Title of Invention

"KERATIN DYEING COMPOUNDS, KERATIN DYEING COMPOSITIONS CONTAINING THEM, AND USE THEREOF"

Abstract Tricyclic 5-6-5 heteroaromatic keratin dyeing compounds having two heteroatoms. Compositions for the oxidative dyeing of keratin fibers, comprising a medium suitable for dyeing and one or more tricyclic 5-6-5 heteroaromatic keratin dyeing compounds having two heteroatoms. A method for oxidative dyeing of keratin fibers, comprising applying such compositions in the presence of an oxidizing agent, for a period sufficient to develop the desired coloration.
Full Text Field of Invention
This invention relates to tricyclic 5-6-5 heteroaromatic keratin dyeing compounds
having two heteroatoms, compositions for the oxidative dyeing of keratin fibers
(preferably hair) comprising such compounds, and use thereof.
Background of the Invention
The most extensively used method currently employed to color hair is by an
oxidative process that utilizes one or more oxidative hair coloring agents in combination
with one or more oxidizing agents.
Commonly, a peroxy oxidizing agent is used in combination with one or more
developers or couplers, generally small molecules capable of diffusing into hair, In this
procedure, a peroxide material, such as hydrogen peroxide, activates the developers so
that they react with the couplers to form larger sized compounds in the hair shaft to give a
variety of shades and colors.
A wide variety of developers and couplers have been employed in such oxidative
hair coloring systems and compositions. However, there still exists a need for additional
keratin dyeing compounds that can act as both developers and couplers that safely
provide color benefits.
Summary of the Invention
This invention relates to tricyclic 5-6-5 heteroaromatic keratin dyeing compounds
having two heteroatoms according to the formulas defined herein. This invention also
relates to a composition for the oxidative dyeing of keratin fibers, comprising a medium
suitable for dyeing and one or more tricyclic 5-6-5 heteroaromatic keratin dyeing
compounds having two heteroatoms. This invention further relates to a method for
oxidative dyeing of keratin fibers, comprising applying such compositions in the presence
of an oxidizing agent, for a period sufficient to develop the desired coloration. The
keratin dyeing compounds of the present invention can act as a developer and/or a
coupler.
It is to be understood that within the scope of this invention, numerous potentially
and actually tautomeric compounds are involved. Thus, for example, 2-mercaptopyridine
(I) exists under known conditions in the pyridine-2-thione tautomer form (II).
It is to be understood that when this development refers to a particular structure, all of the
reasonable additional tautomeric structures are included. In the art, tautomeric structures
are frequently represented by one single structure and the present invention follows this
general practice.
Detailed Description of the Invention
While the specification concludes with claims that particularly point out and
distinctly claim the invention, it is believed the present invention will be better
understood from the following description. ;
The present invention relates to tricyclic 5-6-5 heteroaromatic keratin dyeing
compounds having two heteroatoms. The compounds of the present invention can act as
developers and/or couplers that safely provide color benefits.
Herein, "comprising" means that other steps and other ingredients which do not
affect the end result can be added. This term encompasses the terms "consisting of and
"consisting essentially of. The compounds/compositions and methods/processes of the
present invention can comprise, consist of, and consist essentially of the essential
elements and limitations of the invention described herein, as well as any of the
additional or optional ingredients, components, steps, or limitations described herein.
All percentages, parts and ratios are based upon the total weight of the
compositions of the present invention, unless otherwise specified. All such weights as
they pertain to listed ingredients are based on the active level and, therefore, do not
include solvents or by-products that may be included in commercially available materials,
unless otherwise specified. The term "weight percent" may be denoted as "wt.%" herein.
Except as otherwise noted, all amounts including part, percentages, and
proportions are understood to be modified by the word "about", and amounts are not
intended to indicate significant digits. Except as otherwise noted, the articles "a", "an",
and "the" mean "one or more".
As used herein, the term "keratin" refers to a scleroprotein found in epidermal
tissues and modified into hard structures such as horns, hair, and nails. Thus, "keratinous
fibers" refers to those found in hair, skin and nails and various animal body parts such as
horns, hooves and feathers.
As used herein, the term "hair" refers to keratinous fibers on a living, e.g. a
person, or non-living body, e.g. in a wig, hairpiece, or other aggregation of non-living
keratinous fibers. Mammalian, preferably human, hair is a preferred. Notably, hair,
wool, fur, and other keratinous fibers are suitable substrates for coloring by the
compounds and compositions described herein.
As used herein, the term "keratin dyeing compounds" refers to compounds that
may be used in the composition to act as developers, couplers, or both, in order to provide
color to ketatinous fibers.
As used herein, the term "keratin dyeing composition" refers to the composition
containing one or more keratin dyeing compounds, including the compounds described
herein.
As used herein, "cosmetically acceptable" means that ingredients which the term
describes are suitable for use in contact with the skin or hair of humans and lower animals
without undue toxicity, incompatibility, instability, irritation, allergic response, and the
like.
I. Keratin Dyeing Compounds
The inventive compounds are tricyclic 5-6-5 heteroaromatic keratin dyeing
compounds having two heteroatoms according to the following formulas:
wherein Y and Z are selected from the group consisting of NA1, S, and O;
wherein R1, R2, R3, R4, R5 and R6 are the same or different and are selected from
the group consisting of:
(a) C-linked monovalent substituents selected from the group consisting of:
(i) substituted or unsubstituted, straight or branched, alkyl, mono- or polyunsaturated
alkyl, heteroalkyl, aliphatic, heteroaliphatic, or
heteroolefinic systems,
(ii) substituted or unsubstituted, mono- or poly-cyclic aliphatic, aryl, or
heterocyclic systems, and
(iii) substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl systems;
wherein said systems of (i), (ii) and (iii) comprise from about 1 to
about 10 carbon atoms and from about 0 to about 5 heteroatoms
selected from the group consisting of O, S, N, P, and Si;
wherein substituents of the substituted systems of the C-linked monovalent
substituents are selected from the group consisting of amino, hydroxyl,
alkylamino (linear, branched, or cyclic C1-C5), dialkylamino (linear,
branched, or cyclic C1-C5), hydroxyalkylamino (linear, branched, or
cyclic C1-C5), dihydroxyalkylamino (linear, branched, or cyclic C1-C5),
arylamino or substituted arylamino (substituents are halogen, C1-C5 alkyl,
C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino),
heteroarylamino or substituted hetero arylamino (substituents are halogen,
C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino),
arylmethylamino or substituted arylmethylamino (substituents are halogen,
C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino),
and heteroarylmethylamino or substituted heteroarylmethylamino
(substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,
amino, C1-C5 alkylamino),
(b) S-linked monovalent substituents selected from the group consisting of SA1,
S02A', SOsA1, SSA1, SOA1, SOaNA'A2, SNA'A2, and SONA'A2;
(c) 0-linked monovalent substituents selected from the group consisting of OA1,
and ONA'A2;
(d) N-linked monovalent substituents selected from the group consisting of
NA'A2, (NA'A2A3)+, NA]OA2, NA]SA2, NO2, N=NA], N=NOA', NA'CN,
and NA'NA2A3;
(e) monovalent substituents selected from the group consisting of COOA1,
CONA'2) CONA'COA2, C^NA^NA'A2, CN, andX;
(f) fluoroalkyl monovalent substituents selected from the group consisting of
mono-, poly-, and per-fluoro alkyl systems comprising from about 1 to about
12 carbon atoms and from about 0 to about 4 heteroatoms; and
(g) hydrogen;
wherein A1, A2, and A3 are monovalent and are independently selected from the
group consisting of: H; substituted or unsubstituted, straight or branched, alkyl, mono- or
poly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinic systems;
substituted or unsubstituted, mono- or poly-cyclic aliphatic, aryl, or heterocyclic systems;
and substituted or unsubstituted, mono-, poly-, per-fluoro alkyl systems or A1 and A2
together with nitrogen atom to which they are bound form a ring; wherein said systems
comprise from about 1 to about 10 carbon atoms and from about 0 to about 5 heteroatoms
selected from the group consisting of O, S, N, P, and Si;
wherein X is a halogen selected from the group consisting of F, Cl, Br, and I.
In a preferred embodiment, R1, R2, R3, R4, R5, and R6 are selected from the group
consisting of a hydrogen atom; a halogen atom such as chlorine, bromine or fluorine; an
amino substituent, a hydroxyl substituent; a cyano substituent; a Ci-C4 alkyl substituent; a
trifluoromethyl substituent, an alkylamino substituent (e.g., N,N-dimethylamino, N,Ndiethylamino,
N-methylamino, or N-ethylamino); a hydroxyalkylamino substituent (e.g.,
N-(hydroxyethyl)amino, N-hydroxymethylamino, N-hydroxypropylamino, N,Nbis(
hydroxyethyl)amino, N-(2,3-dihydroxypropyl)amino or N,Nbis(
hydroxypropyl)amino); an acetylamido substituent; a carboxyl substituent or its
esters; an alkoxy substituent (e.g., methoxy, ethoxy, propyloxy, benzyloxy,
methoxyethoxy, phenoxyethoxy, 2-cyanoethoxy, phenethyloxy, phenoxyethoxy, pchlorobenzyloxy
or methoxyethylcarbamoylmethoxy); an alkoxyalkyl substituent (e.g.,
methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl or
ethoxypropyl); a carbamoyl substituent; an alkylcarbamoylsubstituent (e.g.,
methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, or diethylcarbamoyl); a
hydroxyalkylcarbamoyl substituent (e.g., 2-hydroxyethylcarbamoyl, bis(2-
hydroxyethyl)carbamoyl, hydroxymethylcarbamoyl, bis(hydroxymethyl)carbamoyl); an
amido substituent; an alkylamido substituent (e.g., acetamido, propionamido, or
butyramido); an alkylcarbonyl substituent (e.g., acetyl, buryryl, or propionyl), an
alkoxycarbonyl substituent (e.g., methoxycarbonyl, ethoxycarbonyl, or
propoxycarbonyl); an aryloxy substituent (e.g., phenoxy, 4-methoxyphenoxy, 4-
nitrophenoxy, 4-cyanophenoxy, 4-methanesulfonamidophenoxy, 4-
methanesulfonylphenoxy, 3-methylphenoxy or 1-naphthyloxy); an acyloxy substituent
(e.g., acetoxy, propanoyloxy, benzolyloxy, 2,4-dichlorobenzolyloxy, ethoxyalkyloxy,
pyruviloyloxy, cinnamoyloxy or myristoyloxy); an alkylthio substituent (e.g.,
methylthio, ethylthio, propylthio, butylthio, 2-cyanoethylthio, benzylthio, phenethylthio,
2-(diethylamino)ethylthio, ethoxyethylthio or phenoxyethylthio); an arylthio substituent
(e.g., phenylthio, 4-carboxyphenylthio, 2-ethoxy-5-tert-butylphenylthio, 2-
carboxyphenylthio or 4-methanesulfonylphenylthio); a heteroarylthio substituent (e.g., 5-
phenyl-2,3,4,5-tetrazolyloxy or 2-benzothiazolyloxy); a heteroaryloxy substituent (e.g.,
5-phenyl-2,3,4,5-tetrazolyloxy or 2-benzothiazolyloxy); a 3-, 4-, 5-, 6-, or 7- membered
heterocycle having at least one nitrogen, oxygen or sulfur atom (e.g., pyridyl, quinolyl,
morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, imidazolyl,
thiadiazolyl, pyrollidine, piperidine, morpholine, piperazine, indoline, hexahydroazepine,
aziridine, and azetidine) and being optionally substituted; an aryl substituent (e.g., phenyl
or naphthyl) which is optionally substituted; a sulfonyl substituent; a sulfmyl
substituent; a phosphonyl substituent; a sulfamoyl substituent; a siloxy substituent; an
acyloxy substituent; a carbamoyloxy substituent; a sulphonamide substituent; an imide
substituent; a ureido substituent; a sulfamoylamino substituent; an
alkoxycarbonylamino substituent; an aryloxycarbonylamino substituent; an
aryloxycarbonyl substituent; and a benzenesulfonamido substituent.
If the compound of the present invention is utilized as a developer, at least one of
R1, R2, R4, or R5 is an amino group, with at least one of the remaining R1, R2, R3, R4, R5,
and R6 being selected from the groups consisting of amino, hydroxyl, a 3-, 4-, 5-, 6-, or 7-
membered heterocycle having at least one nitrogen, oxygen or sulfur atom (e.g., pyridyl,
quinolyl, morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl,
imidazolyl, thiadiazolyl, pyrollidine, piperidine, morpholine, piperazine, indoline,
hexahydroazepine, aziridine, and azetidine) and being optionally substituted, alkylamino
(linear, branched, or cyclic C1-C5), dialkylamino (linear, branched, or cyclic C1-C5),
hydroxyalkylamino (linear, branched, or cyclic C1-C5), dihydroxyalkylamino (linear,
branched, or cyclic C1-C5), arylamino or substituted arylamino (substituents are halogen,
C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino), heteroarylamino
or substituted heteroarylamino (substituents are halogen, C1-C5 alkyl, ClrC5 alkoxy,
trifluoromethyl, amino, C1-C5 alkylamino), arylmethylamino or substituted
arylmethylamino (substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,
amino, C1-C5 alkylamino), and heteroarylmethylamino or substituted
heteroarylmethylamino (substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy,
trifluoromethyl, amino, C1-C5 alkylamino).
If the compound of the present invention is utilized as a coupler, at least one of R1,
R2, R3, R4, R5, and R6 is selected from the group consisting of hydrogen, amino, hydroxyl,
alkylamino (linear, branched, or cyclic C1-C5), hydroxyalkylamino (linear, branched, or
cyclic C1-C5), arylamino or substituted arylamino (substituents are halogen, C1-C5 alkyl,
C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino), heteroarylamino or
substituted heteroarylamino (substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy,
trifluoromethyl, amino, C1-C5 alkylamino), arylmethylamino or substituted
arylmethylamino (substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,
amino, C1-C5 alkylamino), and heteroarylmethylamino or substituted
heteroarylmethylamino (substituents are halogen, C1-C5 alkyl, C1-C5 alkoxy,
trifluoromethyl, amino, C1-C5 alkylamino).
The couplers of the present invention can also accommodate nucleofugic leaving
groups selected from the group consisting of hydrogen, chlorine, cyano, alkoxy, phenoxy,
methylsulfonyoxy, pyridone and pyridazone.
In a preferred embodiment, the couplers of the present invention are utilized in
compositions together with suitable 5-membered ring developers chosen from the
following classes: thiophenes, pyrroles, furans, pyrazoles, imidazoles, thiazoles,
oxazoles, isothiazoles, or isoxazoles. In a more preferred embodiment, the couplers of
the present invention are utilized in compositions together with with developers that are
pyrazoles. In an even more preferred embodiment, the couplers of the present invention
are utilized in compositions together with the following pyrazole developers: 1-methyllH-
pyrazole-4,5-diamine, 2-(4,5-diamino-lH-pyrazol-l-yl)ethanol, 1-isopropyl-lHpyrazole-
4,5-diamine, l-(4-methylbenzyl)- lH-pyrazole-4,5-diamine, 1 -(benzyl)-1Hpyrazole-
4,5-diamine, l-(4-chlorobenzyl)-lH-pyrazole-4,5-diamine and 1-hydroxyethyl-
4,5-diaminopyrazole sulphate. Even more preferably, the couplers of the present
invention are utilized in compositions together with l-methyl-lH-pyrazole-4,5-diamine;
l-hydroxyethyl-4,5-diaminopyrazole sulphate; and 2-(4,5-diamino-lH-pyrazol-lyl)
ethanol. While not being bound to theory, such combinations enable the achievement
of desired more hypsochromic colors (e.g., yellow) relative to conventional combinations
of developers and couplers.
The inventive compounds may be selected from an unsubstituted or substituted
member of the group consisting of benzo[l,2-b;4,5-b']difuran, 5H-l-oxa-5-aza-sindacene,
l-oxa-5-thia-s-indacene, l,5-dmydro-pyrrolo[2,3-f]indole, 5H-l-thia-5-aza-sindacene,
1,5-dithia-s-indacene, benzo[l,2-b;5,4-b']difuran, 7H-l-oxa-7-aza-s-indacene,
l-oxa-7-thia-s-indacene, 1,7-dithia-s-indacene, l,7-dihydro-pyrrolo[3,2-fjindole, 7H-1-
thia-7-aza-s-indacene, benzo[2,l-b;3,4-b']difuran, 8H-l-oxa-8-aza-as-indacene, l-oxa-8-
thia-as-indacene, l,8-dihydro-l,8-diaza-as-indacene, 8H-l-thia-8-aza-as-indacene, 1,8-
dithia-as-indacene, benzo[l,2-b;4,3-b']difuran, 6H-3-oxa-6-aza-as-indacene, 3-oxa-6-thiaas-
indacene, 3,6-dihydro-3,6-diaza-as-indacene, 6H-3-thia-6-aza-as-indacene, and 3,6-
dithia-as-indacene.
Preferred developers and couplers include the following tricyclic 5-6-5
heteroaromatic keratin dyeing compounds having two heteroatoms:
Benzon.2-b:4.5-b'1difuran
(i) Preferred Developers
Preferred benzo[l,2-b;4,5-b']difuran developers are selected from the group
consisting of benzo[l,2-b;4,5-b']difuran-2,6-diamine, N2-ethyl-benzo[l,2-b;4,5-
b']difuran-2,6-diarnine, 2-(6-amino-benzo[l32-b;455-b']difuran-2-ylamino)-ethanol, 2-[(6-
amino-benzo[ 1,2-b;4,5-bl]difuran-2-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 6-pyrrolidin-1 -
yl-benzotl^-b^S-b'Jdifuran^-ylamine, and6-amino-benzo[l,2-b;4,5-b']difuran-2-ol.
(ii) Preferred Couplers
Preferred benzofl-b-b'Jdifuran couplers are selected from the group
consisting of benzo[l,2-b;4,5-b']difuran, benzo[l,2-b;4,5-bl]difuran-2-ylamine,
benzo[l ,2-b;4,5-b']difuran-2-ol, 6-chloro-benzo[l ,2-b;4,5-b']difuran-2-ol, 6-chloro-3-
methoxy-benzo[l,2-b;b']difuran-2-ol, benzo[l,2-b;4,5-b']difuran-4-ol, benzo[l,2-
b^.S-b'Jdifuran^-ylamine, benzotl-b.S-bdifuran-diol, benzo[l,2-b;4,5-
b']difuran-4,8-diol, benzo[l,2-b;4,5-b']difuran-4,8-diamine, benzo[l,2-b;4,5-b']difuran-
3,7-diol, benzofl-b-b'Jdifuran-SJ-diamine, benzo[l,2-b;4,5-b']difuran-3-ol, and
benzo[l,2-b;4,5-b']difuran-3-amine.
5H-1 -Oxa-5-aza-s-indacene
(i) Preferred Developers
Preferred 5H-l-oxa-5-aza-s-indacene developers are selected from the group
consisting of 5H-l-oxa-5-aza-s-indacene-2,6-diamine, 2-(2-amino-5-methyl-5H-l-oxa-
aza-s-indacen-6-ylamino)-ethanol, 2-[(2-amino-5H-l-oxa-5-aza-s-indacen-6-yl)-(2-
hydroxy-ethyl)-amino]-ethanol, 2-(6-amino-5H-1 -oxa-5-aza-s-indacen-2-ylamino)-
ethanol, and 2-pyrrolidin-l-yl-5H-l-oxa-5-aza-s-indacen-6-ylamine.
fii) Preferred Couplers
Preferred 5H-l-oxa-5-aza-s-indacene couplers are selected from the group
consisting of 5H-l-oxa-5-aza-s-indacene, 5H-l-oxa-5-aza-s-indacen-6-ylamine, 5-
methyl-5H-l-oxa-5-aza-s-indacen-6-ylamine, 5-methyl-5H-l-oxa-5-aza-s-indacen-6-ol,
5H-1 -oxa-5-aza-s-indacen-4-ol, 5H-1 -oxa-5-aza-s-indacen-4-ylamine, 5H-1 -oxa-5-aza-sindacen-
2,6-diol, 5H-l-oxa-5-aza-s-indacen-4,8-diol, 5H-l-oxa-5-aza-s-indacen-4,8-
diamine, 5H-l-oxa-5-aza-s-indacen-3,7-diol, 5H-l-oxa-5-aza-s-indacen-3,7-diamine, 5Hl-
oxa-5-aza-s-indacen-3-ol, and 5H-l-oxa-5-aza-s-indacen-3-amine.
(i) Preferred Developers
Preferred l-oxa-5-thia-s-indacene developers are selected from the group
consisting of l-oxa-5-thia-s-indacene-2,6-diamine, 2-(2-amino-l-oxa-5-thia-s-indacen-6-
ylamino)-ethanol, 2-[(2-amino-l-oxa-5-thia-s-indacen-6-yl)-(2-hydroxy-ethyl)-amino]-
ethanol, 2-(6-amino-l-oxa-5-thia-s-indacen-2-ylamino)-ethanol, and 2-pyrrolidin-l-yl-loxa-
5-thia-s-indacen-6-ylamine.
(ii) Preferred Couplers
Preferred l-oxa-5-thia-s-indacene couplers are selected from the group consisting
of l-oxa-5-thia-s-indacene, l-oxa-5-thia-s-indacen-6-ylamme, l-oxa-5-thia-s-indacen-2-
ylamine, l-oxa-5-thia-s-indacen-6-ol, l-oxa-5-thia-s-indacen-4-ol, l-oxa-5-thia-sindacen-
4-ylamine, l-oxa-5-thia-s-indacen-2,6-diol, l-oxa-5-thia-s-indacen-4,8-diol, 1-
oxa-5-thia-s-indacen-4,8-diamine, l-oxa-5-thia-s-indacen-3,7-diol, 1 -oxa-5-thia-sindacen-
3,7-diamine, l-oxa-5-thia-s-indacen-3-ol, and l-oxa-5-thia-s-indacen-3-amine.
1.5-Dihvdro-pvrrolor2.3-flindole
(i) Preferred Developers
Preferred l>5-dihydro-pyrrolo[2,3-f]indole developers are selected from the group
consisting of l,5-dihydro-pyrrolo[2)3-f]indole-2,6-diamine, 2-(6-amino-l;5-dihydropvrrolo[
2,3-f]indol-2-lamino)-ethanol, 2-[(6-ammo-lJ5-dihydro-pyrrolo[2,3-fjindol-2-yl)-
(2-hydroxy-ethyl)-amino]-ethanol, 2-(6-amino-l,5-dihydro-pyrrolo[2,3-f]indol-2-
ylamino)-ethanol, and6-pyrrolidin-l-yl-l)5-dihydro-pyrrolo[253-fjmdol-2-ylamine.
(ii) Preferred Couplers
Preferred l,5-dihydro-pyrrolo[2,3-f]mdole couplers are selected from the group
consisting of l,5-dihydro-pyrrolo[2,3-f]indole, l,5-dmydro-pyrrolo[2,3-f]indol-2-
ylamine, l,5-dihydro-pyrrolo[2)3-fjindol-2-ol, l,5-dihydro-pyrrolo[2J3-fjindol-4-ol, 1,5-
dihydro-pyrrolo[253-f]indol-4-amine, l,5-dihydro-pyirolo[2,3-f]indol-2,6-diol, 1,5-
dihydro-pyrrolo[2,3-f]indol-4,8-diol, l;5-dihydro-pyrrolo[2,3-fjindol-4,8-diamine, 1,5-
dihydro-pyrrolo[2,3-fjindol-3,7-diol, l,5-dihydro-pvrrolo[2,3-f]indol-3,7-diamine, 1,5-
dihydro-pyrrolo[2,3-f]indol-3-ol, and 1,5-dihydro-pyrrolo[253-f]indol-3-aniine.
5H-1 -Thia-5-aza-s-indacene
(i) Preferred Developers
Preferred 5H-l-thia-5-aza-s-indacene developers are selected from the group
consisting of 5H-l-thia-5-aza-s-indacene-2,6-diamine, 5-methyl-5H-l-thia-5-aza-slindacene-2,6-diamine, 2-(6-amino-5H-l-thia-5-aza-s-indacen-2-ylamino)-ethanol, 2-[(6-
amino-5H-1 -thia-5-aza-s-indacen-2-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 2-(2-amino-
5H-1 -thia-5-aza-s-indacen-6-ylamino)-ethanol, and 6-pyrrolidin-1 -yl-5H-1 -thia-5-aza-sindacen-
2-ylamine.
(ii) Preferred Couplers
Preferred 5H-l-thia-5-aza-s-indacene couplers are selected from the group
consisting of 5H-l-thia-5-aza-s-indacene, 5H-l-thia-5-aza-s-indacen-2-ylamine, 5H-1-
thia-5-aza-s-indacen-6-ylamine, 5H-1 -thia-5-aza-s-indacen-2-ol, 5H-1 -thia-5-aza-sindacen-
4-ol, 5H-1 -thia-5-aza-s-indacen-4-ylamine, 5H-1 -thia-5-aza-s-indacen-2,6-diol,
5H-l-thia-5-aza-s-indacen-4,8-diol, 5H-l-thia-5-aza-s-indacen-4,8-diamine, 5H-l-thia-5-
aza-s-indacen-3,7-diol, 5H-l-thia-5-aza-s-indacen-3,7-diamine, 5H-l-thia-5-aza-sindacen-
3-ol, and 5H-l-thia-5-aza-s-mdacen-3-amine.
1,5-Dithia-s-mdacene
(i) Preferred Developers
Preferred 1,5-dithia-s-indacene developers are selected from the group consisting
of 1,5-dithia-s-indacene-2,6-diamine, 2-(6-amino-l ,5-dithia-s-indacen-2-ylamino)-
ethanol, and 2-[(6-amino-1,5-dithia-s-indacen-2-yl)-(2-hydroxy-ethyl)-amino]-ethanol.
(ii) Preferred Couplers
Preferred 1,5-dithia-s-indacene couplers are selected from the group consisting of
l,5-dithia-s-indacen-2-ylarnine, l,5-dithia-s-indacen-2-ol, l,5-dithia-s-indacen-4-ol, 1,5-
dithia-s-indacen-4-ylamine, dithia-s-indacen-2,6-diol, dithia-s-indacen-4,8-diol, dithia-sindacen-
4,8-diamine, dithia-s-indacen-3,7-diol, dithia-s-indacen-3,7-diamine, dithia-sindacen-
3-ol, dithia-s-indacene-3-amine, 1,5-dithia-s-indacene, 2,6-dimethyl-1,5-dithia-sindacene,
3,7-dimethyl-l,5-dithia-s-indacen, and 2-methylbenzo[l,2-b;5,4-b']difuran.
Benzon.2-b:5.4-b'1difuran
(i) Preferred Developers
Preferred benzo[l,2-b;5,4-b']difuran developers are selected from the group
consisting of benzo[l,2-b;5,4-b']difuran-2,3-diamme, 3-amino-benzo[l,2-b;5,4-
b']difuran-2-ol, e-amino-benzotl-bjS-b'Jdifuran.S-diol, and benzo[l,2-b;5,4-
b']difuran-2,3,5,6-tetraamine.
(ii) Preferred Couplers
Preferred benzofl-bS-b'Jdifuran couplers are selected from the group
consisting of benzo[l,2-b;5,4-b']dii:uran-2-ylarnme, 3-chloro-benzo[l,2-b;5,4-b']diftiran-
2-ol, benzo[l,2-b;5,4-b']difuran-2,6-diol, 6-amino-benzo[lb;5,44)']difuran-2-ol, 3-(2-
hydroxy-benzo[l,2-b;5,4-b']difuran-3-yl)-5,5-dimethyl-oxazolidine-2,4-dione, benzo[l,2-
b;5,4-b']difuran-4-ol, benzo[l,2-b;5,4-b']difuran-4-amine, benzo[l,2-b;5,4-b']difuran-4,8-
diol, benzo[l,24;5,4-b']difuran-4,8-diamme, benzo[l,2-b;5,4-b']difuran-3,7-diol,
benzo[l,2-b;5,4-b']difuran-3,7-diamine, benzo[l,2-b;5,4-b']difuran-3-ol, benzo[l,2-b;5,4-
b'jdifuran-3-amine, benzo[l,2-b;5,4-b']difuran, 256-dimethylbenzo[l,2-b;5,4-bl]difuran,
3,7-dimethylbenzo[l,2-b;554-b']difuran, and2-methylbenzo[l,2-b;5,4-b']difuran.
7H-1 -Oxa-7-aza-s-indacene
(i) Preferred Developers
Preferred 7H-l-oxa-7-aza-s-indacene developers are selected from the group
consisting of 7-Methyl-7H-l-oxa-7-aza-s-indacene-5,6-diamine, 5-amino-7-methyl-7H-loxa-
7-aza-s-indacen-6-ol, 3,6-diammo-7-methyl-7H-l-oxa-7-aza-s-indacene-2,5-diol, and
7-methyl-7H-l-oxa-7-aza-s-indacene-2,3,5,6-terraamine.
(ii) Preferred Couplers
Preferred 7H-l-oxa-7-aza-s-indacene couplers are selected from the group
consisting of 7-Methyl-7H-l-oxa-7-aza-s-indacen-6-ylamine, 3-(6-hydroxy-7-methyl-7Hl-
oxa-7-aza-s-indacen-5-yl)-5,5-dimethyl-oxazolidine-2,4-dione, 6-amino-7-methyl-7H-
1 -oxa-7-aza-s-indacen-2-ol, 7-methyl-7H-1 -oxa-7-aza-s-indacene-2,6-diamine, 7H-1 -oxa-
7-aza-s-indacen-4-ol, 7H-1 -oxa-7-aza-s-indacen-4-amine, 7H-1 -oxa-7-aza-s-indacen-4,8-
diol, 7H-l-oxa-7-aza-s-indacen-4,8-diamine, 7H-l-oxa-7-aza-s-indacen-3,7-diol, 7H-1-
oxa-7-aza-s-indacen-3,7-diamine, 7H-1 -oxa-7-aza-s-indacen-3-ol, 7H-1 -oxa-7-aza-sindacen-
3-amine, 7H-l-oxa-7-aza-s-indacene, 2,6-dimethyl-7H-l-oxa-7-aza-s-indacene,
3,5-diinethyl-7H-l-oxa-7-aza-s-indacene, and2-methyl-7H-l-oxa-7-aza-s-indacene.
1 -Oxa-7-thia-s-indacene
(i) Preferred Developers
Preferred l-oxa-7-thia-s-indacene developers are selected from the group
consisting of l-oxa-7-thia-s-indacene-5,6-diamine, 6-amino-l-oxa-7-thia-s-indacen-5-ol,
5-amino-l-oxa-7-thia-s-indacen-6-ol, l-oxa-7-thia-s-indacene-253,5s6-tetraamine, and
2,6-diamino- l-oxa-7-thia-s-indacene-3,5-diol. J
(ii) Preferred Couplers
Preferred l-oxa-7-thia-s-indacene couplers are selected from the group consisting
of l-oxa-7-thia-s-indacen-2-ol, l-oxa-7-thia-s-indacene-2,6-diamine, 3-(6-hydroxy-l-oxa-
7-thia-s-indacen-5-yl)-5,5-dimethyl-oxazolidine-2,4-dione, l-oxa-7-thia-s-indacen-4-ol,
1 -oxa-7-thia-s-indacen-4-amine, 1 -oxa-7-thia-s-indacen-4,8-diol, 1 -oxa-7-thia-s-indacen-
4,8-diamine, l-oxa-7-thia-s-indacen-3,7-diol, l-oxa-7-thia-s-indacen-3,7-diamine, 1-oxa-
7-thia-s-indacen-3-ol, l-oxa-7-thia-s-indacen-3-amine, l-oxa-7-thia-s-indacene, 2,6-
dimethyl-l-oxa-7-thia-s-indacene, 3,5-dimethyl-l-oxa-7-thia-s-indacene, and 2-methyl-loxa-
7-thia-s-indacene.
1,7-Dithia-s-indacene
(i) Preferred Developers
Preferred 1,7-dithia-s-indacene developers are selected from the group consisting
of l,7-dithia-s-indacene-2,3-diamine, 2-amino-l,7-dithia-s-indacen-3-ol, 3-amino-l,7-
dithia-s-indacen-2-ol, l,7-dithia-s-indacene-2,3,5,6-tetraamine, and 2,6-diamino-l,7-
dithia-s-indacene-3,5-diol.
(ii) Preferred Couplers
Preferred 1,7-dithia-s-indacene couplers are selected from the group consisting of
l,7-dithia-s-indacen-2-ylamine, l,7-dithia-s-indacen-2-ol, l,7-dithia-s-indacene-2,6-
diamine, 3 -(2-hydroxy-1,7-dithia-s-indacen-3 -yl)-5,5-dimethyl-oxazolidine-2,4-dione,
l,7-dithia-s-indacen-4-ol, l,7-dithia-s-indacen-4-amine, l,7-dithia-s-indacen-4,8-diol,
l,7-dithia-s-indacen-4,8-diamine, l,7-dithia-s-indacen-3,7-diol, l,7-dithia-s-indacen-3,7-
diamine, l,7-dithia-s-indacen-3-ol, l,7-dithia-s-indacen-3-amine, 1,7-dithia-s-indacene,
2,6-dimethyl-1,7-dithia-s-indacene, 3,5-dimethyl-1,7-dithia-s-indacene, and 2-methyl-1,7-
dithia-s-indacene.
1.7-Dihydro-pvrrolor3.2-f|mdole
(i) Preferred Developers
Preferred l,7-dihydro-pyrrolo[3,2-fjindole developers are selected from the group
consisting of 1 -methyl-l,7-dihydro-pyrrolo[3,2-f]indole-2,3-diamine, l,7-dimethyl-l,7-
dihydro-pyrrolo[3,2-f]indole-2,3-diamine, 3-amino-l-methyl-l,7-dihydro-pyrrol
o[3,2-f]indol-2-ol, and2-amino-l-methyl-l,7-dihydro-pyrrolo[3,2-f]indol-3-ol.
(ii) Preferred Couplers
Preferred l,7-dihydro-pyrrolo[3,2-fjindole couplers are selected from the group
consisting of l,7-dmydro-pyrrolo[3,2-fjindole, l-methyl-l,7-dihydro-pynx>lo[3,2-fjindol2-
ylamine, 1 -methyl-1,7-dihydro-pyrrolo[3,2-f]indol-2-ol, 1,7-dimethyl-1,7-dihydropyirolo[
3,2-f]indole-2,6-diol, l,7-dihydro-pyrrolo[3,2-f]indol-4-ol, 1,7-dihydropyrrolo[
3,2-f]indol-4-amine, l,7-dihydro-pyrrolo[3,2-f|indol-4,8-diol, 1,7-dihydropyrrolo[
3,2-f]indol-4,8-diamine, l,7-dihydro-pyrrolo[3,2-f]indol-3,7-diol, 1,7-dihydropyirolo[
3,2-f]indol-3,7-diamine, l,7-dihydro-pyrrolo[3,2-f]indol-3-ol, 1,7-dihydropyrrolo[
3,2-f]indol-3-amine, 2,6-dimemyl-l,7-dihydro-pyrrolo[3,2-i]indole) 3,5-
dimethyl-l,7-dihydro-pyrrolo[3,2-f]indole, and 2-methyl-l,7-dihydro-pyrrolo[3,2-
fjindole.
7H-1 -Thia-7-aza-s-indacene
(i) Preferred Developers
Preferred 7H-1 -thia-7-aza-s-indacene developers are selected from the group
consisting of 7H-l-thia-7-aza-s-indacene-2,3-diamine, 3-amino-7H-l-thia-7-aza-sindacen-
2-ol, 2-amino-7H-l-thia-7-aza-s-indacen-3-ol, 7-methyl-7H-l-thia-7-aza-sindacene-
2,3-diamine, 5-amino-7-methyl-7H-l-thia-7-aza-s-indacen-6-ol, and 6-amino-7-
methyl-7H-1 -thia-7-aza-s-indacen-5-ol.
(ii) Preferred Couplers
Preferred 7H-1-thia-7-aza-s-indacene couplers are selected from the group
consisting of 7H-1-thia-7-aza-s-indacene, 7H-l-thia-7-aza-s-indacen-2-ylamine, 7H-1-
thia-7-aza-s-indacen-2-ol, 7-methyl-7H-1 -thia-7-aza-s-indacene-2,6-diol, 7-methyl-7H-1
thia-7-aza-s-indacen-6-ol, 7-methyl-7H-1 -thia-7-aza-s-indacen-6-ylamine, 7H-1 -thia-7-
aza-s-indacen-4-ol, 7H-1 -thia-7-aza-s-indacen-4-amine, 7H-1 -thia-7-aza-s-indacen-4,8-
diol, 7H-l-thia-7-aza-s-indacen-4,8-diamine, 7H-l-thia-7-aza-s-indacen-3,7-diol, 7H-1-
thia-7-aza-s-indacen-3,7-diamine, 7H-1 -thia-7-aza-s-indacen-3-ol, 7H-1 -thia-7-aza-sindacen-
3-amine, 2,6-dimethyl-7H-1 -thia-7-aza-s-indacene, 3,5-dimethyl-7H-1 -thia-7-
aza-s-indacene, and 2-methyl-7H-l-thia-7-aza-s-indacene.
Benzol. l-b:3.4-b'1difuran
(i) Preferred Developers
Preferred benzo[2,l-b;3,4-b']difuran developers are selected from the group
consisting of benzo[2,l-b;3,4-b']difuran-2,7-diamine, 2-(7-amino-benzo[2,l-b;3,4-
b']difuran-2-ylamino)-ethanol, 2-[(7-amino-benzo[2,1 -b;3,4-b']difuran-2-yl)-(2-hydroxyethyl)-
amino]-ethanol, 7-pyrrolidin-l-yl-benzo[2,l-b;3,4-b']difuran-2-ylamine, and 7-
ammo-benzo[2,l-b;3,4-b']difuran-2-ol.
(ii) Preferred Couplers
Preferred benzo[2,l-b;3,4-b']difuran couplers are selected from the group
consisting of benzo[25l-b;3,4-b'Jdiftiran-2-ylamine, benzo[2,l-b;3,4-b']difuran-2-ol, 3-(2-
hydroxy-benzop.l-b-bdifuran-S-yO-S-dimethyl-oxazolidine-dione, benzo[2,lb;
3,4-b']difuran-4-ol, benzop-b-bdifuran^-amine, benzo[2,l-b;3,4-b']difuran-4,5-
diol , benzo[2,l-b;3)4-b']diruran-3,6-diamine, benzo[25l-b;3,4-b']difuran-2,7-diol,
benzo[2,l-b;3,4-b'Jdifuran-3-ol, benzo[2j4;3,4-b]dimran-3-amine, benzo[2,l-b;3,4-
b']difuran, 2,7-dimethyl-benzo[2,l-b;3,4-b']difuran, 3,6-dirnethyl-benzo[2,l-b;3,4-
b'Jdifuran, and 2-methyl-benzo[2,l-b;3,4-b']difuran.
8H-1 -Oxa-8-aza-as-indacene
(i) Preferred Developers
Preferred 8H-l-oxa-8-aza-as-indacene developers are selected from the group
consisting of 8H-l-oxa-8-aza-as-indacene-2,7-diamine, 2-(2-amino-8-methyl-8H-l-oxa-
8-aza-as-indacen-7-ylamino)-ethanol, 2-[(2-amino-8-methyl-8H-l-oxa-8-aza-as-indacen-
7-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 7-amino-8H-l-oxa-8-aza-as-indacen-2-ol, 2-
amino-8-methyl-8H-1 -oxa-8-aza-as-indacen-7-ol, 8-methyl-N2-propyl-8H-1 -oxa-8-azaas-
indacene-2,7-diamine, and 8-methyl-2-pyrrolidin-l-yl-8H-l-oxa-8-aza-as-indacen-7-
ylamine.
(ii) Preferred Couplers
Preferred 8H-l-oxa-8-aza-as-indacene couplers are selected from the group
consisting of 8H-l-oxa-8-aza-as-indacen-2-ol, 8-methyl-8H-l-oxa-8-aza-as-indacen-7-
ylamine, 6-chloro-8-methyl-8H-1 -oxa-8-aza-as-indacen-7-ylamine, 2-(2-amino-8-methyl-
8H-1 -oxa-8-aza-as-indacen-7-yloxy)-ethanol, 8H-1 -oxa-8-aza-as-indacen-4-ol, 8H-1 -oxa-
8-aza-as-indacen-4-amine, 8H-1 -oxa-8-aza-as-indacen-4,5-diol, 8H-1 -oxa-8-aza-asindacen-
S-diamine, 8H-l-oxa-8-aza-as-indacen-2,7-diol, 8H-l-oxa-8-aza-as-indacen-3-
ol, 8H-l-oxa-8-aza-as-indacen-3-amine, 8H-l-oxa-8-aza-as-indacene, 2,7-dimethyl-8Hl-
oxa-8-aza-as-indacene, 3,6-dimethyl-8H-l-oxa-8-aza-as-indacene, and 2-methyl-8H-loxa-
8-aza-as-indacene.
1 -Oxa-8-thia-as-indacene
(i) Preferred Developers
Preferred l-oxa-8-thia-as-indacene developers are selected from the group
consisting of l-oxa-8-thia-as-indacene-2,7-diamine, 2-(2-amino-l-oxa-8-thia-as-indacen-
7-ylamino)-ethanol, 2-[(2-amino-1 -oxa-8-thia-as-indacen-7-yl)-(2-hydroxy-ethyl)-
amino]-ethanol, 7-amino-l-oxa-8-thia-as-indacen-2-ol, 2-amino-l-oxa-8-thia-as-indacen-
7-ol, N2-propyl-l-oxa-8-thia-as-indacene-2,7-diamine, and 2-pyrrolidin-l-yl-l-oxa-8-
thia-as-indacen-7-ylamine.
(ii) Preferred Couplers
Preferred l-oxa-8-thia-as-indacene couplers are selected from the group consisting
of l-oxa-8-thia-as-indacen-2-ol, l-oxa-8-thia-as-mdacen-7-ylamine, 6-chloro-l-oxa-8-
thia-as-indacen-7-ylamine, 2-(2-amino-l-oxa-8-thia-as-indacen-7-yloxy)-ethanol, 1-oxa-
8-thia-as-indacen-4-ol , l-oxa-8-thia-as-indacen-4-amine, l-oxa-8-thia-as-indacen-4,5-
diol , l-oxa-8-thia-as-indacen-3,6-diamme, l-oxa-8-thia-as-indacen-2,7-diol, l-oxa-8-
thia-as-indacen-3-ol, l-oxa-8-thia-as-indacen-3-amine, l-oxa-8-thia-as-indacene, 2,7-
dimethyl-l-oxa-8-thia-as-indacene, 3,6-dimethyl-l-oxa-8-thia-as-indacene, and 2-methyll-
oxa-8-thia-as-indacene.
1.8-Dihydro-1.8-diaza-as-indacene
(i) Preferred Developers
Preferred l,8-dihydro-l,8-diaza-as-indacene developers are selected from the
group consisting of 1,8-dihydro-l,8-diaza-as-mdacene-2,7-diamine, 2-(7-amino-l,8-
dihydro-1,8-diaza-as-indacen-2-ylamino)-ethanol, 2-[(7-amino-1,8-dihydro-1,8-diaza-asindacen-
2-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 7-amino-l,8-dihydro-l,8-diaza-asindacen-
2-ol, 7-amino-1,8-dihydro-1,8-diaza-as-indacen-2-ol, N7-propyl-1,8-dihydro-1,8-
diaza-as-indacene-2,7-diamine, and 7-pyrrolidin-1 -yl-1,8-dihydro-1,8-diaza-as-indacen-2-
ylamine.
(ii) Preferred Couplers
Preferred 1,8-dihydro-1,8-diaza-as-indacene couplers are selected from the group
consisting of l,8-dihydro-l,8-diaza-as-indacene, 1,8-dihydro-l,8-diaza-as-indacen-2-ol,
1,8-dihydro-l,8-diaza-as-indacen-2-ylamine, 3-chloro-1,8-dihydro-1,8-diaza-as-indacen-
2-ylamine, 2-(7-amino-l,8-dihydro-l,8-diaza-as-indacen-2-yloxy)-ethanol, 1,8-dihydrol,
8-diaza-as-indacen-4-ol , l,8-dihydro-l,8-diaza-as-indacen-4-amine, l,8-dihydro-l,8-
diaza-as-indacen-4,5-diol , l,8-dihydro-l,8-diaza-as-indacen-3,6-diamine, 1,8-dihydro-
1,8-diaza-as-indacen-2,7-diol, 1,8-dihydro-1,8-diaza-as-indacen-3-ol, 1,8-dihydro-1,8-
diaza-as-indacen-3-amine, 1,8-dihydro-l ,8-diaza-as-indacene, 2,7-dimethyl-1,8-dihydro-
1,8-diaza-as-indacene, 3,6-dimethyl-l,8-dihydro-l,8-diaza-as-indacene, and 2-methyl-
1,8-dihydro-1,8-diaza-as-indacene.
8H-l-Thia-8-aza-as-indacene
(i) Preferred Developers
Preferred 8H-l-thia-8-aza-as-indacene developers are selected from the group
consisting of 8H-l-thia-8-aza-as-indacene-2,7-diamine, 2-(7-amino-8H-l-thia-8-aza-asindacen-
2-ylamino)-ethanol, 2-[(7-amino-8H-1 -thia-8-aza-as-indacen-2-yl)-(2-hydroxyethyl)-
amino]-ethanol, 2-amino-8H-l-thia-8-aza-as-indacen-7-ol, 7-amino-8H- l-thia-8-
aza-as-indacen-2-ol, N7-propyl-8H-l-thia-8-aza-as-indacene-2,7-diamine, and 7-
pynx lidin-l-yl-8H-l-thia-8-aza-as-indacen-2-ylamine.
(ii) Preferred Couplers
Preferred 8H-l-thia-8-aza-as-indacene couplers are selected from the group
consisting of 8H-l-thia-8-aza-as-indacene, 8H-l-thia-8-aza-as-indacen-7-ol, 8H-l-thia-8-
aza-as-indacen-2-ylamine, 3-chloro-8H-l-thia-8-aza-as-indacen-2-ylamine, 2-(7-amino-
8H-1 -thia-8-aza-as-indacen-2-yloxy)-ethanol, 8H-1 -thia-8-aza-as-indacen-4-ol, 8H-1 -
thia-8-aza-as-indacen-4-amine, 8H-1 -thia-8-aza-as-indacen-4,5-diol, 8H- l-thia-8-aza-asindacen-
3,6-diamine, 8H-l-thia-8-aza-as-indacen-2,7-diol, 8H-l-thia-8-aza-as-indacen-3-
ol, 8H-l-thia-8-aza-as-indacen-3-amine, 2,7-dimethyl-8H-l-thia-8-aza-as-indacene, 3,6-
dimethyl-8H-l-thia-8-aza-as-indacene, and2-methyl-8H-l-thia-8-aza-as-indacene.
1,8-Dithia-as-indacene
(i) Preferred Developers
Preferred 1,8-dithia-as-indacene developers are selected from the group consisting
of 1,8-dithia-as-indacene-2,7-diamine, 2-(7-amino-l ,8-dithia-as-indacen-2-ylamino)-
ethanol, 2-[(7-amino-1,8-dithia-as-indacen-2-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 7-
amino-l,8-dithia-as-ndacen-2-ol, N7-propyl-l,8-dithia-as-indacene-2,7-diamine, and 7-
pyrrolidin-1-yl-1,8-dithia-as-indacen-2-ylamine.
(ii) Preferred Couplers
Preferred 1,8-dithia-as-indacene couplers are selected from the group consisting of
l,8-dithia-as-indacen-2-ol, l,8-dithia-as-indacen-2-ylamine, 3-chloro-l,8-dithia-asindacen-
2-ylamine, 7-methoxy-1,8-dithia-as-indacen-2-ylamine, 1,8-dithia-as-indacen-4-
ol, l,8-dithia-as-indacen-4-amine, l,8-dithia-as-indacen-4,5-diol, 1,8-dithia-as-indacen3,6-
diamine, l,8-dithia-as-indacen-2,7-diol, l,8-dithia-as-indacen-3-ol, 1,8-dithia-asindacen-
3-amine, 1,8-dithia-as-indacene, 2 J-dimethyl-1,8-dithia-as-indacene, 3,6-
dimethyl-1,8-dithia-as-indacene, and 2-methyl-l,8-dithia-as-indacene.
BenzoF 1.2-b:4.3-b'1difuran
(i) Preferred Developers
Preferred benzo[l,2-b;4,3-b']difuran developers are selected from the group
consisting of benzo[l,2-b;4,3-b']difuran-2,7-diamine, N7-ethyl-benzo[l,2-b;4,3-
b']difuran-2,7-diamme, 2-(7-amino-benzo[l ,2-b;4,3-b']difuran-2-ylamino)-emanol, 2-[(7-
ammo-benzo[l,2-b;4,3-bl]difuran-2-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 7-pyrrolidin-lyl-
benzo[l,2-b;4,3-b']difuran-2-ylamine, 7-amino-benzo[lJ2-b;4}3-bl]difuran-2-ol) 1-
methyl-benzofl-b.S-bdifuran-diamine, 2,7-diamino-benzo[l,2-b;4,3-b']difuran-
1-carbonitrile, and S-chloro-methyl-benzotl-b.S-b'Jdifuran-ylamine.
(ii) Preferred Couplers
Preferred benzo[l,2-b;4,3-b']difuran couplers are selected from the group
consisting of benzo[l,2-b;4,3-b']difuran-2-ol, benzo[l,2-b;4,3-b']difuran-2-ylamine, 7-
chloro-benzo[l b;4,3-b']difuran-2-ol, 3-(7-hydroxy-benzo[l ,2-b;4,3-b']difuran-2-yl)-
5,5-dimethyl-oxazolidine-2,4-dione, benzo[l,2-b;4,3-b']difuran-4-ol, benzo[l ,2-b;4,3-
b'jdifuran-4-amine, benzo[l ,2-b;4,3-b']difuran-1,8-diol, benzo[ 1,2-b;4,3-b']difuran-1,8-
diamine, benzo[l,2-b;4,3-b']difuran-2,7-diolJ benzofl-b.S-bdifuran-l-ol, benzo[l,2-
b;4,3-b']difuran-l-amine, benzo[l,2-b;4,3-b']difuran, 2,7-dimethyl- benzo[l,2-b;4,3-
b'Jdifuran, l,8-dimethyl-benzo[l,2-b;4,3-bl]difuran, and 2-methyl-benzo[l,2-b;4,3-
b'Jdifuran.
6H-3-Oxa-6-aza-as-indacene
(i) Preferred Developers
Preferred 6H-3-oxa-6-aza-as-indacene developers are selected from the group
consisting of 6H-3-oxa-6-aza-as-indacene-2,7-diamine, N7-ethyl-6H-3-oxa-6-aza-asindacene-
2,7-diamine, 2-(2-ammo-6-methyl-6H-3-oxa-6-aza-as-indacen-7-ylamino)-
ethanol, 2-[(2-ammo-6H-3-oxa-6-aza-as-indacen-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol,
7-pyrrolidin-1 -yl-6H-3-oxa-6-aza-as-indacen-2-ylamine, 2-amino-6H-3-oxa-6-aza-asindacen-
7-ol, 2-(7-amino-6,8-dimethyl-6H-3-oxa-6-aza-as-mdacen-2-ylamino)-ethanol,
2-[(7-amino-6H-3-oxa-6-aza-as-indacen-2-yl)-(2-hydroxy-ethyl)-amino]-ethanol, and 8-
chloro-2-pyrrolidin-l-yl-6H-3-oxa-6-aza-as-indacen-7-ylamine.
(ii) Preferred Couplers
Preferred 6H-3-oxa-6-aza-as-indacene couplers are selected from the group
consisting of 6H-3-oxa-6-aza-as-indacene, 6-methyl-6H-3-oxa-6-aza-as-indacen-7-ol,
6H-3-oxa-6-aza-as-indacen-2-ylamine, 6-Methyl-6H-3-oxa-6-aza-as-indacen-7-ylamine,
3-(7-hydroxy-6-methyl-6H-3-oxa-6-aza-as-indacen-2-yl)-5,5-dimethyl-oxazolidine-2,4-
dione, 6H-3-oxa-6-aza-as-indacen-4-ol, 6H-3-oxa-6-aza-as-indacen-4-ainine, 6H-3-oxa-
6-aza-as-indacen-l,8-diol, 6H-3-oxa-6-aza-as-indacen-l,8-diamine, 6H-3-oxa-6-aza-asmdacen-
2,7-diol, 6H-3-oxa-6-aza-as-indacen-l-ol, 6H-3-oxa-6-aza-as-indacen-l-amine3
2,7-dimethyl-6H-3-oxa-6-aza-as-indacene, l,8-dimethyl-6H-3-oxa-6-aza-as-indacene,
and 2-methyl-6H-3 -oxa-6-aza-as-indacene.
3 -Oxa-6-thia-as-indacene
(i) Preferred Developers
Preferred 3-oxa-6-thia-as-indacene developers are selected from the group
consisting of 3-oxa-6-thia-as-indacene-2,7-diamine, N7-ethyl-3-oxa-6-thia-as-indacene-
2,7-diamine, 2-(2-amino-3-oxa-6-thia-as-indacen-7-ylamino)-ethanol, 2-[(2-amino-3-oxa-
6-thia-as-indacen
-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 7-pyrrolidin-l-yl-3-oxa-6-thia-as-indacen-2-
ylamine, 2-arnino-3-oxa-6-thia-as-indacen-7-ol, 2-(7-amino-8-methyl-3-oxa-6-thia-asindacen-
2-ylamino)-ethanol, 2-[(7-amino-3-oxa-6-thia-as-indacen-2-yl)-(2-hydroxyethyl)-
amino]-ethanol, and 8-chloro-2-pyrrolidin-1 -yl-3-oxa-6-thia-as-indacen-7-ylamine.
(ii) Preferred Couplers
Preferred 3-oxa-6-thia-as-indacene couplers are selected from the group consisting
of 3-oxa-6-thia-as-indacen-7-ol, 3-oxa-6-thia-as-indacen-2-ylamine, 3-oxa-6-thia-asindacen-
7-ylamine, 3-(7-hydroxy-3-oxa-6-thia-as-indacen-2-yl)-5,5-dimethyloxazolidine-
2,4-dione, 3-oxa-6-thia-as-indacen-4-ol, 3-oxa-6-tliia-as-indacen-4-amine, 3-
oxa-6-thia-as-indacen-1,8-diol, 3-oxa-6-thia-as-indacen-1,8-diamine, 3 -oxa-6-thia-asindacen-
2,7-diol, 3-oxa-6-thia-as-indacen-l-ol, 3-oxa-6-thia-as-indacen-l-amine, 3-oxa-
6-thia-as-indacene, 2,7-dimethyl-3-oxa-6-thia-as-indacene, 1,8-dimethyl-3-oxa-6-thia-asindacene,
and 2-methyl-3-oxa-6-thia-as-indacene.
3.6-Dihvdro-3.6-diaza-as-indacene
(i) Preferred Developers
Preferred 3,6-dihydro-3,6-diaza-as-indacene developers are selected from the
group consisting of 3,6-dihydro-3,6-diaza-as-indacene-2,7-diamine, N7-ethyl-3,6-
dihydro-3,6-diaza-as-indacene-2,7-diamine, 2-(7-amino-3,6-dihydro-3,6-diaza-asindacen-
2-ylamino)-ethanol, 2-[(7-amino-3,6-dihydro-3,6-diaza-as-indacen-2-yl)-(2-
hydroxy-ethyl)-amino]-ethanol, 7-pyrrolidin-l-yl-3,6-dihydro-3,6-diaza-as-indacen-2-
ylamine, 7-amino-3,6-dihydro-3,6-diaza-as~mdacen-2-ol, 2-(7-arnino-6,8-dimethyl-3,6-
dihydro-3,6-diaza-as-indacen-2-ylamino)-ethanol, 2-[(7-amino-6-methyl-3,6-dihydro-3,6-
diaza-as-indacen-2-yl)-(2-hydroxy-ethyl)-amino]-ethanol, and l-chloro-3-methyl-7-
pyrrolidin-1 -yl-3,6-dihydro-3,6-diaza-as-indacen-2-ylamine.
(ii) Preferred Couplers
Preferred 3,6-dihydro-3,6-diaza-as-indacene couplers are selected from the group
consisting of 3,6-dihydro-3,6-diaza-as-indacene, 3-methyl-3,6-dihydro-3,6-diaza-asindacen-
2-ol, 3,6-dihydro-3,6-diaza-as-indacen-2-ylamine, 3-methyl-3,6-dihydro-3,6-
diaza-as-indacen-2-ylamine, 3-(7-hydroxy-6-methyl-3,6-dihydro-3,6-diaza-as-indacen-2-
yl)-5,5-dimethyl-oxazolidine-2,4-dione, 3,6-dihydro-3,6-diaza-as-indacen-4-ol, 3,6-
dihydro-3,6-diaza-as-indacen-4-amine, 3,6-dihydro-3,6-diaza-as-indacen-l,8-diol, 3,6-
dihydro-3,6-diaza-as-indacen-l,8-diamine, 3,6-dihydro-3,6-diaza-as-indacen-2,7-diol,
3,6-dihydro-3,6-diaza-as-indacen-l-ol, 3,6-dihydi-o-3,6-diaza-as-indacen-l-amine, 3,6-
dihydro-3,6-diaza-as-indacene, 2,7-dimethyl-3,6-dihydro-3,6-diaza-as-indacene, 1,8-
dimethyl-3,6-dihydro-3,6-diaza-as-indacene, and 2-methyl-3,6-dihydro-3,6-diaza-asindacene.
6H-3-Thia-6-aza-as-indacene
(i) Preferred Developers
Preferred 6H-3-thia-6-aza-as-indacene developers are selected from the group
consisting of 6H-3-thia-6-aza-as-indacene-2,7-diamine, N7-ethyl-6H-3-thia-6-aza-asmdacene-
2,7-diamine, 2-(2-amino-6H-3-thia-6-aza-as-indacen-7-ylamino)-ethanol, 2-[(2-
amino-6H-3-thia-6-aza-as-indacen-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 7-pyrrolidin-
1 -yl-6H-3-thia-6-aza-as-indacen-2-ylamine, 2-amino-6H-3-thia-6-aza-as-indacen-7-ol, 2-
(7-amino-6,8-dimethyl-6H-3-thia-6-aza-as-indacen-2-ylamino)-ethanol, 2-[(7-amino-6-
methyl-6H-3-thia-6-aza-as-indacen-2-yl)-(2-hydroxy-ethyl)-amino]-ethanol, and 8-
chloro-6-methyl-2-pyrrolidm-1 -yl-6H-3 -thia-6-aza-as-indacen-7-ylamine.
(ii) Preferred Couplers
Preferred 6H-3-thia-6-aza-as-indacene couplers are selected from the group
consisting of 6H-3-thia-6-aza-as-indacene, 6-methyl-6H-3-thia-6-aza-as-indacen-7-ol,
6H-3-thia-6-aza-as-indacen-2-ylamine, 6-methyl-6H-3-thia-6-aza-as-indacen-7-ylamine,
3-(7-hydroxy-6-methyl-6H-3-thia-6-aza-as-indacen-2-yl)-5,5-imethyl-oxazolidine-2,4-
dione, 6H-3-thia-6-aza-as-indacen-4-ol, 6H-3-thia-6-aza-as-mdacen-4-amine, 6H-3-thia-
6-aza-as-indacen-l,8-diol, 6H-3-thia-6-aza-as-indacen-l,8-diamine, 6H-3-thia-6-aza-asindacen-
2,7-diol, 6H-3-thia-6-aza-as-indacen-1 -ol, 6H-3-thia-6-aza-as-indacen-1 -amine,
6H-3-thia-6-aza-as-indacene, 2,7-dimethyl-6H-3-thia-6-aza-as-indacene, 1,8-dimethyl-
6H-3-thia-6-aza-as-indacene, and2-methyl-6H-3-thia-6-aza-as-indacene.
3,6-Dithia-as-indacene
(i) Preferred Developers
Preferred 3,6-dithia-as-indacene developers are selected from the group consisting
of 3,6-dithia-as-indacene-2,7-diamine, N7-ethyl-3,6-dithia-as-indacene-2,7-diamine, 2-(7-
amino-3,6-dithia-as-indacen-2-ylamino)-ethanol, 2-[(7-amino-3,6-dithia-as-indacen-2-yl)-
(2-hydroxy-ethyl)-amino]-ethanol, 7-pyrrolidm-l-yl-3,6-dithia-as-indacen-2-ylamine, 7-
amino-3,6-dithia-as-indacen-2-ol, 3-[(7-amino-8-methyl-3,6-dithia-as-indacen-2-yl)-(2-
hydroxy-ethyl)-arnino]-propane-1,2-diol, 1 -(7-amino-356-dithia-as-indacen-2-ylamino)-
butan-2-ol, and l-chloro-7-pyrrolidin-l-yl-3,6-dithia-as-indacen-2-ylamine.
(ii) Preferred Couplers
Preferred 3,6-dithia-as-indacene couplers are selected from the group consisting of
3,6-dithia-as-indacen-2-ol, 3,6-dithia-as-indacen-2-ylamine, 7-chloro-3,6-dithia-asindacen-
2-ol, 3-(7-hydroxy-3,6-dithia-as-indacen-2-yl)-5J5-dimethyl-oxazolidine-2}4-
dione, 3,6-dithia-as-indacen-4-ol, 3,6-dithia-as-indacen-4-amine, 3,6-dithia-as-indacen-
1,8-diol, 3,6-dithia-as-indacen-l,8-diamine, 3,6-dithia-as-indacen-2,7-diol, 3,6-dithia-asindacen-
1-ol, 3,6-dithia-as-indacen-l-amine, 3,6-dithia-as-indacene, 2,7-dimethyl-3,6-
dithia-as-indacene, l,8-dmiethyl-3,6-dithia-as-indacene, and 2-methyl-3,6-dithia-asindacene.
Especially preferred developers of the present invention are selected from the
group consisting of benzo[l,2-b;4,5-b']difuran-2,6-diamine, 6-pyrrolidin-l-yl-benzo[l,2-
b;4,5-bl]difuran-2-ylamine, 6-amino-benzo[l)2-b;4,5-bl]difuran-2-ol, 5H-l-oxa-5-aza-sindacene-
2,6-diamine, 2-(6-amino-5H- l-oxa-5-aza-s-indacen-2-ylamino)-ethanol, 2-
pyrrolidin-1 -yl-5H-1 -oxa-5-aza-s-indacen-6-ylamine, 1 -oxa-5-thia-s-indacene, 1 -oxa-5-
thia-s-indacene-2,6-diamine, 2-[(2-amino-1 -oxa-5-thia-s-indacen-6-yl)-(2-hydroxyethyl)-
amino]-ethanol, 2-pyrrolidin-l-yl-l-oxa-5-thia-s-indacen-6-ylamine, 1,5-dihydropyrrolo[
2)3-f]indole-2,6-diamine, 6-pyrrolidin-l-yl-l,5-dihydro-pyrrolo[2,3-fIindol-2-
ylamine, 5H-l-thia-5-aza-s-indacene-2,6-diamine, 2-(6-amino-5H-l-thia-5-aza-s-indacen-
2-ylamino)-ethanol, 6-pyrrolidin-1 -yl-5H-1 -thia-5-aza-s-indacen-2-ylamine, 1,5 -dithia-sindacene-
2,6-diamine, 2-[(6-amino-l,5-dithia-s-indacen-2-yl)-(2-hydroxy-ethyl)-amino]-
ethanol, benzo[l,2-b;5,4-b']difuran-2,3-diamine, 3-amino-benzo[l,2-b;5,4-b']difuran-2-ol,
7-methyl-7H-1 -oxa-7-aza-s-indacene-5,6-diamine, l-oxa-7-thia-s-indacene-5,6-diamine,
6-amino-l-oxa-7-thia-s-indacen-5-ol, l,7-dithia-s-indacene-2,3-diainine5 2-amino-l,7-
dithia-s-indacen-3-ol, ls7-dithia-s-indacene-2,3-diamine, 2-amino-l,7-dithia-s-indacen-3-
ol, l-methyl-l,7-dihydro-pyrrolo[3,2-f]indole-2,3-diamine, 7H-l-thia-7-aza-s-indacene-
2,3-diamine, 3-amino-7H-l-thia-7-aza-s-indacen-2-olJ benzo[2,l-b;3,4-b']difuran-2,7-
diamine, 7-pyrrolidin-l-yl-benzo[2,l-b;3,4-bl]difuran-2-ylamine, 7-amino-benzo[2,lb;
3,4-b']difuran-2-ol, 8H-l-oxa-8-aza-as-indacene, 8H-l-oxa-8-aza-as-indacene-2,7-
diamine, 8-inethyl-2-pyrrolidin-l-yl-8H-l-oxa-8-aza-as-indacen-7-ylamine) l-oxa-8-thiaas-
indacene-2,7-diamine, 2-amino-l-oxa-8-thia-as-indacen-7-ol, l,8-dihydro-l,8-diazaas-
indacene-2,7-diamine, 7-amino-1,8-dihydro-1,8-diaza-as-indacen-2-ol, 8H-1 -thia-8-
aza-as-indacene, 8H-1 -thia-8-aza-as-indacene-2,7-diamine, 7-pyrrolidin-1 -yl-8H-1 -thia-
8-aza-as-indacen-2-ylamine, 7-amino-l,8-dithia-as-ndacen-2-ol, 7-pyrrolidin-l-yl-l,8-
dithia-as-indacen-2-ylamine, benzo[l,2-b;4,3-b']difuran-2,7-diamine, 7-pyrrolidin-1 -ylbenzo[
l,2-b;4,3-bl]diruran-2-ylamine, 7-amino-benzo[l,2-b;4,3-b']diruran-2-ol5 6H-3-
oxa-6-aza-as-indacene-2,7-diamine, 2-[(2-araino-6H-3-oxa-6-aza-as-indacen-7-yl)-(2-
hydroxy-ethyl)-amino]-ethanol, 2-amino-6H-3-oxa-6-aza-as-indacen-7-ol, 3-oxa-6-thiaas-
indacene-2,7-diamine, 2-[(2-amino-3-oxa-6-thia-as-indacen-7-yl)-(2-hydroxy-ethyl)-
amino]-ethanol, 2-amino-3-oxa-6-thia-as-indacen-7-ol, 3,6-dihydro-3,6-diaza-asindacene,
3,6-dihydro-3)6-diaza-as-indacene-2,7-diamine, 2-[(7-amino-3,6-dihydro-3,6-
diaza-as-indacen-2-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 7-pyrrolidin-l-yl-3,6-dihydro-
3,6-diaza-as-indacen-2-ylamines 7-amino-3,6-dihydro-3,6-diaza-as-indacen-2-ol, 6H-3-
thia-6-aza-as-indacene-2,7-diamine, 2-[(2-amino-6H-3-thia-6-aza-as-indacen-7-yl)-(2-
hydroxy-ethyl)-amino]-ethanol, 2-amino-6H-3-thia-6-aza-as-indacen-7-ol, 2-[(7-amino-
methyl-6H-3-thia-6-aza-as-indacen-2-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 3,6-dithiaas-
indacene-2,7-diamine, 2-(7-amino-3,6-dithia-as-indacen-2-ylamino)-ethanol, 2-[(7-
amino-3,6-dithia-as-indacen-2-yl)-(2-hydroxy-ethyl)-ammo]-ethanol, 7-amino-3,6-dithiaas-
indacen-2-ol, 3-[(7-airuno-8-memyl-3,6-dithia-as-indacen-2-yl)-(2-hydroxy-ethyl)-
amino]-propane-l,2-diol, l-(7-amino-3,6-dithia-as-indacen-2-ylamino)-butan-2-ol.
Especially preferred couplers of the present invention are selected from the group
consisting of benzo[l,2-b;4,5-b']difuran, benzo[l,2-b;4,5-b']difuran-2-ylamme,
benzo[l,2-b;4,5-b']difuran-2-ol, benzo[l,2-b;4,5-b']difuran-2,6-diol, benzo[l,2-b;4,5-
b']difuran-3,7-diol, benzo[l,2-b;4,5-b']dimran-3,7-diamme, 5H-l-oxa-5-aza-s-indacene,
5H-l-oxa-5-aza-s-indacen-6-ylamine, 5H-l-oxa-5-aza-s-indacen-2,6-diol, 5H-l-oxav-5-
aza-s-indacen-3,7-diol, 5H-l-oxa-5-aza-s-indacen-3,7-diamine, l-oxa-5-thia-s-indacene,
1 -oxa-5-thia-s-indacen-6-ylamine, l-oxa-5-thia-s-indacen-2-ylamine, l-oxa-5-thia-sindacen-
6-ol, l-oxa-5-thia-s-indacen-2,6-diol, l-oxa-5-thia-s-indacen-3,7-diol, l-oxa-5-
thia-s-indacen-3,7-diamine, l,5-dihydro-pyrrolo[2,3-fjindole, l,5-dihydro-pyrrolo[2,3-
f]indol-2-ylamine, 1 ,5-dihydro-pyrrolo[2,3-f]indol-2-ol, l,5-dihydro-pyrrolo[2,3-fjindol-
2,6-diol, l,5-dihydi-o-pyrrolo[2,3-f]indol-3,7-diol, l,5-diliydro-pyrrolo[2,3-fjindol-3,7-
diamine, 5H-l-thia-5-aza-s-indacene, 5H-l-thia-5-aza-s-indacen-2-ylamine, 5H-l-thia-5-
aza-s-indacen-6-ylamine, 5H-l-thia-5-aza-s-indacen-2-ol, 5H-l-Thia-5-aza-s-indacen-
2,6-diol, 5H-l-Thia-5-aza-s-indacen-3,7-diol, 5H-l-Thia-5-aza-s-indacen-3,7-diamine5
1,5-dithia-s-indacen-2-ylamine, 1,5-dithia-s-indacen-2-ol, dithia-s-indacen-2,6-diol,
dithia-s-indacen-3,7-diol, dithia-s-indacen- 3,7-diamine, benzo [2,1 -b; 3,4-b'] difuran-2-
ylamine, benzo[2,l-b;3,4-b']difuran-2-ol, benzo[l,2-b;5,4-b']difuran-2,6-diol, benzo[l,2-
b;5,4-b']difuran-3,7-diol, benzo[l,2-b;5,4-b']difuran-3,7-diamine, 6-dimethylbenzo[l,2-
b;5,4-b']difuran, 3,7-dimethylbenzo[l,2-b;5,4-b']difuran, 7H-l-oxa-7-aza-s-indacene, 7-
Methyl-7H-l-oxa-7-aza-s-indacen-6-ylamine, 6-amino-7-methyl-7H-l-oxa-7-aza-sindacen-
2-ol, 7H-1 -oxa-7-aza-s-indacen-3,7-diol, 7H-1 -oxa-7-aza-s-indacen-3,7-diamine,
2,6-dimethyl-7H-1 -oxa-7-aza-s-indacene, 3,5-dimethyl-7H-1 -oxa-7-aza-s-indacene, 1 -
oxa-7-thia-s-indacen-2-ol, l-Oxa-7-thia-s-indacen-3,7-diol, 1 -Oxa-7-thia-s-indacen-3,7-
diamine, l-Oxa-7-thia-s-indacene, 2,6-dimethyl-l-Oxa-7-thia-s-indacene, 1,7-dithia-sindacen-
2-ylamine, 1,7-dithia-s-indacen-2-ol, l,7-dithia-s-indacen-3,7-diol, 1,7-dithia-sindacen-
3,7-diamine, 1,7-dithia-s-indacene, 2,6-dimethyl-l,7-dithia-s-indacene, 1,7-
dihydro-pyrrolo[3,2-f]indole, l-methyl-l,7-dihydro-pyrrolo[3,2-fjindol-2-ylamine, 1-
methyl-l,7-dihydro-pyrrolo[3,2-f]indol-2-ol, l,7-dimethyl-l,7-dihydro-pyrrolo[3,2-
fjindole-2,6-diol, l,7-dihydro-pyrrolo[3,2-fJindol-3,7-diol, l,7-dihydro-pyrrolo[3,2-
f]indol-357-diamine, 2,6-dimethyl-1,7-dihydro-pyrrolo[3,2-f]indole, 7H-1 -thia-7-aza-sindacene,
7H-l-thia-7-aza-s-indacen-2-ylamine, 7H-l-thia-7-aza-s-indacen-2-ol, 7-
methyl-7H-l-thia-7-aza-s-indacene-2,6-diol, 7-methyl-7H-l-thia-7-aza-s-indacen-6-ol, 7-
Methyl-7H-1 -th.ia-7-aza-s-indacen-6-ylamine, 7H-1 -thia-7-aza-s-indacen-3,7-diol, 2,6-
dimethyl-7H-l-thia-7-aza-s-indacene, benzo[2,l-b;3,4-b']difiiran-2-ylamine, benzo[2,lb;
3,4-b']difiiran-2-ol, benzol-b-bdifuranJ-diol, 2,7-dimethyl-benzo[2,l-b;3,4-
b'jdifuran, 8H-l-oxa-8-aza-as-indacen-2-ol, 8-methyl-8H-l-oxa-8-aza-as-indacen-7-
ylamine, 8H-1 -oxa-8-aza-as-indacen-3,6-diamine, 8H-1 -oxa-8-aza-as-indacen-2,7-diol,
2,7-dimethyl-8H-l-oxa-8-aza-as-indacene, l-oxa-8-thia-as-indacen-2-ol, l-oxa-8-thia-asindacen-
7-ylamine, 1 -oxa-8-thia-as-indacen-3,6-diamine, 1 -oxa-8-thia-as-indacen-2,7-
diol, 2,7-dimethyl-l-oxa-8-thia-as-indacene, l,8-dihydro-l,8-diaza-as-indacene, 1,8-
dihydro-1,8-diaza-as-indacen-2-ol, 1,8-dihydro-1,8-diaza-as-indacen-2-ylamine, 1,8-
dihydro-1,8-diaza-as-indacen-3,6-diamine, 1,8-dihydro-1,8-diaza-as-indacen-2,7-diol,
2,7-dimethyl-l,8-dihydro-l,8-diaza-as-indacene, 8H-l-thia-8-aza-as-indacene, 8H-1-
thia-8-aza-as-indacen-7-ol, 8H-l-thia-8-aza-as-indacen-2-ylamine, 8H-l-thia-8-aza-asindacen-
3,6-diamine, 8H-l-thia-8-aza-as-indacen-2,7-diol, 2,7-dimethyl-8H-l-thia-8-azaas-
indacene, l,8-dithia-as-indacen-2-ol, l,8-dithia-as-indacen-2-ylamine, 1,8-dithia-asindacen-
3,6-diamine, l,8-dithia-as-indacen-2,7-diol, 2,7-dimethyl-l,8-dithia-as-indacene,
benzo[l,2-b;4,3-b']difuran-2-ol, benzo[l,2-b;4,3-bl]difuran-2-ylamine, benzo[l,2-b;4,3-
b']difuran-l,8-diamine, benzo[l,2-b;4,3-b']difuran-2,7-diol, 6H-3-oxa-6-aza-as-iiidacene,
6-methyl-6H-3-oxa-6-aza-as-indacen-7-ol, 6H-3-oxa-6-aza-as-indacen-2-ylamine, 6-
Methyl-6H-3 -oxa-6-aza-as-indacen-7-ylamine, 6H-3 -oxa-6-aza-as-indacen-2,7-diol, 6H-
3-oxa-6-aza-as-indacen-1,8-diol, 3-oxa-6-thia-as-indacen-7-ol, 3-oxa-6-thia-as-indacen-
ylamine, 3-oxa-6-thia-as-indacen-7-ylamine, 3-oxa-6-thia-as-indacen-l,8-diol, 3-oxa-6-
thia-as-indacen-l,8-diamine, 3-oxa-6-thia-as-indacen-2,7-dioI, 3,6-dihydro-3,6-diaza-asindacene,
3-methyl-3,6-dihydro-3,6-diaza-as-indacen-2-ol, 3,6-dihydro-3,6-diaza-asindacen-
2-ylamine, 3-methyl-3,6-dihydro-3,6-diaza-as-indacen-2-ylamine, 3,6-dihydro-
3,6-diaza-as-indacen-l,8-diol, 3,6-dihydro-3,6-diaza-as-indacen-l58-diamme, 3,6-
dihydro-3,6-diaza-as-indacen-2,7-diol, 6H-3-thia-6-aza-as-indacene, 6-methyl-6H-3-thia-
6-aza-as-indacen-7-ol, 6H-3-thia-6-aza-as-indacen-2-ylamine, 6-methyl-6H-3-thia-6-azaas-
indacen-7-ylamine, 6H-3-thia-6-aza-as-indacen-l,8-diol, 6H-3-thia-6-aza-as-indacen-
1,8-diamine, 6H-3-thia-6-aza-as-indacen-2,7-diol, 3,6-dithia-as-indacen-2-ol, 3,6-dithiaas-
indacen-2-ylamine, 3,6-dithia-as-mdacen-l,8-diol, 3,6-dithia-as-indacen-l,8-diamine}
and3,6-dithia-as-indacen-2,7-diol.
Synthesis Examples
The following are non-limiting synthesis examples of the present invention.
Example A: l,5-dihydro-pyrTolo[2,3-fJindole, obtainable from the following synthesis
strategy:
Treatment of indoline 1 is converted to N-acetyl-5-aminoindoline 2 by three step
procedure: (1) acetylation with acetic anhydride and p-toluenesulfonic acid, (2) nitration
with nitric acid in sulfuric acid, and (3) hydrogenation with hydrogen and Pd-C. Reaction
of 2 with bromoacetaldehyde diethyl acetal in the presence of sodium carbonate followed
by treatment with trifluoroacetic anhydride and triethylamine gives rise to compound 3.
Cyclization of 3 in a mixture of trifluoroacetic anhydride and trifluoroacetic acid
produces compound 4. Dehydroration of 4 with DDQ affords compound 5. Deprotection
of 5 with potassium hydroxide in methanol gives l,5-dihydro-pyrrolo[2,3-fjindole
(Tetrahedron Lett. 1991, 32 (38), 5035).
Example B: l,8-Dihydro-l,8-diaza-as-indacene-2,7-diamine obtainable from the
following synthesis strategy:
The condensation of 2,3-dinitro-p-xylene 1 with N,N-dimethylformamide diethyl acetal
in DMF produces the trans, trans-bis-enamine 2. Reductive cyclization of 2 with
hydrogen and Pd/C gives the benzodipyrrole 5. Compounds 3 and 4 are intermediates
during the reduction. Bromination of benzodipyrrole 5 with NBS affords the dibromo
compound 6. Nitration of 6 produces compound 7 which is subject to catalytic
hydrogenation to produce l,8-dmydro-l,8-diaza-as-mdacene-2,7diarnine (J. Chem. Soc.
Chem. Commun. 1987, 1176)
Example C: 1,5-Dithia-s-indacene-4-ol obtainable from the following synthesis
strategy:
Reaction of thiophene-3-carbaldehyde 1 with 2,3-dibromothiophene 2 in the presence of
butyl lithium produces (3-bromothiophen-2-yl)(thiophen-3-yl)methanol 3. Reduction of
3 with LiAlHU produces 3-bromo-2-((thiophen-3-yl)methyl)thiophene 4. Treatment of
compound 4 with butyl lithium and carbon dioxide produces 2-((thiophen-3-
yl)methyl)thiophene-3-carboxylic acid 5. Cyclization of compound 5 with PC15 and
SnCU produces the desired l,5-Dithia-s-indacene-4-ol IX (J. Org. Chem., 1971, 26,
4004).
II. Keratin Dyeing Composition Components
The inventive compositions for the oxidative dyeing of keratin fibers comprise the
hair-dyeing compound described above in the hair-dyeing compounds section and a
medium suitable for dyeing. The inventive compositions may further comprise additional
components known, conventionally used, or otherwise effective for use in oxidative dye
compositions, including but limited to: developer dye compounds; coupler dye
compounds; direct dyes; oxidizing agents; thickeners; chelants; pH modifiers and
buffering agents; carbonate ion sources and radical scavenger systems; anionic, cationic,
nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof; anionic, cationic,
nonionic, amphoteric or zwitterionic polymers, or mixtures thereof; fragrances; buffers;
dispersing agents; peroxide stabilizing agents; natural ingredients, e.g. proteins and
protein derivatives, and plant materials (e.g. aloe, chamomile and henna extracts);
silicones (volatile or non-volatile, modified or non-modified), film-forming agents,
ceramides, preserving agents; and opacifiers.
Some adjuvants referred to above, but not specifically described below, which are
suitable are listed in the International Cosmetics Ingredient Dictionary and Handbook, (8th
ed.; The Cosmetics, Toiletry, and Fragrance Association). Particularly, vol. 2, sections 3
(Chemical Classes) and 4 (Functions) are useful in identifying specific adjuvants to
achieve a particular purpose or multipurpose.
A. Medium Suitable for Dyeing
The medium suitable for dyeing may be selected from water, or a mixture of water
and at least one organic solvent to dissolve the compounds that would not typically be
sufficiently soluble in water. Suitable organic solvents for use herein include, but are not
limited to: Cl to C4 lower alkanols (e.g., ethanol, propanol, isopropanol), aromatic
alcohols (e.g. benzyl alcohol and phenoxyethanol); polyols and polyol ethers (e.g.,
carbitols, 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether,
diethylene glycol monoethyl ether, monomethyl ether, hexylene glycol, glycerol, ethoxy
glycol), and propylene carbonate. When present, organic solvents are typically present in
an amount ranging from 1% to 30%, by weight, of the composition. Preferred solvents
are water, ethanol, propanol, isopropanol, glycerol, 1,2-propylene glycol, hexylene
glycol, ethoxy diglycol, and mixtures thereof. Additional mediums suitable for dyeing
may include oxidizing agents as described below.
B. Auxiliary Developers
Suitable developers for use in the compositions described herein include, but are
not limited to p-phenylenediamine derivatives, e.g. benzene- 1,4-diamine (commonly
known as p-phenylenediamine), 2-methyl-benzene- 1,4-diamine, 2-chloro-benzene-1,4-
diamine, N-phenyl-benzene-1,4-diamine, N-(2-ethoxyethyl)benzene-1,4-diamine, 2-[(4-
amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, (commonly known as N,N-bis(2-
hydroxyethyl)-p-phenylenediamine) (2,5-diamino-phenyl)-methanol, l-(2'-
Hydroxyethyl)-2,5-diaminobenzene, 2-(2,5-diamino-phenyl)-ethanol, N-(4-
aminophenyl)benzene-1,4-diamine, 2,6-dimethyl-benzene-1,4-diamine, 2-isopropylbenzene-
1,4-diamine, 1 -[(4-aminophenyl)amino]-propan-2-ol, 2-propyl-benzene-1,4-
diamine, 1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2-ol, N4,N4,2-
trimethylbenzene-1,4-diamine, 2-methoxy-benzene-1,4-diamine, 1 -(2,5-
diaminophenyl)ethane-l,2-diol, 2,3-dimethyl-benzene-l ,4-diamine, N-(4-amino-3-
hydroxy-phenyl)-acetamide, 2,6-diethylbenzene-1,4-diamine, 2,5-dimethylbenzene-1,4-
diamine, 2-thien-2-ylbenzene-1,4-diamine, 2-thien-3-ylbenzene-1,4-diamine, 2-pyridin-3-
ylbenzene-1,4-diamine, 1,1 '-bipheny 1-2,5-diamine, 2-(methoxymethyl)benzene-1,4-
diamine, 2-(aminomethyl)benzene- 1,4-diamine, 2-(2,5-diaminophenoxy)ethanol, N-[2-
(2,5-diaminophenoxy)ethyl]-acetamide, N,N-dimethylbenzene-1,4-diamine, N,Ndiethylbenzene-
1,4-diamine, N,N-dipropylbenzene-1,4-diamine, 2-[(4-
aminophenyl)(ethyl)amino]ethanol, 2-[(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)-
amino]-ethanol, N-(2-methoxyethyl)-benzene-1,4-diamine, 3 - [(4-
aminophenyl)amino]propan-1 -ol, 3-[(4-aminophenyl)-amino]propane-1,2-diol, N- {4-[(4-
aminophenyl)amino]butyl}benzene-1,4-diamine, and 2-[2-(2-{2-[(2,5-diaminophenyl)-
oxy]ethoxy}ethoxy)ethoxy]benzene-1,4-diamine; l,3-Bis(N(2-Hydroxyethyl)-N-(4-
amino-phenyl)amino)-2-propanol; 2,2'-[ 1,2-Ethanediyl-bis-(oxy-2,1 -ethanediyloxy)]-bisbenzene-
1,4-diamine; N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; p-aminophenol
derivatives such as: 4-amino-phenol (commonly known as p-aminophenol), 4-
methylamino-phenol, 4-amino-3-methyl-phenol, 4-amino-2-hydroxymethyl-phenol, 4-
amino-2-methyl-pheriol, 4-amino-1 -hydroxy-2-(2'-hydroxyethylaminomethyl)benzene,
amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid, l-(5-amino-2-
hydroxy-phenyl)-ethane-1,2-diol, 4-amino-2-(2-hydroxy-ethyl)-phenol, 4-amino-3 -
(hydroxymethyl)phenol, 4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)-phenol, 4-
amino-2-fluoro-phenol; l-Hydroxy-2,4-diaminobenzene; l-(2'-Hydroxyethyloxy)-2,4-
diaminobenzene; 2,4-Diamino-5-methylphenetol; o-phenylenediamine derivatives such
as: 3,4-Diamiiiobenzoic acid and salts thereof; o-aminophenol derivatives such as: 2-
amino-phenol (commonly known as o-aminophenol), 2,4-diaminophenol, 2-amino-5-
methyl-phenol, 2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide, and
2-amino-4-methyl-phenol; and heterocyclic derivatives such as: pyrimidine-2,4,5,6-
tetramine (commonly known as 2,4,5,6-tetraaminopyridine), 1-methyl-lH-pyrazole-4,5-
diamine, 2-(4,5-diamino-lH-pyrazol-l-yl)ethanol, N2,N2-dimethyl-pyridine-2,5-diamine,
2-[(3-amino-6-methoxypyridin-2-yl)amino]ethanol, 6-methoxy-N2-methyl-pyridine-2,3-
diamine, 2,5,6-triaminopyrirnidin-4(lH)-one, pyridine-2,5-diamine, 1-isopropyl-lHpyrazole-
4,5-diamine, l-(4-methylbenzyl)-lH-pyrazole-4,5-diamine, 1-(benzyl)-1Hpyrazole-
4,5-diamine, l-(4-chlorobenzyl)-lH-pyrazole-4,5-diamine, pyrazolo[l,5-a]-
pyrimidine-3,7-diamine, 5,6,7-trimethylpyrazolo[l,5-a]pyrimidin-3-ylamme
hydrochloride, 7-methylpyrazolo[l,5-a]pyrimidin-3-ylamine hydrochloride, 2,5,6,7-
teramethyl-pyrazolo[l,5-a]pyrimidin-3-ylamine hydrochloride, 5,7-di-tertbutylpyrazolo[
l ,5-a]pyrimidin-3-ylamine hydrochloride, 5,7-di-trifluoromethylpyrazolo[
l,5-a]pyrimidin-3-ylamine hydrochloride, 2-methylpyrazolo[l,5-a]pyrimidin-
3,7-diamine hydrochloride; 4-Hydroxy-2,5,6-triaminopyrimidine; l-(2'hydroxyethyl)-
amino-3,4-methylene dioxybenzene; and l-Hydroxyethyl-4,5-diaminopyrazole sulphate.
Additional developers are selected from the group consisting of A^-(3-
furylmethyl)benzene-1,4-diamine; N-Thiophen-3-ylmethyl-benzene-1,4-diamine; N-(2-
furylmethyl)benzene-1,4-diamine; N-Thiophen-2-ylmethyl-benzene-1,4-diamine; 4-
Hydroxy-benzoic acid (2,5-diamino-benzylidene)-hydrazide; 3-(2,5-Diamino-phenyl)-Nethyl-
acrylamide; 2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine; 2-[3-(4-
Amino-phenylamino)-propenyl]-benzene-1,4-diamine; 2-(6-Methyl-pyridin-2-yl)-
benzene-1,4-diamine; 2-Pyridin-2-yl-benzene-1,4-diamine; 2-[3-(4-Amino-phenylamino)-
propenylj-benzene-1,4-diamine; 2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-
diamine; 3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide; 2-Thiazol-2-yl-benzene-1,4-
diamine; 4-Hydroxy-benzoic acid (2,5-diamino-benzylidene)-hydrazide; 3'-Fluorobiphenyl-
2,5-diamine; 2-Propenyl-benzene-1,4-diamine; 2'-Chloro-biphenyl-2,5-diamine;
N-Thiophen-3-ylmethyl-benzene-l,4-diamine;7V-(3-furylrnethyl)benzene-l,4-diamine; 4'-
Methoxy-biphenyl-2,5-diamine; N-(4-Amino-benzyl)-benzene-l ,4-diamine; 2-Methyl-5-
[(1 -H-pyrrol-2-ylmethyl)-amino]-phenol; 5-[(Furan-2-ylmethyl)-amino]-2-methylphenol;
5-Isopropylamino-2-methyl-phenol; Biphenyl-2,4,4'-triamine hydrochloride; 5-
(4-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride; 5-
Phenylaminomethyl-benzene-1,3-diamine hydrochloride; 2-[4-Amino-2-(3,5-diaminobenzylamino)-
phenoxy]-ethanol hydrochloride; 5-(3-Amino-phenyl)aminomethylbenzene-
1,3-diamine hydrochloride; N-(2-Amino-benzyl)-benzene-1,3-diamine
hydrochloride; N-Furan-2-ylmethyl-benzene- 1,3-diamine hydrochloride; 2-[(3-Aminophenylamino)-
methyl]-phenol hydrochloride; 4-Amino-2-propylaminomethyl-phenol;
hydrochloride; N-Benzo[l,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride; N-
[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-
acrylamide; hydrochloride; 4-Amino-2-(isopropylamino-methyl)-phenol; hydrochloride;
4-Thiophen-3-yl-benzene-l,3-diamine; hydrochloride hydrochloride; 5-
Phenylaminomethyl-benzene- 1,3-diamine hydrochloride; 5-(3-Aminophenyl)
aminomethyl-benzene-1,3-diamine hydrochloride; 4-Thiophen-3-yl-benzene-l ,3-
diamine; hydrochloride; 2',4'-Diamino-biphenyl-4-ol; hydrochloride; 5-Cyclobutylamino-
2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol; 4-Amino-2-(pyridin-3-
ylaminomethyl)-phenol; 5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine
hydrochloride; 5-Allylaminomethyl-benzene-l,3-diamine hydrochloride; N-(4-Aminobenzyl)-
benzene-1,3-diamine hydrochloride; N-Benzyl-benzene-1,3-diamine
hydrochloride; 3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride; N-(4-
Methoxy-benzyl)-benzene-1,3-diamine hydrochloride; N-Thiophen-2-ylmethyl-benzene-
1,3-diamine hydrochloride; 4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-
phenol; hydrochloride; 2',4'-Diamino-biphenyl-4-ol hydrochloride; Biphenyl-2,4,4'-
triamine; 5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride; 2-[4-
Amino-2-(3,5-diamino-benzylammo)-phenoxy]-ethanol hydrochloride; 5-
Allylaminomethyl-benzene-1,3-diamine hydrochloride; 5-(3-Aminophenyl)
aminomethyl-benzene-1,3-diamine hydrochloride; N-(4-Amino-benzyl)-benzene-
1,3-diamine hydrochloride; N-Benzyl-benzene-1,3-diamine hydrochloride; 3-[(3-Aminophenylamino)-
methyl]-phenol hydrochloride; N-(2-Amino-benzyl)-benzene-1,3-diamine
hydrochloride; N-(4-Memoxy-benzyl)-benzene-1,3-diamine hydrochloride; N-Furan-2-
ylmethyl-benzene-1,3-diamine hydrochloride; 2-[(3-Amino-phenylamino)-methyl]-
phenol hydrochloride; N-Thiophen-2-ylmethyl-benzene-1,3 -diamine hydrochloride; NBenzo[
1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride; N-[4-Amino-2-(2-
hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamide
hydrochloride; 4-Amino-2-propylaminomethyl-phenol; hydrochloride; 4-Amino-2-
(isopropylamino-methyl)-phenol hydrochloride; 4-Amino-2-[(2-hydroxy-5-nitrophenylamino)-
methyl]-phenol hydrochloride; 2-Methyl-5-[( 1 -H-pyrrol-2-ylmethyl)-
aminoj-phenol; 5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol; 5-Isopropylamino-2-
methyl-phenol; 5 -Cyclobutylamino-2-methyl-phenol; 4- Amino-2 -(pyridin-3 -
ylaminomethyl)-phenol; and 5-Cyclobutylamino-2-methyl-phenol.
Preferred developers include but are not limited to: p-phenylenediamine
derivatives such as: 2-methyl-benzene-l,4-diamine; benzene-1,4-diamine; l-(2,5-
diamino-phenyl)-ethanol; 2-(2,5-diamino-phenyl)-ethanol; N-(2-methoxyethyl)benzene-
1,4-diamine; 2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol; l-(2,5-
diaminophenyl)ethane-1,2-diol; 1 -(2'-Hydroxyethyl)-2,5-diaminobenzene; 1,3-Bis(N(2-
Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol; 2,2'-[ 1,2-Ethanediyl-bis-(oxy-2,1 -
ethanediyloxy)]-bis-benzene-1,4-diamine; N,N-Bis(2-hydroxyethyl)-p-phenylinediamine;
and mixtures thereof; p-aminophenol derivatives such as: 4-amino-phenol, 4-
methylamino-phenol, 4-amino-3-methyl-phenol, 4-amino-2-methoxymethyl-phenol; l-(5-
amino-2-hydroxy-phenyl)-ethane-l,2-diol; l-Hydroxy-2,4-diaminobenzene; l-(2'-
Hydroxyethyloxy)-2,4-diaminobenzene; 4-Amino-2-aminomethylphenol; 2,4-Diamino-5-
methylphenetol; 4-Amino-1 -hydroxy-2-(2'-hydroxyethylaminomethyl)benzene; 1-
methoxy-2-amino-4-(2'hydroxyethylamino)benzene; 5-aminosalicylic acid and salts
thereof; and mixtures thereof; o-phenylenediamine derivatives such as: 3,4-
Diaminobenzoic acid and salts thereof; o-aminophenol derivatives such as: 2-aminophenol,
2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol, N-(4-amino-3-hydroxyphenyl)-
acetamide; 2-amino-4-methyl-phenol; and mktures thereof; and heterocyclic
derivatives such as: pyrimidine-2,4,5,6-tetramine; l-methyl-lH-pyrazole-4,5-diamine; 2-
(4,5-diamino-1 H-pyrazol-1 -yl)ethanol; 1 -(4-methylbenzyl)-1 H-pyrazole-4,5-diamine; 1 -
(benzyl)- lH-pyrazole-4,5-diamine; N2,N2-dimethyl-pyridine-2,5-diamine; 4-Hydroxy2,5,6-
triaminopyrimidine; l-(2'hydroxyethyl)-amino-3,4-methylenedioxybenzene; and 1-
Hydroxyethyl-4,5-diaminopyrazole sulphate; and mixtures thereof.
More preferred developers include: 2-methyl-benzene-l,4-diamine; benzene-1,4-
diamine; N,N-Bis(2-hydroxyethyl)-p-phenylenediamine; 4-amino-phenol; 4-
methylamino-phenol; 4-amino-3-methyl-phenol; l-Hydroxy-2,4-diaminobenzene; 2-
amino-phenol; 2-amino-5-methyl-phenol; 2-amino-6-methyl-phenol; 1-methyl-lHpyrazole-
4,5-diamine; l-Hydroxyethyl-4,5-diaminopyrazole sulphate; 2-(4,5-diaminolH-
pyrazol-l-yl)ethanol; and mixtures thereof.
C. Auxiliary Couplers
Suitable couplers for use in the compositions described herein include', but are not
limited to: phenols, resorcinol and naphthol derivatives such as: naphthalene- 1,7-diol,
benzene-l,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol,
naphthalene-l,5-diol, naphthalene-2,7-diol, benzene-1,4-diol, 2-methyl-benzene-l,3-diol,
7-amino-4-hydroxy-naphthalene-2-sulfonic acid, 2-isopropyl-5-methylphenol, 1,2,3,4-
tetrahydro-naphthalene-1,5-diol, 2-chloro-benzene-1,3-diol, 4-hydroxy-naphthalene-1 -
sulfonic acid, benzene-1,2,3-triol, naphthalene-2,3-diol, 5-dichloro-2-methylbenzene-l,3-
diol, 4,6-dichlorobenzene-1,3-diol, 2,3-dihydroxy-[l,4]naphthoquinone; and 1-Acetoxy-
2-methylnaphthalene; m-phenylenediamines such as: 2,4-diaminophenol, benzene-1,3-
diamine, 2-(2,4-diamino-phenoxy)-ethanol, 2-[(3-arnino-phenyl)-(2-hydroxy-ethyl)-
aminoj-ethanol, 2-mehyl-benzene-.l,3-diamine, 2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2-
hydroxy-ethyl)-amino]-ethanol, 4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-l,3-
diamine, 2-(2,4-diamino-phenyl)-ethanol, 2-(3-amino-4-methoxy-phenylamino)-ethanol,
4-(2-amino-ethoxy)-benzene-l,3-diamine, (2,4-diamino-phenoxy)-acetic acid, 2-[2,4-
diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, 4-ethoxy-6-methyl-benzene-1,3-
diamine, 2-(2,4-diamino-5-methyl-phenoxy)-ethanol, 4,6-dimethoxy-benzene-l,3-
diamine, 2-[3-(2-hydroxy-ethylamino)-2-methyl-phenylamino]-ethanol, 3-(2,4-diaminophenoxy)-
propan- l-ol, N-[3-(dimethylamino)phenyl]urea, 4-methoxy-6-methylbenzene-
1,3-diamine, 4-fluoro-6-methylbenzene-l,3-dianiineJ 2-({3-[(2-hydroxyethyl)amino]-4,6-
dimethoxyphenyl} -amino)ethanol, 3 -(2,4-diaminophenoxy)-propane-1,2-diol, 2-[2-
amino-4-(methylamino)-phenoxy]ethanol, 2-[(5-amino-2-ethoxy-phenyl)-(2-hydroxyethyl)-
amino]-ethanol, 2-[(3-aminophenyl)amino]ethanol, 2,4-Diamino-5-(2'-
hydroxyethyloxy)toluene; N,N-Dimethyl-3-ureidoaniline; N-(2-aminoethyl)benzene-1,3-
diamine, 4- {[(2,4-diamino-phenyl)oxy]methoxy} -benzene-1,3 -diamine, 1 -methyl-2,6-
bis(2-hydroxyethylamino)benzene; and 2,4-dimethoxybenzene-l,3-diamine; maminophenols
such as: 3-amino-phenol, 2-(3-hydroxy-4-methyl-phenylamino)-acetamide,
2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl-phenol, 5-(2-hydroxyethylamino)-
2-methyl-phenol, 5-amino-2,4-dichloro-phenol, 3-amino-2-methyl-phenol,
3-amino-2-chloro-6-methyl-phenol, 5-amino-2-(2-hydroxy-ethoxy)-phenol5 2-chloro-5-
(2,2,2-trifluoro-ethylamino)-phenolJ 5-amino-4-chloro-2-methyl-phenol, 3-
cyclopentylamino-phenol, 5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol, 5-
amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol, 3-(diethylamino)phenol, 5-
amino-4-fluoro-2-methylphenol, 5 -amino-4-etb.oxy-2-metb.ylpb.enol, 3-amino-2,4-
dichloro-phenol, 3-[(2-methoxyethyl)amino]phenol, 3-[(2-hydroxyethyl)amino]phenol, 5-
amino-2-ethyl-phenol, 5-amino-2-methoxyphenol, 5-[(3-hydroxy-propyl)amino]-2-
methylphenol, 3-[(3-hydroxy-2-methylphenyl)-amino]propane-l ,2-diol, 3-[(2-
hydroxyethyl)amino]-2-methylphenol; l-Methyl-2-hydroxy-4-(2'-hydroxyethyl)aminobenzene;
l,3-Bis-(2,4-Diaminophenoxy)propane;. l-Hydroxy-2-methyl-5-amino-6-
chlorobenzene; and heterocyclic derivatives such as^: 3,4-dihydro-2H-l,4-benzoxazin-6-
ol, 4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 6-methoxyquinolin-8-amine, 4-
methylpyridine-2,6-diol, 2,3-dihydro-l,4-benzodioxin-5-ol, l,3-benzodioxol-5-ol, 2-(l,3-
benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol, 5-chloropyridine-2,3-diol,
2,6-dimethoxypyridine-3,5-diamine, l,3-benzodioxol-5-amine, 2-{[3,5-diamino-6-(2-
hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol, lH-indol-4-ol, 5-amino-2,6-
dimethoxypyridin-3-ol, lH-indole-5,6-diol, lH-indol-7-ol, lH-indol-5-ol, lH-indol-6-ol,
6-bromo-l,3-benzodioxol-5-ol, 2-aminopyridin-3-ol, pyridine-2,6-diamine, 3-[(3,5-
diaminopyridin-2-yl)oxy]propane-1,2-diol, 5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1,3-
diol, lH-indole-2,3-dione, indoline-5,6-diol, 3,5-dimethoxypyridine-2,6-diamine, 6-
methoxypyridine-2,3-diamine; 3]4-dihydro-2H-l,4-benzoxazin-6-amine; 4-hydroxy-Nmethylindole,
lH-5-methylpyrazol-5-one, l-phenyl-3-methylpyi-azol-5-one, 2,6-
dimethylpyrazolo[l,5-b]-l,2,4-triazole, 2,6-dimethyl[3,2-c]-l,2,4-triazole, 6-
methylpyrazolo-[ 1,5-a]benzimidazole, 2,6-dihydroxypyridine, 2,6-dihydroxy-3,4-
dimethylpyridine, 5-methylpyrazolo[5,1 -e]-1,2,3-triazole, 5-methyl-6-chloropyrazolo[5,1 -
e]-l,2,3,-triazole, 5-phenylpyrazolo[5,l-e]-l,2,3-triazole and its addition salts, lH-2,6-
dimethylpyrazolo[l,5-b]-l,2,4-triazole tosylate, 7,8-dicyano-4-methylimidazolo-[3,2-
a]imidazole, 2)7-dimethylpyrazolo[l,5-a]pyrimidin-5-one, 2,5-dimethylpyrazolo[l,5-
a]pyrimidin-7-one, and 2-methyl-5-methoxymethyl-pyrazolo[l,5-a]pyiimidin-7-one; 6-
Hydroxybenzomorpholine; and 3-Amino-2-methylamino-6-methoxypyridine; 1-Phenyl-
3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one.
Additional couplers are selected from the group consisting of N-(3-
furylmethyl)benzene-1,4-diamine; N-Thiophen-3-ylmethyl-benzene-1,4-diamine; N-(2-
rurylmethyl)benzene-1,4-diamine; N-Thiophen-2-yknethyl-benzene-1,4-diamine; 4-
Hydroxy-benzoic acid (2,5-diamino-benzylidene)-hydrazide; 3-(2,5-Diamino-phenyl)-Nethyl-
acrylamide; 2-[3-(3-Amino-phenylamino)-propenyl]-benzene-l,4-diamine; 2-[3-(4-
Amino-phenylamino)-propenyl]-benzene-1,4-diamine; 2-(6-Methyl-pyridin-2-yl)-
benzene-1,4-diamine; 2-Pyridin-2-yl-benzene-1,4-diamine; 2-[3-(4-Amino-phenylamino)-
propenylj-benzene-1,4-diamine; 2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-
diamine; 3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide; 2-Thiazol-2-yl-benzene-1,4-
diamine; 4-Hydroxy-benzoic acid (2,5-diamino-benzylidene)-hydrazide; 3-Fluorobiphenyl-
2,5-diamine; 2-Propenyl-benzene-1,4-diamine; 2'-Chloro-biphenyl-2,5-diamine;
N-Thiophen-3-ylmethyl-benzene-1,4-diamine; A^-(3-furylmethyl)benzene-1,4-diamine; 4'-
Methoxy-biphenyl-2,5-diamine; N-(4-Amino-benzyl)-benzene-l,4-diamine; 2-Methyl-5-
[(1 -H-pyrrol-2-ylmethyl)-amino]-phenol; 5 - [(Furan-2-ylmethyl)-amino]-2-methylphenol;
5-Isopropylamino-2-methyl-phenol; Biphenyl-2,4,4'-triamine hydrochloride; 5-
(4-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride; 5-
Phenylaminomethyl-benzene-1,3-diamine hydrochloride; 2-[4-Amino-2-(3,5-diaminobenzylamino)-
phenoxy]-ethanol hydrochloride; 5-(3-Amino-phenyl)aminomethylbenzene-
1,3-diamine hydrochloride; N-(2-Amino-benzyl)-benzene-1,3-diamine
hydrochloride; N-Furan-2-ylmethyl-benzene-l,3-diamine hydrochloride; 2-[(3-Aminophenylamino)-
methyl]-phenol hydrochloride; 4-Amino-2-propylaminomethyl-phenol;
hydrochloride; N-Benzo[l,3]dioxol-5-ylmethyl-benzene-l,3-diamine hydrochloride; N-
[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-
acrylamide; hydrochloride; 4-Amino-2-(isopropylamino-methyl)-phenol; hydrochloride;
4-Thiophen-3-yl-benzene-l,3-diamine; hydrochloride hydrochloride; 5-
Phenylaminomethyl-benzene-l,3-diamine hydrochloride; 5-(3-Aminophenyl)
aminomethyl-benzene-1,3-diamine hydrochloride; 4-Thiophen-3 -yl-benzene-1,3-
diamine; hydrochloride; 2',4'-Diamino-biphenyl-4-ol; hydrochloride; 5-Cyclobutylamino2-
methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol; 4-Amino-2-(pyridin-3-
ylaminomethyl)-phenol; 5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine
hydrochloride; 5-Allylaminomethyl-benzene-1,3-diamine hydrochloride; N-(4-Aminobenzyl)-
benzene-1,3-diamine hydrochloride; N-Benzyl-benzene-1,3-diamine
hydrochloride; 3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride; N-(4-
Methoxy-benzyl)-benzene-1,3-diamine hydrochloride; N-Thiophen-2-ylmethyl-benzene-
1,3-diamine hydrochloride; 4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-
phenol; hydrochloride; 2',4'-Diamino-biphenyl-4-ol hydrochloride; Biphenyl-2,4,4'-
triamine; 5-(4-Amino-phenyl)aminomethyl-benzene-l,3-diamine hydrochloride; 2-[4-
Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride; 5-
Allylaminomethyl-benzene-l,3-diamme hydrochloride; 5-(3-Aminophenyl)
aminomethyl-benzene-1,3-diamine hydrochloride; N-(4-Amino-benzyl)-benzene-
1,3-diamine hydrochloride; N-Benzyl-benzene-l,3-diamine hydrochloride; 3-[(3-Aminophenylamino)-
methyl]-phenol hydrochloride; N-(2-Amino-benzyl)-benzene-1,3-diamine
hydrochloride; N-(4-Methoxy-benzyl)-benzene-l,3-djamine hydrochloride; N-Furan-2-
ylmethyl-benzene-l,3-diamine hydrochloride; 2-[(3-Amino-phenylamino)-methyl]-
phenol hydrochloride; N-Thiophen-2-yhnethyl-benzene-1,3-diamine hydrochloride; NBenzo[
l ,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride; N-[4-Amino-2-(2-
hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamide
hydrochloride; 4-Amino-2-propylaminomethyl-phenol; hydrochloride; 4-Amino-2-
(isopropylamino-methyl)-phenol hydrochloride; 4-Amino-2-[(2-hydroxy-5-nitrophenylamino)-
methyl]-phenol hydrochloride; 2-Methyl-5-[(l -H-pyrrol-2-ylmethyl)-
aminoj-phenol; 5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol; 5-Isopropylamino-2-
methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol; 4-Amino-2-(pyridin-3 -
ylaminomethyl)-phenol; and 5-Cyclobutylamino-2-methyl-phenol.
Preferred couplers include but are not limited to: phenol, resorcinol, and naphthol
derivatives such as: naphthalene-1,7-diol, benzene-1,3-diol, 4-chlorobenzene-l,3-diol,
naphthalen-1-ol, 2-methyl-naphthalen-l-ol, naphthalene- 1,5-diol, naphthalene-2,7-diol,
benzene-1,4-diol, 2-methyl-benzene-1,3-diol, and 2-isopropyl-5-methylphenol; 1,2,4-
Trihydroxybenzene; l-Acetoxy-2-methylnaphthalene;and mixtures thereof; mphenylenediamine
derivatives such as: benzene-1,3-diamine, 2-(2,4-diamino-phenoxy)-
ethanol, 4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-l,3-diamine, 2-(3-amino-4-
methoxy-phenylamino)-ethanol, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-
ethanol, and 3-(2,4-diamino-phenoxy)-propan-l-ol; 2,4-Diamino-5-(2lhydroxyethyloxy)
toluene; N,N-Dirnethyl-3-ureidoaniline; 2,4-Diamino-5-
fluorotoluenesulfatehydrate; l-methyl-2,6-bis(2-hydroxyethylamino)benzene; and
mixtures thereof; m-aminophenol derivatives such as: 3-amino-phenol, 5-amino-2-
methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol, and 3-amino-2-methylphenol;
l-Methyl-2-hydroxy-4-(2'-hydroxyethyl)aminobenzene; l-Hydroxy-3-amino-2,4-
dichlorobenzene; l,3-Bis-(2,4-Diaminophenoxy)propane; l-Hydroxy-2-methyl-5-ammo-
6-chlorobenzene; 5-Amino-4-chloro-2-methylphenol; and mixtures thereof; and
heterocyclic derivatives such as: 3)4-dihydro-2H-l,4-benzoxazin-6-ol, 4-methyl-2-
phenyl-2,4-dihydro-3H-pyrazol-3-one3 l,3-benzodioxol-5-ol, l^-benzodioxol-S-amine,
lH-indol-4-ol, lH-indole-5,6-diol, lH-indol-7-ol, lH-indol-5-oi, lH-indol-6-ol, 1Hindole-
2,3-dione, pyridine-2,6-diamine, 2-aminopyridin-3-ol, 4-hydroxy-N-methylindole,
lH-5-methylpyrazol-5-one, l-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[l,5-
b]-l,2,4-triazole, 2,6-dimethyl[3,2-c]-l,2,4-triazoles 6-methylpyrazolo-[l,5-
ajbenzimidazole; 2,6-dihydroxypyridine; 2,6-dihydroxy-3,4-dimethylpyridine; 6-
Hydroxybenzomorpholine; 2,6-Dihydroxy-3,4-dimethylpyridine; 3,5-Diamino-2,6-
dimethoxypyridine; 3-Amino-2-methylamino-6-methoxypyridine; l-Phenyl-3-methyl-5-
pyrazolone-2,4-dihydro-5)2-phenyl-3H-pyrazole-3-one; and mixtures thereof.
More preferred couplers include: benzene-l,3-diol; 4-chlorobenzene-l,3-diol; 2-
methyl-benzene-l,3-diol; benzene-1,3-diamine; 3-amino-phenol; 5-amino-2-methylphenol;
l-Methyl-2-hydroxy-4-(2'-hydroxyethyl)aminobenzene; 4-methyl-2-phenyl-2,4-
dihydro-3H-pyrazol-3-one; 2-aminopyridin-3-ol; l-phenyl-3-methylpyrazol-5-one; 1-
Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5)2-phenyl-3H-pyrazole-3-one; and mixtures
thereof.
Additional preferred developers and couplers include 5-methoxymethyl-2-
aminophenol, 5-ethyl-2-aminophenol, 5-phenyl-2-aminophenol, and 5-cyanoethyl-2-
aminophenol.
Further preferred developers and couplers include:
5-membered heteroaromatic keratin dyeing compounds with one, two, or three
heteroatoms relating to the following compounds:
wherein Z is selected from the group consisting of S and O;
wherein Y is selected from the group consisting of NA1, S and 0;
Bicyclic fused 5-5 heteroaromatic keratin dyeing compounds with two or three
heteroatoms relating to the following compounds:
wherein Y and Z are independently selected from the group consisting of NA1, S
and O;
Bicyclic 5-5 heteroaromatic compounds having a ring junction nitrogen according to the
following formulas:
wherein Y is selected from the group consisting of S and O;
Tricyclic 5-6-5 heteroaromatic keratin dyeing compounds having two heteroatoms
wherein Y and Z are selected from the group consisting of NA1, S, and 0;
Bicyclic 5-6 heteroaromatic keratin dyeing compounds with one ring junction nitrogen
and one or two extra heteroatoms according to the following formulas:
Tricyclic fused 6-5-6 heteroaromatic keratin dyeing compounds having one heteroatom
according to the following formula:
wherein Y is independently selected from the group consisting of NA1, S and 0;
5-membered aza heteroaromatic keratin dyeing compounds with an N-hydroxy or Namino
group and derivatives thereof, according to the following formulas:
wherein BI, Ba, 63, and 64 are selected froth the group consisting of CH and N;
wherein the corresponding R1, R2, R3,and R4 is absent when B is N;
Bicyclic 5-6 systems of aza heteroaromatic keratin dyeing compounds wherein the 5-
membered rings have one to three nitrogen atoms and an N-hydroxy or N-amino group
and derivatives thereof, according to the following jformulas:
wherein B\ and 62 are independently selected from CH or N;
wherein the corresponding R1 and R2 is absent when B is N;
Bicyclic fused 5-5-membered aza heteroaromatic keratin dyeing compounds with an Nhydroxy
or N-amino group and derivatives thereof, according to the following formulas:
Bicyclic fused 5-5-membered aza heteroaromatic keratin dyeing compounds having a ring
junction nitrogen and an N-hydroxy or N-amino group and derivatives thereof, according
to the following formulas:
Bicyclic fused 5-5-membered aza heteroaromatic keratin dyeing compounds having a ring
junction nitrogen and an N-hydroxy or N-amino group and derivatives thereof, according
to the following formulas:
wherein BI, 62, 63, 84, and 65 are selected from the group consisting of CH and N;
wherein the corresponding R1,R2, R3, R4 , and R5 is absent when B is N;
N-oxides of six-membered rings with one or two nitrogen atoms according to the
following formulas:
wherein Y is selected from the group consisting of CHb, NR7, O or S;
Bicyclic 5-5 (1:2) heteroaromatic N-oxide keratin dyeing compounds and derivatives
thereof, according to the following formulas:
wherein Y and Z are selected from the group consisting of NR5, O and S;
Mono N-oxide derivatives of 5-membered heteroaromatic compounds and derivatives
thereof, according to the following formulas:
R3
wherein Y is O, NR5 or S;
Mono- or di- N-oxide derivatives of bicyclic 5-6 (2:0, 3:0,2:1, 3:1) heteroaromatic
compounds and derivatives thereof, according to the following formulas:
wherein Y is selected from the group consisting of NR , O or S;
N-oxide derivatives of bicyclic 5-6 heteroaromatic compounds with a ring junction N
(0:1,1:0 & 1:1) and derivatives thereof, according to the following formulas:
wherein all of the aforementioned R groups are the same or different and are selected
from the group consisting of:
(a) C-linked monovalent substituents selected from the group consisting of:
(i) substituted or unsubstituted, straight or branched, alkyl, mono- or polyunsaturated
alkyl, heteroalkyl, aliphatic, heteroaliphatic, or
heteroolefinic systems,
(ii) substituted or unsubstituted, mono- or poly-cyclic aliphatic, aryl, or
heterocyclic systems, and
(iii) substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl systems;
wherein said systems of (i), (ii) and (iii) comprise from about 1 to
about 10 carbon atoms and from about 0 to about 5 heteroatoms
selected from the group consisting of 0, S, N, P, and Si;
wherein substituents of the substituted; systems of the C-linked monovalent
substituents are selected from the grbup consisting of amino, hydroxyl,
alkylamino (linear, branched, or cyclic C1-C5), dialkylamino (linear,
branched, or cyclic C1-C5), hydroXyalkylamino (linear, branched, or
cyclic C1-C5), dihydroxyalkylamino (linear, branched, or cyclic C1-C5),
arylamino or substituted arylamino (sxibstituents are halogen, C1-C5 alkyl,
C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino),
heteroarylamino or substituted heteroarylamino (substiruents are halogen,
C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino),
arylmethylamino or substituted arylmethylamino (substituents are halogen,
C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl, amino, C1-C5 alkylamino),
and heteroarylmethylamino or substituted heteroarylmethylamino
(substiruents are halogen, C1-C5 alkyl, C1-C5 alkoxy, trifluoromethyl,
amino, C1-C5 alkylamino), , ;
(b) S-linked monovalent substiruents selected from the group consisting of SA1,
SO2A1, SO3A', SSA1, SOA1, SOzNA'A2, $NA'A2, and SONA'A2;
(c) O-linked monovalent substituents selected from the group consisting of OA1,
and ONA'A2;
(d) N-linked monovalent substituents selected from the group consisting of
NA'A2, (NA]A2A3)+, NA'OA2, NAISA2,.NO2, N=NA', N^NOA1, NA]CN,
andNA'NA2A3;
(e) monovalent substituents selected from the group consisting of COOA1,
CONA
2, CONA'COA2, C(=NAI)NA1A2, CN, and X;
(f) fluoroalkyl monovalent substituents selected from the group consisting of
mono-, poly-, and per-fluoro alkyl systems comprising from about 1 to about
12 carbon atoms and from about 0 to about4 heteroatoms; and
(g) hydrogen,
wherein A1, A2, and A3 are monovalent and ate independently selected from the
group consisting of: H; substituted or unsubstituted, straight or branched, allcyl, mono- or
poly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefmic systems;
substituted or unsubstituted, mono- or poly-cyclic aliphatic, aryl, or heterocyclic systems;
and substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl systems, or A1 and A2
together with nitrogen atoms to which they are bound form a ring; wherein said systems
comprise from about 1 to about 10 carbon atoms and from about 0 to about 5 heteroatoms
selected from the group consisting of O, S, N, P, and Si;
wherein X is a halogen selected from the group consisting of F, Cl, Br, and I.
D. Direct Dyes
The inventive compositions may also comprise compatible direct dyes, in an
amount sufficient to provide additional coloring, particularly with regard to intensity.
Typically, such an amount will range from 0.05% to 4%, by weight, of the composition.
Suitable direct dyes include but are not limited to: Acid Yellow 1, Acid Orange 3,
Disperse Red 17, Basic Brown 17, Acid Black 52, Acid Black 1, Disperse Violet 4, 4-
Nitro-o-Phenylenediamine, 2-Nitro-p-Phenylenediamine, Picramic Acid, HC Red No. 13,
l,4-Bis-(2'-Hydroxyethyl)-amino-2-nitrobenzene, HC Yellow No. 5, HC Red No. 7, HC
Blue No. 2, HC Yellow No. 4, HC Yellow No. 2, HC Orange No. 1, HC Red No. 1, 2-
Chloro-5-m'tro-N-Hydroxyethyl-p-phenylenediamine, HC Red No. 3, 4-Amino-3-
nitrophenol, 2-Hydroxyethylamino-5-nitroanisole, 3-nirro-p-Hydroxyethylaminophenol,
2-amino-3-nitrophenol, 6-nitro-o-toluidine, 3-methylamino-4-nitrophenoxyethanol, 2-
nitro-5-glycerymethylanaline, HC Yellow No. 11, HC Violet No. 1, HC Orange No. 2,
HC Orange No. 3, HC Yellow No. 9, 4-Nitrophenyl Aminoethylurea, HC Red No. 10,
HC Red No. 11, 2-Hydroxyethyl picramic acid, HC Blue No. 12, HC Yellow No. 6,
Hydroxyethyl-2-nitro-p-toluidine, HC Yellow No. 12, HC Blue No. 10, HC Yellow No.
7, HC Yellow No. 10, HC Blue No. 9, N-ethyl-3-nitro PABA, 4-amino-2-nitrophenylamine-
2'-carboxylic acid, 2-chloro-6-ethylamino-4-nitrophenol, 6-Nitro-2,5-
pyridinediamine, HC Violet No. 2, 2-amino-6-chloro-4-nitrophenol, 4-
hydroxypropylamino-3-nitrophenol, HC Yellow No. 13, l,2,3,4-Tetrahydro-6-
nitrochinoxalin, HC Red No. 14, HC Yellow No. 15, HC Yellow No. 14, 3-Amino-6-
methylamino-2-nitropyridine, 2,6-diamino-3-((pyridine-3-yl)azo)pyridine, Basic Red No.
118, Basic Orange No. 69, N-(2-nitro-4-aminophenyl)-allylamine, 4-[(4-Amino-3-
methylphenyl)(4-Imino-3-methyl-2,5-Cyclohexadien-1 -ylidene) Methyl]-2-Methylbenzeneamine-
Hydrochloride, lH-Imidazolium,2-[[4-(dimethyl-amino)phenyl]azo]-l,3-
dimethylchloride, Pyridinium, l-methyl-4-[(methylphenyl-hydrazono)methyl]-, methyl
sulfate, IH-Imidazolium, 2-[(4-aminophenyl)azo]-l,3-dimethyl, chloride, Basic Red 22,
Basic Red 76, Basic Brown 16, Basic Yellow 57, 7-(2',4'-Dimethyl-5'-sulfophenylazo)-5-
sulfo-8-hydroxynaphtlialene, Acid Orange 7, Acid Red 33, l-(3'-Nitro-5'-sulfo-6'-
oxophenylazo)-oxo-naphthalene chromium complex, Acid Yellow 23, Acid Blue 9, Basic
Violet 14, Basic Blue 7, Basic Blue 26, Sodium salt of mixture of mono- & disulfonic
acids (mainly the latter) of quinophthlanone or 2-quinolylindandione, Basic Red 2, Basic
Blue 99, Disperse Red 15, Acid Violet 43, Disperse Violet 1, Acid Blue 62, Pigment Blue
15, Acid Black 132, Basic Yellow 29, Disperse Black 9, l-(N-Methylmorpholiniumpropylamino)-
4-hydroxy-anthraquinone methylsulfate, HC Blue No. 8, HC Red No. 8,
HC Green No. 1, HC Red No. 9, 2-Hydroxy-l,4-naphthoquinone, Acid Blue 199, Acid
Blue 25, Acid Red 4, Henna Red, Indigo, Cochenille, HC Blue 14, Disperse Blue 23,
Disperse Blue 3, Violet 2, Disperse Blue 377, Basic Red 51, Basic Orange 31, Basic
Yellow 87, and mixtures thereof. Preferred direct dyes include but are not limited to:
Disperse Black 9, HC Yellow 2, HC Yellow 4, HC Yellow 15, 4-nitro-ophenylenediamine,
2-amino-6-chloro-4-nitrophenol, HC Red 3, Disperse Violet 1, HC
Blue 2, Disperse Blue 3, Disperse Blue 377, Basic Red 51, Basic Orange 31, Basic
/
Yellow 87, and mixtures thereof.
E. Oxidizing Agent
The inventive compositions may comprise an oxidizing agent, present in an
amount sufficient to bleach melanin pigment in hair and/or cause formation of dye
chromophores from oxidative dye precursors (including developers and/or couplers when
present). Typically, such an amount ranges from 1% to 20%, preferably from 3% to 15%,
more preferably from 6% to 12%, by weight, of the developer composition. Inorganic
peroxygen materials capable of yielding hydrogen peroxide in an aqueous medium are
preferred, and include but are not limited to: hydrogen peroxide; inorganic alkali metal
peroxides (e.g. sodium periodate and sodium peroxide); organic peroxides (e.g. urea
peroxide, melamine peroxide); inorganic perhydrate salt bleaching compounds (e.g. alkali
metal salts of perborates, percarbonates, perphosphates, persilicates, and persulphates,
preferably sodium salts thereof), which may be incorporated as monohydrates,
tetrahydrates, etc.; alkali metal bromates; enzymes; and mixtures thereof. Preferred is
hydrogen peroxide.
F. Thickeners
The inventive compositions may comprise a thickener in an amount sufficient to
provide the composition with a viscosity so that it can be readily applied to the hair
without unduly dripping off the hair and causing mess. Typically, such an amount will be
at least 0.1%, preferably at least 0.5%, more preferably, at least 1%, by weight, of the
composition.
Preferred for use herein are salt tolerant thickeners, including but not limited to:
xanthan, guar, hydroxypropyl guar, scleroglucan, methyl cellulose, ethyl cellulose
(available as AQUACOTE (TM)), hydroxyethyl cellulose (NATROSOL (TM)),
carboxymethyl cellulose, hydroxypropylmethyl cellulose, macrocrystalline cellulose,
hydroxybutylmethyl cellulose, hydroxypropyl cellulose (available as KLUCEL (TM)),
hydroxyethyl ethyl cellulose, cetyl hydroxyethyl cellulose (available as NATROSOL
(TM) Plus 330), N-vinylpyrollidone (available as POVIDONE (TM)), Acrylates/Ceteth-
20 Itaconate Copolymer (available as STRUCTURE (TM) 3001), hydroxypropyl starch
phosphate (available as STRUCTURE (TM) ZEA), polyethoxylated urethanes' or
polycarbamyl polyglycol ester (e.g. PEG-150/Decyl/SMDI copolymer (available as
ACULYN(TM) 44), PEG-150/Stearyl/SMDI copolymer. available as ACULYN(TM) 46),
trihydroxystearin (available as THIXCIN(TM)), acrylates copolymer (e.g. available as
ACULYN(TM) 33) or hydrophobically modified acrylate copolymers (e.g. Acrylates /
Steareth-20 Methacryiate Copolymer (available as ACULYN(TM) 22), non-ionic
amphophilic polymers comprising at least one fatty chain and at least one hydrophilic unit
selected from polyether urethanes comprising at least one fatty chain, and blends of
Ceteth - 10 phosphate, Di-cetyl phosphate and Cetearyl alcohol (available as
CRODAFOS(TM) CES).
G. Chelants
The inventive compositions may comprise chelants in an amount sufficient to
reduce the amount of metals available to interact with formulation components,
particularly oxidizing agents, more particularly peroxides. Typically such an amount will
range from at least 0.25%, preferably at least 0.5%, by weight, of the composition.
Suitable chelants for use herein include but are not limited to: diamine-N,N'-dipolyacid,
monoamine monoamide-N,N'-dipolyacid, and N,N'-bis(2-
hydroxybenzyl)ethylenediamine-N,N'-diacetic acid chelants (preferably EDDS
(ethylenediaminedisuccinic acid)), carboxylic acids (preferably aminocarboxylic acids),
pb.ospb.onic acids (preferably aminophosphonic acids) and polyphosphoric acids (in
particular straight polyphosphoric acids), their salts and derivatives.
H. pH Modifiers and Buffering agents
The inventive compositions may further comprise a pH modifier and/or buffering
agent in an amount that is sufficiently effective to adjust the pH of the composition to fall
within a range from 3 to 13, preferably from 8 to 12, more preferably from 9 to 11.
Suitable pH modifiers and/or buffering agents for use herein include, but are not limited
to: ammonia, alkanolamides such as monoethanolamine, diethanolamine, triethanolamine,
monopropanolamine, dipropanolamine, tripropanolamine, tripropanolamine, 2-amino-2-
methyl-1-propanol, and 2-amino-2-hydroxymethyl-l,3,-propandiol and guanidium salts,
alkali metal and ammonium hydroxides and carbonates, preferably sodium hydroxide and
ammonium carbonate, and acidulents such as inorganic and inorganic acids, e.g.,
phosphoric acid, acetic acid, ascorbic acid, citric acid or tartaric acid, hydrochloric acid,
and mixtures thereof.
I. Carbonate ion source and Radical Scavenger System
The inventive compositions may comprise a system comprising a source of
carbonate ions, carbamate ions and or hydrocarbonate ions, and a radical scavenger, in a
sufficient amount to reduce damage to the hair during the coloring process. Typically,
such an amount will range from 0.1% to 15%, preferably 0.1% to 10%, more preferably
1% to 7%, by weight of the composition, of the carbonate ion, and from 0.1% to 10%,
preferably from 1% to 7%, by weight of the composition, of radical scavenger.
Preferably, the radical scavenger is present at an amount such that the ratio of radical
scavenger to carbonate ion is from 1:1 to 1:4. The radical scavenger is preferably
selected such that it is not an identical species as the alkalizing agent.
Suitable sources for the ions include but are not limited to: sodium carbonate,
sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate,
guanidine carbonate, guanidine hydrogen carbonate, lithium carbonate, calcium
carbonate, magnesium carbonate, barium carbonate, ammonium carbonate, ammonium
hydrogen carbonate and mixtures thereof. Preferred sources of carbonate ions are sodium
hydrogen carbonate and potassium hydrogen carbonate. Also preferred are ammonium
carbonate, and ammonium hydrogen carbonate.
The radical scavenger is a species that can react with a carbonate radical to
convert the carbonate radical by a series of fast reactions to a less reactive species.
Preferably, when the radical scavenger comprises an N atom, it has a pKa 7 to prevent
the protonation of the nitrogen. Preferred radical scavengers may be selected from the
classes of alkanolamines, amino sugars, amino acids and mixtures thereof, and may
include, but are not limited to: monoethanolamine, 3-amino-l-propanol, 4-amino-lbutanol,
5-amino-l-pentanol, l-amino-2-propanol, l-amino-2-butanol, l-amino-2-
pentanol, l-amino-3-pentanol, l-amino-4-pentanol, 3-amino-2-methylpropan-l-ol, 1-
amino-2-methylpropan-2-ol, 3-aminopropane-l,2-diol, glucosamine, Nacetylglucosamine,
glycine, arginine, lysine, proline, glutamine, histidine, serine,
tryptophan and potassium, sodium and ammonium salts of the above and mixtures
thereof. Other preferred radical scavenger compounds include benzylamine, glutamic
acid, imidazole, di-tert-butylhydroxytoluene, hydroquinone, catechol and mixtures
thereof.
III. Methods of Manufacture
The compounds of this invention may be obtained using conventional methods. A
general description of how to make the compounds is provided above and specific
examples are provided below. The compositions of this invention may also be obtained
using conventional methods. The keratin dyeing compositions may be formed as
solutions, preferably as aqueous or aqueous-alcohol solutions. The hair dye product
compositions may preferably be formed as thick liquids, creams, gels, or emulsions
whose composition is a mixture of the dye compound and other dye ingredients with
conventional cosmetic additive ingredients suitable for the particular preparation.
IV. Methods of Use
The inventive keratin dyeing compositions may be used by admixing them with a
suitable oxidant, which reacts with the oxidative dye precursors to develop the hair dye
product composition. The oxidant is usually provided in an aqueous composition, which
normally is provided as a separate component of the finished keratin dyeing product
system and present in a separate container. Upon mixing the keratin dyeing composition,
the adjuvants are provided in the hair dye composition as it is applied to the hair to
achieve desired product attributes, e.g., pH, viscosity, rheology, etc.
The keratin dyeing composition, as it is applied to the hair, can be weakly acidic,
neutral or alkaline according to their composition, typically having a pH from 6 to 11,
preferably from 7 to 10, more preferably from 8 to 10. The pH of the developer
composition is typically acidic, and generally the pH is from 2.5 to 6.5, preferably from 3
to 5. The pH of the hair compositions may be adjusted using a pH modifier as mentioned
above.
In order to use the keratin dyeing composition, the above-described compositions
are mixed immediately prior to use and a sufficient amount of the mixture is applied to
the hair, according to the hair abundance, generally from 60 to 200 grams. Upon such
preparation the hair dye composition is applied to the hair to be dyed and remains in
contact with the hair for an amount of time effective to dye the hair. Typically, the hair
dye composition is allowed to act on the hair for 2 to 60, preferably 15 to 45, more
preferably, 30 minutes, at a temperature ranging from 15° to 50°C. Thereafter, the hair is
rinsed with water, to remove the hair dye composition and dried. If necessary, the hair is
washed with a shampoo and rinsed, e.g., with water or a weakly acidic solution, such as a
citric acid or tartaric acid solution, and dried. Optionally, a separate conditioning product
may also be provided.
Together, components of the keratin dyeing composition form a system for dyeing
hair. This system may be provided as a kit comprising in a single package separate
containers of the keratin dyeing composition components or other hair treatment product,
and instructions for use.
Examples
The following are non-limiting examples of the compositions of the present
invention. The examples are given solely for the purpose of illustration and are not to be
construed as limitations of the present invention, as many variations thereof are possible
without departing from the spirit and scope of the invention, which would be recognized
by one of ordinary skill in the art. In the examples, all concentrations are listed as weight
percent, unless otherwise specified.
The following compositions can be used for dyeing hair. The dyeing composition
is mixed with an equal weight of a 20-volume hydrogen peroxide solution (6% by
weight). The resulting mixture is applied to the hair and permitted to remain in contact
62.
with the hair for 30 minutes. This dyed hair is then shampooed and rinsed with water and
dried.
Common base (CB) for dyeing
Ingredients
Propylene glycol
Ammonium hydroxide
Ethoxydiglycol
Ethanolamine
Oleic acid
Hexylene glycol
Cocamidopropyl betaine
Oleth-10
Oleth-2
Dilinoleic acid
C12-C15 Pareth-3
Soytrimonium chloride
Sodium metasilicate
Erythorbic acid
EDTA
Sodium sulfite
1 -Phenyl-3-methyl-5-pyrazolone
Weight
00
9.5
5
4
4.5
1
6
3.5
0.3
0.3
1.5
0.5
7
0.05
0.5
0.03
0.3
0.2
Ingredients
1 ,5-Dihydro-pyrrolo[2,3-
fjindole
N,N-Bis(2-hydroxyetyl)-pphenylendiamine
4-Aminophenol
4-Amino-2-methylphenol
3-Aminophenol
5-Amino-2-methylphenol
1-Naphthol
Resorcinol
2-Methylresorcinol
l-Hydroxyethyl-4,5-
diaminopyrazole
Common base (CB)
Water
1
0.05
0.1
0.2
0.1
0.05
0.15
44.1
8
qs
2
0.04
0.02
0.02
0.1
44.1
8
qs
3
0.03
0.3
0.02
0.1
0.4
44.1
8
qs
4
0.01
0.4
0.4
44.1
8
qs
5
0.05
0.2
0.02
0.1
44.1
8
qs
6
0.15
0.4
0.5
0.2
44.1
8
qs
7
0.2
0.02
0.2
0.04
0.4
44.1
8
qs
Ingredients
1 ,7-Dihydro-pyrrolo[3,2-fIindoIe
N,N-Bis(2-hydroxyetyl)-pphenylendiamine
8
0.3
0.33
9
.0.2
0.02
10
0.2
11
0.1
12
0.1
13
0.2
14
0.6
4-Aminophenol
4-Amino-2-methylphenol
3-Aminophenol
5 - Amino-2-methylphenol
1-Naphthol
Resorcinol
2-Methylresorcinol
1 -Hydroxyethyl-4,5 -
diaminopyrazole
Common base (CB)
Water
0.5
0.3
0.3
0.4
44.1
8
qs
1
0.4
0.1
0.6
44.1
8
qs
0.7
0.4
0.1
0.6
44.1
8
qs
1.2
2.5
0.1
0.2
44.1
8
qs
0.9
2.5
0.1
0.2
44.1
8
qs
1.2
1
0.6
0.4
44.1
8
qs
0.3
0.8
0.1
44.1
8
qs
Ingredients
8H-1 -oxa-8-aza-as-indacene-2,7-
diamine
N,N-Bis(2-hydroxyetyl)-pphenylendiarnine
4-Aminophenol
4- Amino-2-methylphenol
3-Aminophenol
5-Amino-2-methylphenol
1-Naphthol
Resorcinol
2-Methylresorcinol
1 -Hydroxyethyl-4,5-
diaminopyrazole
Common base (CB)
Water
15
1
0.4
1.4
44.1
8
qs
16
0.1
0.6
0.5
0.5
0.6
44.1
8
qs
17
0.5
1.5
i
2
44.1
8
qs
18
0.5
1
1.5
44.1
8
qs
19
0.1
0.1
0.1
0.2
0.5
44.1
8
qs
20
0.1
0.8
0.8
0.1
0.1
0.2
0.8
44.1
8
qs
21
0.5
0.1
0.1
0.1
0.1
0.5
0.1
44.1
8
qs
Ingredients
1 ,5-dithia-s-indacen-4-ol
1 ,5-dihydro-pyrrolo [2,3 -
f]indol-4-ol
N,N-Bis(2-hydroxyetyl)-pphenylendiamine
p-Phenylenediamine
4-Aminophenol
4- Amino-2-methylphenol
3-Aminophenol
5-Amino-2-methylphenol
1-Naphthol
Resorcinol
2-Methylresorcinol
l-Hydroxyethyl-4,5-
22
0.3
0.1
0.5
0.3
0.3
0.4
23
0.5
0.1
1
0.4
0.2
0.2
0.5
24
0.4
0.3
0.1
0.2
0.2
0.1
0.4
0.1
25
0.3
0.4
0.2
0.5
0.3
0.3
26
0.5
0.1
1
0.4
0.2
0.2
0.5
27
0.4
0.3
0.1
0.2
0.2
0.1
0.4
0.1
28
0.3
0.4
0.2
0.5
0.3
0.3
diaminopyrazole
Common base (CB)
Water
44.18
qs
44.18
qs
44.18
qs
44.18
qs
44.18
qs
44.18
qs
44.18
qs
While particular embodiments of the present invention have been illustrated and
described, it would be obvious to those skilled in the art that various other changes and
modifications can be made without departing from the spirit and scope of the invention.
It is therefore intended to cover in the appended claims all such changes and
modifications that are within the scope of this invention.
All documents cited in the Background, Summary of the Invention, and Detailed
Description of the Invention are, in relevant part, incorporated herein by reference; the
citation of any document is not to be construed as an admission that it is prior art with
respect to the present invention.










We Claim:
1. A keratin dyeing composition comprising:
(A) a medium suitable for dyeing;
(B) one or more tricyclic 5-6-5 heteroaromatic keratin dyeing
compounds having two heteroatoms according to the following formulas:
(Formula Removed)
wherein Y and Z are independently selected from the group consisting of NA1, S, andO;
wherein R1, R2, R3, R4, R5 and R6 are the same or different and are selected from the group consisting of:
(a) C-linked monovalent substituents selected from the group consisting of:
(i) substituted or unsubstituted, straight or branched, alkyl, mono- or polyunsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinic systems, (ii) substituted or unsubstituted, mono- or poly-cyclic aliphatic, aryl, or
heterocyclic systems, and
(iii) substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl
systems;
wherein said systems of (i), (ii) and (iii) comprise from 1 to 10 carbon
atoms and from 0 to 5 heteroatoms selected from the group consisting
ofO, S,N,P,andSi;
(b) S-linked monovalent substituents selected from the group consisting of
SA1,
SO2A1, SO3A1, SSA1, SOA1, SO2NA1A2, SNA1A2, and SONA1A2;
(c) O-linked monovalent substituents selected from the group consisting of
OA1,
and ONA1A2;
(d) N-linked monovalent substituents selected from the group consisting of NA1A2, (NA1A2A3)+, NA1OA2, NA1SA2, NO2, N=NA1, N=NOA1, NA1CN, NA1NA2A3;
(e) monovalent substituents selected from the group consisting of COOA1, CONA12, CONA1COA2, C(=NA1)NA1A2, CN, and X;
(f) fluoroalkyl monovalent substituents selected from the group consisting of mono-, poly-, and per-fluoro alkyl systems comprising from 1 to 12 carbon atoms and from 0 to 4 heteroatoms; and
(g) hydrogen;
wherein A1, A2, and A3 are monovalent and are independently selected from the group consisting of: H; substituted or unsubstituted, straight or branched, alkyl, mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinic systems; substituted or unsubstituted, mono- or poly-cyclic aliphatic, aryl, or heterocyclic systems; and substituted or unsubstituted, mono-, poly-, per-fluoro alkyl systems or A1 and A2 together with nitrogen atom to which they are bound form a ring; wherein said systems comprise from 1 to 10 carbon atoms and from 0 to 5 heteroatoms selected from the group consisting of O, S, N, P, and Si; and
wherein X is a halogen selected from the group consisting of F, CI, Br, and I; and
(C) at least one five-membered ring developer selected from the group
consisting of thiophenes, pyrroles, furans, pyrazoles, imidazoles, thiazoles,
oxazoles, isothiazoles, and isoxazoles, preferably a pyrazole,
wherein said five-membered ring developer is selected from the group consisting of 1-methyl-lH-pyrazole-4,5-diamine, 2-(4,5-diamino-lH-pyrazol-l-y)ethanol, 1 -isopropyl-1 H-pyrazole-4,5-diamine, 1 -(4-methylbenzyl)-1 H-pyrazole-4,5-diamine, 1 -(benzyl)-1 H-pyrazole-4,5-diamine, 1 -(4-chlorobenzyl)-1 H-pyrazole-4,5-diamine, and l-hydroxyethyl-4,5-diaminopyrazole sulphate.
2. The composition of claim 1 wherein said R1, R2, R3, R4, R5, and R6 are independently selected from the group consisting of a hydrogen atom; a halogen atom; an amino substituent; a hydroxyl substituent; a cyano substituent; a C1-C4 alkyl substituent; a trifiuoromethyl substituent; an alkylamino substituent; a hydroxyalkylamino substituent; an acetylamido substituent; a carboxyl substituent or its esters; an alkoxy substituent; an alkoxyalkyl substituent; a carbamoyl substituent; an alkylcarbamoyl substituent; a hydroxyalkylcarbamoyl substituent; an amido substituent; an alkylamido substituent; an alkylcarbonyl substituent; an alkoxycarbonyl substituent; an aryloxy substituent; an acyloxy substituent; an alkylthio substituent; an arylthio substituent; a heteroarylthio substituent; a heteroaryloxy substituent; a thiocyano substituent; a 3-, 4-, 5-, 6-, or 7-membered heterocycle having at least one nitrogen, oxygen or sulfur atom; an aryl substituent which is optionally substituted; a sulfonyl substituent; a sulfinyl substituent; a phosphonyl substituent; a sulfamoyl substituent; a siloxy substituent; an acyloxy substituent; a carbamoyloxy substituent; a sulphonamide substituent; an imide substituent; a ureido substituent; a sulfamoylamino substituent; an alkoxycarbonylamino substituent; an aryloxycarbonylamino substituent; an aryloxycarbonyl substituent; and a benzenesulfonamido substituent.
3. The composition of claim 1 wherein said tricyclic 5-6-5 heteroaromatic keratin dyeing compound having two heteroatoms is selected from an unsubstituted or substituted member of the group consisting of benzo[l,2-b;4,5-b']difuran, 5H-l-oxa-5-aza-s-indacene, l-oxa-5-thia-s-indacene, l,5-dihydro-pyrrolo[2,3-f]indole, 5H-1-thia-5-aza-s-indacene, 1,5-dithia-s-indacene, benzo[l,2-b;5,4-b']difuran, 7H-l-oxa-7-aza-s-indacene, l-oxa-7-thia-s-indacene, 1,7-dithia-s-indacene, 1,7-dihydro-pyrrolo[3,2-f]indole, 7H-l-thia-7-aza-s-indacene, benzo[2,l-b;3,4-b']difuran, 8H-1-oxa-8-aza-as-indacene, l-oxa-8-thia- as-indacene, 1,8-dihydro-l ,8-diaza-as-indacene, 8H-l-thia-8-aza-as-indacene, 1,8-dithia- as-indacene, benzo[l,2-b;4,3-b']difuran, 6H-
3-oxa-6-aza-as-indacene, 3-oxa-6-thia-as- indacene, 3,6-dihydro-3,6-diaza-as-indacene, 6H-3-thia-6-aza-as-indacene, and 3,6dithia- as-indacene.
4. The composition of any one of the preceding claims further comprising
at least one additional component selected from auxiliary developers, auxiliary
couplers, direct dyes, oxidizing agents, thickeners, chelants, pH modifiers, buffering
agents, and carbonate ion source and radical scavenger systems.
5. The composition of any one of the preceding claims for dyeing hair by
applying said composition and rinsing hair.
6. A kit comprising:
(a) the composition according to anyone of claims 1 to 4;
(b) an oxidizing agent; and
(c) auxiliary couplers and/or auxiliary developers.

Documents:

5437-delnp-2006-abstract.pdf

5437-delnp-2006-assignments.pdf

5437-DELNP-2006-Claims-(15-02-2010).pdf

5437-delnp-2006-claims.pdf

5437-DELNP-2006-Correspondence-Others (15-02-2010).pdf

5437-DELNP-2006-Correspondence-Others-(13-04-2010).pdf

5437-DELNP-2006-Correspondence-Others-(25-06-2009).pdf

5437-delnp-2006-correspondence-others-1.pdf

5437-delnp-2006-correspondence-others.pdf

5437-delnp-2006-description (complete).pdf

5437-DELNP-2006-Form-1-(15-02-2010).pdf

5437-delnp-2006-form-1.pdf

5437-delnp-2006-form-18.pdf

5437-delnp-2006-form-2.pdf

5437-delnp-2006-form-26.pdf

5437-DELNP-2006-Form-3-(25-06-2009).pdf

5437-delnp-2006-form-3.pdf

5437-delnp-2006-form-5.pdf

5437-DELNP-2006-Others-Documents-(25-06-2009).pdf

5437-delnp-2006-pct-210.pdf

5437-delnp-2006-pct-237.pdf

5437-delnp-2006-pct-304.pdf

5437-delnp-2006-pct-373.pdf


Patent Number 241242
Indian Patent Application Number 5437/DELNP/2006
PG Journal Number 27/2010
Publication Date 02-Jul-2010
Grant Date 24-Jun-2010
Date of Filing 19-Sep-2006
Name of Patentee THE PROCTER AND GAMBLE COMPANY
Applicant Address ONE PROCTER & GAMBLE PLAZA, CINCINNATI, OHIO 45202 (US)
Inventors:
# Inventor's Name Inventor's Address
1 GLENN, ROBERT, WAYNE, JR. TRUSCOTT KNOWLE HILL, VIRGINIA WATER SURREY GU25 4HZ (GB)
2 LIM, MUILL 5922 TAYLOR DRIVE, WEST CHESTER, OHIO 45069 (US)
3 GARDLIK, JOHN, MICHAEL 9109 MILLCLIFF DRIVE, CINCINNATI, OHIO 45231 (US)
4 JONES, STEVAN, DAVID 966 HATCH STREET, CINCINNATI, OHIO 45202 (US)
5 MURPHY, BRYAN, PATRICK 974 ARNOLD PALMER DRIVE, LOVELAND, OHIO 45140 (US)
6 REES, CHARLES, WAYNE 67 HILLGATE PLACE, LONDON W87SS (GB)
PCT International Classification Number A61K 7/13
PCT International Application Number PCT/US05/007345
PCT International Filing date 2005-03-02
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/550,106 2004-03-04 U.S.A.