 42-44 (1978), No. 17434.
Particularly suitable couplers are the following substances or the salts
thereof: N-(3-dimethylaminophenyl)urea, 2,6-diaminopyridine,
2-amino-4-[(2-hydroxyethyl)amino]-anisole,
2,4-diamino-1-fluoro-5-methylbenzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methylbenzene,
2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,
2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene,
2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)pyridine,
2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine,
1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene,
1,3-diamino-4-(2,3-dihydroxypropoxy)benzene,
1,3-diamino-4-(3-hydroxypropoxy)benzene,
1,3-diamino-4-(2-methoxyethoxy)benzene,
2,4-diamino-1,5-di(2-hydroxyethoxy)benzene, 1-(2-aminoethoxy)-2,4-diaminobenzene,
2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene, 2,4-diaminophenoxyacetic
acid, 3-[di(2-hydroxyethyl)amino]aniline,
4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,
5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline,
3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)propane, di(2,4-diaminophenoxy)methane,
1,3-diamino-2,4-dimethoxybenzene, 2,6-bis-(2-hydroxyethyl)aminotoluene,
4-hydroxyindole, 3-dimethylaminophenol, 3-diethyl-aminophenol, 5-amino-2-methylphenol,
5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,
5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol,
5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol,
3-amino-2-chloro-6-methylphenol, 3-aminophenol, 2-[(3-hydroxyphenyl)amino]acetamide,
5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,
5-[(2-hydroxyethyl)amino]-2-methylphenol, 3-[(2-hydroxyethyl)amino]phenol,
3-[(2-methoxyethyl)amino]phenol, 5-amino-2-ethylphenol,
5-amino-2-methoxyphenol, 2-(4-amino-2-hydroxyphenoxy)ethanol,
5-[(3-hydroxypropyl)amino]-2-methylphenol,
3-[(2,3-dihydroxypropyl)amino]-2-methylphenol,
3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine,
2,6-dihydroxy-3,4-dimethylpyridine, 5-amino-4-chloro-2-methyl-phenol, 1-naphthol,
2-methyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxy-naphthalene,
2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-methyl-1-naphthol
acetate, 1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,
2-chloro-1,3-dihydroxy-benzene, 1,2-dichloro-3,5-dihydroxy-4-methylbenzene,
1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,
3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline,
5-[(2-hydroxyethyl)amino]-1,3-benzodioxole,
6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid,
3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4-dihydro-1,4(2H)benzoxazine,
3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxyindole, 5,6-dihydroxyindoline,
5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole and 2,3-indolinedione.
Suitable persulfate salts are, for example, potassium persulfate, sodium persulfate
or ammonium persulfate and a mixture thereof.
The ready-to-use colorant (A) contains the persulfate salts in a total amount
from about 0.01 to 10 weight percent and preferably from about 0.1 to 5 weight
percent.
In addition to the compounds of formula (I) and the coupler, the colorant of
the invention can optionally also contain other common, physiologically
harmless direct dyes from the group of cationic and anionic dyes, disperse dyes,
azo dyes, quinone dyes and tri-phenylmethane dyes.
The ready-to-use colorant (A) contains the direct dyes in an amount from about
0.01 to 10 weight percent and preferably from about 0.1 to 5 weight percent.
In addition to the compounds of formula (I), the colorant of the invention can
optionally also contain common developers, for example 1,4-diaminobenzene (p-phenylenediamine),
1,4-diamino-2-methylbenzene (p-toluylenediamine),
1,4-diamino-2-(thiophen-2-yl)benzene, 1,4-diamino-2-thiophen-3-yl)benzene,
4-(2,5-diaminophenyl)-2-[(diethylamino)methyl]thiophene,
2-chloro-3-(2,5-diaminophenyl)thiophene, 1,4-diamino-2-(pyridin-3-yl)benzene,
2,5-diaminobiphenyl, 2,5-diamino-4'-(1-methylethyl)-1,1'-biphenyl,
2,3',5-triamino-1,1'-biphenyl, 1,4-diamino-2-methoxymethylbenzene,
1,4-diamino-2-aminomethylbenzene, 1,4-diamino-2-[(phenylamino) methyl]benzene,
1,4-diamino-2{[ethyl-(2-hydroxyethyl)amino]methyl}benzene,
1,4-diamino-2-hydroxymethylbenzene, 4-[di(2-hydroxyethyl)amino]aniline,
4-{[(4-aminophenyl)methyl]amino}aniline, 4-[(4-aminophenylamino)methyl]phenol,
1,4-diamino-N-(4-pyrrolidin-1-ylbenzyl)benzene,
1,4-diamino-N-furan-3-ylmethylbenzene,
1,4-diamino-N-thiophen-2-ylmethylbenzene,
1,4-diamino-N-furan-2-ylmethylbenzene, 1,4-diamino-N-thiophen-3-ylmethylbenzene,
1,4-diamino-N-benzylbenzene, 1,4-diamino-2-(1-hydroxyethyl)-benzene,
1,4-diamino-2-(2-hydroxyethyl)benzene,
1,3-bis-[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,
1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane,
2,5-diamino-4'-hydroxy-1,1'-biphenyl, 2,5-diamino-2'-trifluoromethyl-1,1'-biphenyl,
2,4',5-triamino-1,1'-bi-phenyl, 4-aminophenol, 4-amino-3-methylphenol,
4-methylaminophenol, 4-amino-2-(amino-methyl)phenol,
4-amino-2-[(2-hydroxyethyl)amino]methylphenol, 4-amino-2-(methoxymethyl)phenol,
5-aminosalicylic acid, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-(1H)-pyrimidone,
4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole, 4,5-diamino-1-pentyl-1H-pyrazole,
4,5-diamino-1-(phenylmethyl)-1H-pyrazole,
4,5-diamino-1-(4-methoxyphenyl)methyl-1H-pyrazole, 2-aminophenol,
2-amino-6-methylphenol, 2-amino-5-methylphenol, 1,2,4-trihydroxybenzene,
2,4-diaminophenol, 1,4-dihydroxybenzene or
2-{[(4-aminophenyl)amino]methyl}-1,4-diaminobenzene.
The compounds of formula (I) and the couplers and additional developers are
contained in the ready-to-use colorant (A) in a total amount from about 0.01 to
10 weight percent and preferably from about 0.1 to 5 weight percent, each.
As a rule, the compounds of formula (I) and the couplers are stored separately
and just before use are mixed with one another, and the persulfate salt is
added to them. If the compounds of formula (I), the couplers and the persulfate
salt are solids, however, it is also possible to package them together and
shortly before use to prepare the ready-to-use colorant (A) by mixing the
compounds of formula (I), the couplers and the persulfate salt with water or
with a liquid preparation containing the other ingredients of the agent.
As a rule, the colorant of the invention consists therefore of several components
that are to be mixed before use. The agent is preferably in the form of a
2-component kit consisting of a dye carrier composition (A1) containing the
compound of formula (I) and another dye carrier composition (A2) containing the
couplers and the persulfate salts, or of a 3-component kit consisting of a dye
carrier composition (A1) containing the compound of formula (I), another dye
carrier composition (A2) containing the couplers, and a third component (A3)
containing the persulfate salts.
Another object of the present invention is a multicomponent kit consisting of
an agent of component (A1) and an agent of component (A2), the persulfate
possibly being packaged as component (A3) separately from component (A2), and
optionally of a pH-adjusting agent (alkalinizing agent or acid). Naturally, the
agents of components (A1) and (A2) can also consist of several individual
components to be mixed only just before use. Also possible is a 2-component kit
with a first component that consists of one of the compounds of formula (I),
the coupler and the persulfate salts and optionally other powders containing
other common powdered cosmetic additives, and with a second component that
consists of water or of a liquid cosmetic preparation. Particularly preferred,
however, is a 2-component kit consisting of an agent of component (A1) and an
agent of component (A2).
The aforementioned direct dyes can be used in component (A1) and/or component
(A2) in a total amount from about 0.02 to 20 weight percent and preferably from
0.2 to 10 weight percent, whereas each of the couplers and additional
developers can be contained in the dye carrier component [component (A1) or
component (A2)] in a total amount from about 0.02 to 20 weight percent and
preferably from about 0.2 to 10 weight percent.
Components (A1) and (A2) as well as the ready-to-use colorant (A) can be
formulated, for example, as a solution, particularly an aqueous or
aqueous-alcoholic solution, or as a cream, a gel or an emulsion. The
preparations consist of a mixture of the compound of formula (I) or of the
couplers with additives commonly used in such preparations.
Additives that are commonly used in colorants in the form of solutions, creams,
emulsions, gels or aerosol foams are, for example, solvents such as water,
lower aliphatic alcohols, for example ethanol, n-propanol and isopropanol or
glycols such as glycerol and 1,2-propanediol, moreover wetting agents or
emulsifiers from the classes of anionic, cationic, amphoteric or nonionic
surface-active substances, such as the fatty alcohol sulfates, ethoxylated
fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethyl-ammonium
salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols,
fatty alkanolamides, ethoxylated fatty esters, furthermore thickeners such as
the higher fatty alcohols, starch or cellulose derivatives, perfumes, hair
pretreatment agents, conditioners, hair swelling agents, preservatives,
moreover vaseline, paraffin oil and fatty acids and also hair-care agents such
as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine.
The said constituents are employed in amounts commonly used for such purposes,
for example the wetting agents and emulsifiers at a concentration from about
0.5 to 30 weight percent [always based on component (A1) or (A2)], the
thickeners in an amount from about 0.1 to 25 wt. % [always based on component
(A1) or (A2)] and the hair-care agents at a concentration from about 0.1 to 5.0
weight percent [always based on component (A1) or (A2)].
The pH of the ready-to-use colorant (A) and of the dye carrier compositions
(A1) and (A2) is about 3 to 12 and preferably about 6 to 10, the pH of the ready-to-use colorant (A) as a rule being adjusted by mixing component (A1)
with component (A2) and optionally with the persulfates. To adjust the pH of
components (A1) and (A2) and of the ready-to-use colorant (A) to the value
desired for coloring, however, it is also possible, if needed, to use
alkalinizing agents, for example ammonia, alkali metal hydroxides, alkaline
earth metal hydroxides, alkali metal acetates, alkaline earth metal acetates,
alkali metal carbonates or alkaline earth metal carbonates, or else acids, for
example lactic acid, acetic acid, tartaric acid, phosphoric acid, hydrochloric
acid, citric acid, ascorbic acid or boric acid.
The ready-to-use colorant is prepared just before use by mixing components (A1)
and (A2) or (A1), (A2) and (A3)--optionally adding an alkalinizing agent or an
acid--and then applying the mixture to the fibers, particularly human hair.
Depending on the color depth desired, said mixture is allowed to act on the
hair for about 5 to 60 minutes and preferably for about 15 to 30 minutes at a
temperature from about 20 to 50.degree. C. and particularly from about 30 to
40.degree. C. The fibers are then rinsed with water, optionally washed with a
shampoo and then dried.
The colorant of the invention produces a uniform and lasting coloration of the
fibers, particularly keratin fibers, for example human hair. A wide range of
yellow to blue color shades can thus be obtained. Resistance to perspiration is
achieved to a particularly high degree.
The following examples will explain the subject matter of the invention in
greater detail without limiting its scope.
EXAMPLES
Example 1
Synthesis of 3,4-dimethyl-2(3H)-thiazolone-1-methylethylidene)-hydrazone
##STR00003##
21 g (200 mmoles) of 4-methyl-3-thiosemicarbazide in 1000 mL of acetone was
heated under reflux for 2 hours. To the solution was then added dropwise 20.4 g
(220 mmoles) of chloroacetone. The reaction mixture was allowed to reflux for 7
hours after which it was concentrated. The crude product thus obtained was recrystallized
from acetone. This gave 23 g of an orange powder (63% of the theoretical).
Melting point 139-139.6.degree. C.
.sup.1H-NMR (DMSO, 300 MHz): .delta.=6.72 [s, broad, 1H, H--C(5)]; .delta.=3.67
(s, 3H, N--CH3); .delta.=2.27 [d, J=0.9 Hz, 3H, CH3--C(4)]; .delta.=2.17 (s,
3H, CH3); .delta.=2.07 (s, 3H, CH3).
.sup.13C-NMR (DMSO 300 MHz): .delta.=169.16; .delta.=164.14; .delta.=139.02
[C(4)]; .delta.=103.36 [C(5)]; .delta.=34.47 (CH.sub.3N); .delta.=24.60;
.delta.=19.91; .delta.=13.53 [CH.sub.3--C(4)].
MS(ESI): 184 [M+H].sup.+ (100).
Examples 2-9
Synthesis of Derivatives of Formula (I) (General Method of Synthesis)
##STR00004##
4 mmoles of substituted thiosemicarbazide in 20 mL of acetone was heated under
reflux for 2 hours. To the solution was then added dropwise 4.4 mmoles of an
.alpha.-chloroketone. The reaction mixture was heated under reflux for 7 hours
and then concentrated. The resulting 2(3H)-thiazolone-1-(methylethylidene)hydrazone
was recrystallized from acetone.
2. 3-Methyl-4-phenyl-2(3H)-thiazolone-1-(methylethylidene)hydrazone
From 4-methyl-3-thiosemicarbazide and phenacyl chloride.
Yield: 1 g (100% of the theoretical)
ESI-MS: 246 [M+H].sup.+ (100)
3. 4-tert Butyl-3-methyl-2(3H)-thiazolone-1-(methylethylidene)hydrazone
From 4-methyl-3-thiosemicarbazide and 1-chloro-3,3-dimethyl-2-butanone
Yield: 0.67 g (75% of the theoretical)
ESI-MS: 226 [M+H].sup.+ (100)
4. 3-Allyl-4-methyl-2(3H)-thiazolone-1-(methylethylidene)hydrazone
From 4-allyl-3-thiosemicarbazide and chloroacetone
Yield: 0.32 g (39% of the theoretical)
ESI-MS: 210 [M+H].sup.+l (100)
5. 3-Allyl-4-phenyl-2(3H)-thiazolone-1-(methylethylidene)hydrazone
From 4-allyl-3-thiosemicarbazide and phenacyl chloride
Yield: 0.57 g (53% of the theoretical)
ESI-MS: 272 [M+H].sup.+ (100)
6. 3-Allyl-4-tert butyl-2(3H)-thiazolone-1-(methylethylidene)hydrazone
From 4-allyl-3-thiosemicarbazide and 1-chloro-3,3-dimethyl-2-butanone
Yield: 0.53 g (53% of the theoretical)
ESI-MS: 252 [M+H].sup.+ (100)
7. 3,4-Diphenyl-2(3H)-thiazolone-1-(methylethylidene)hydrazone
From 4-phenyl-3-thiosemicarbazide and phenacyl chloride
Yield: 0.83 g (68% of the theoretical)
ESI-MS: 308 [M+H].sup.+ (100)
8. Ethyl{2-[(1-methylethylidene)hydrozone]-3-phenyl-2,3-dihydro-1,3-thiazo-
l-4-yl}-acetat
From 4-phenyl-3-thiosemicarbazide and ethyl 4-chloroacetate
Yield: 0.34 g (27% of the theoretical)
ESI-MS: 318 [M+H].sup.+(100)
9. 3,4,5-Trimethyl-2(3H)-thiazolone-1-(methylethylidene)hydrazone
From 4-methyl-3-thiosemicarbazide and 3-chloro-2-butanone
Yield: 0.27 g (34% of the theoretical)
ESI-MS: 198 [M+H].sup.+ (100)
Examples 10-15
Colorants with 3,4-dimethyl-2(3H)-thiazolone-1-(methylethylidene)hydrazone
TABLE-US-00001 Component (A1) 4.00 g of decylpolyglucose (Plantaren .RTM.
2000), 50% aqueous solution 0.20 g disodium ethylenediaminetetraacetate hydrate
5.00 g of ethanol 0.46 g of 3,4-dimethyl-2(3H)-thiazolone-1-(methylethylidene) hydrazone
to 100.00 g water, demineralized Component (A2) Y g of coupler as per Table 1
0.80 g of potassium persulfate
The afore-mentioned components (A1) and (A2) were uniformly mixed with one
another at room temperature (20-25.degree. C.) or with slight heating
(35-40.degree. C.) If necessary, the pH of the resulting ready-to-use colorant
(A) was adjusted to the value indicated in Table 1 with sodium hydroxide,
sodium carbonate or ammonia.
The ready-to-use hair colorant was applied to bleached buffalo hair and
uniformly distributed with a brush. After an exposure time of 30 minutes at
40.degree. C., the hair was washed with a commercial shampoo and then dried.
The amount of coupler used and the coloration obtained are summarized in the
following Table 1.
TABLE-US-00002 TABLE 1 Example Coupler used No. (amount in g) pH Color Shade 10
1,3-diaminobenzene (0.27 g) 9.9 Bordeaux red 11 2,4-diamino-1-(2-hydroxyethoxy)-
10.0 dark brown-violet benzene sulfate (0.67 g) 12
N-(3-dimethylaminophenyl)urea 9.5 blue (0.44 g) 13 3-aminophenol (0.27 g) 9.6
strawberry red 14 5-amino-2-methylphenol (0.31 g) 9.6 red-orange 15
1,3-dihydroxybenzene (0.27 g) 9.0 red
Examples 16-55
Colorants with 2(3H)-thiazolone-1-(methylethylidene)hydrazones of formula (I)
TABLE-US-00003 Component (A1) 4.00 g of decylpolyglucose (Plantaren .RTM.
2000), 50% aqueous solution 0.20 g of disodium ethylenediaminetetraacetate
hydrate 5.00 g of ethanol X g of 2(3H)-thiazolone-1-(methylethylidene)hydrazone
of formula (I) to 100.00 g water, demineralized Component (A2) Y g of coupler
as per Table 2 0.80 g of potassium persulfate
The afore-mentioned components (A1) and (A2) were uniformly mixed with one
another at room temperature (20-25.degree. C.) or with slight heating
(35-40.degree. C.). If necessary, the pH of the resulting ready-to-use colorant
(A) was adjusted to the value indicated in Table 2 with sodium hydroxide,
sodium carbonate or ammonia.
The ready-to-use hair colorant was applied to bleached hair and uniformly
distributed with a brush. After an exposure time of 30 minutes at 40.degree.
C., the hair was washed with a commercial shampoo and then dried.
The amount of 2(3H)-thiazolone-1-(methylethylidene)hydrazones of formula (I)
and of the coupler used as well as the coloration obtained are summarized in
the following Table 2.
TABLE-US-00004 TABLE 2 Derivative of Formula (I) as Example per Example No.
Coupler Used No. (amount in g) (amount in g) pH Color Shade 16 Example 2
1,3-diaminobenzene 9.6 Bordeaux red (0.61 g) (0.27 g) 17 Example 3
1,3-diaminobenzene 9.6 Bordeaux red (0.56 g) (0.27 g) 18 Example 4
1,3-diaminobenzene 9.6 Bordeaux red (0.52 g) (0.27 g) 19 Example 5 1,3-diaminobenzene
9.6 light Bordeaux red (0.68 g) (0.27 g) 20 Example 6 1,3-diaminobenzene 9.6
Bordeaux red (0.63 g) (0.27 g) 21 Example 7 1,3-diaminobenzene 9.6 gray beige
(0.77 g) (0.27 g) 22 Example 8 1,3-diaminobenzene 9.6 light Bordeaux red (0.79
g) (0.27 g) 23 Example 9 1,3-diaminobenzene 9.6 Bordeaux red (0.49 g) (0.27 g)
24 Example 2 2,4-diamino-1-(2-hydro- 9.6 dark Bordeaux red (0.61 g) xyethoxy)benzene
sulfate (0.67 g) 25 Example 3 2,4-diamino-1-(2-hydro- 9.6 dark Bordeaux red
(0.56 g) xyethoxy)benzene sulfate (0.67 g) 26 Example 4 2,4-diamino-1-(2-hydro-
9.6 dark Bordeaux red (0.52 g) xyethoxy)benzene sulfate (0.67 g) 27 Example 5
2,4-diamino-1-(2-hydro- 9.6 dark Bordeaux red (0.68 g) xyethoxy)benzene sulfate
(0.67 g) 28 Example 6 2,4-diamino-1-(2-hydro- 9.6 dark Bordeaux red (0.63 g) xyethoxy)benzene
sulfate (0.67 g) 29 Example 7 2,4-diamino-1-(2-hydro- 9.6 brown (0.77 g) xyethoxy)benzene
sulfate (0.67 g) 30 Example 8 2,4-diamino-1-(2-hydro- 9.6 dark Bordeaux red
(0.79 g) xyethoxy)benzene sulfate (0.67 g) 31 Example 9 2,4-diamino-1-(2-hydro-
9.6 dark Bordeaux red (0.49 g) xyethoxy)benzene sulfate (0.67 g) 32 Example 2
N-(3-dimethylamino- 9.5 light blue (0.61 g) phenyl)urea (0.44 g) 33 Example 3
N-(3-dimethylamino- 9.5 light blue (0.56 g) phenyl)urea (0.44 g) 34 Example 4
N-(3-dimethylamino- 9.5 blue (0.52 g) phenyl)urea (0.44 g) 35 Example 5
N-(3-dimethylamino- 9.5 light blue (0.68 g) phenyl)urea (0.44 g) 36 Example 6
N-(3-dimethylamino- 9.5 light blue (0.63 g) phenyl)urea (0.44 g) 37 Example 7
N-(3-dimethylamino- 9.5 very light blue (0.77 g) phenyl)urea (0.44 g) 38
Example 8 N-(3-dimethylamino- 9.5 light blue (0.79 g) phenyl)urea (0.44 g) 39
Example 9 N-(3-dimethylamino- 9.5 light blue (0.49 g) phenyl)urea (0.44 g) 40
Example 2 3-aminophenol 9.6 dark blond (0.61 g) (0.27 g) 41 Example 3
3-aminophenol 9.6 strawberry red (0.56 g) (0.27 g) 42 Example 4 3-aminophenol
9.6 strawberry red (0.52 g) (0.27 g) 43 Example 5 3-aminophenol 9.6
copper-brown (0.68 g) (0.27 g) 44 Example 6 3-aminophenol 9.6 strawberry red (0.63
g) (0.27 g) 45 Example 7 3-aminophenol 9.6 brown (0.77 g) (0.27 g) 46 Example 8
3-aminophenol 9.6 light strawberry red (0.79 g) (0.27 g) 47 Example 9
3-aminophenol 9.6 strawberry red (0.49 g) (0.27 g) 48 Example 2
1,3-dihydroxybenzene 10.0 light red-orange (0.61 g) (0.27 g) 49 Example 3
1,3-dihydroxybenzene 10.0 light red-orange (0.56 g) (0.27 g) 50 Example 4
1,3-dihydroxybenzene 10.0 red-orange (0.52 g) (0.27 g) 51 Example 5
1,3-dihydroxybenzene 10.0 very light red-orange (0.68 g) (0.27 g) 52 Example 6
1,3-dihydroxybenzene 10.0 red-orange (0.63 g) (0.27 g) 53 Example 7
1,3-dihydroxybenzene 10.0 beige (0.77 g) (0.27 g) 54 Example 8
1,3-dihydroxybenzene 10.0 light red-orange (0.79 g) (0.27 g) 55 Example 9
1,3-dihydroxybenzene 10.0 red-orange (0.49 g) (0.27 g)
Unless otherwise indicated, all percentages given in the present patent
application are by weight.
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