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WO2002003938A1 - Iodo-containing organic couplers for use in oxidative hair dyeing - Google Patents

Iodo-containing organic couplers for use in oxidative hair dyeing Download PDF

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Publication number
WO2002003938A1
WO2002003938A1 PCT/US2001/020024 US0120024W WO0203938A1 WO 2002003938 A1 WO2002003938 A1 WO 2002003938A1 US 0120024 W US0120024 W US 0120024W WO 0203938 A1 WO0203938 A1 WO 0203938A1
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Prior art keywords
aminophenol
methyl
phenylenediamine
hydroxyethyl
dihydroxyindole
Prior art date
Application number
PCT/US2001/020024
Other languages
French (fr)
Inventor
Giuseppe Prota
Gottfried Wenke
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Clairol Incorporated
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Priority to AU2001268691A priority Critical patent/AU2001268691A1/en
Publication of WO2002003938A1 publication Critical patent/WO2002003938A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/347—Phenols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/415—Aminophenols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings

Definitions

  • inorganic iodide compounds such as alkali metal, alkaline earth metal and ammonium iodide
  • inorganic iodide compounds can be employed as catalysts for speeding up the time for the oxidative dyeing of hair to provide mild and fast dyeing.
  • inorganic iodide compounds such as alkali metal, alkaline earth metal and ammonium iodide
  • Iodine-containing couplers of this invention also include, for example, 1-iodo-2-hydroxynaphth ⁇ l and 5-iodo-6-hydroxyquinoline of the formulae
  • the following compositions, shown in Table 1 were used for dyeing the Piedmont hair.
  • the dyeing solution comprised 0.042 mmole primary intermediate and 0.042 mmole coupler in 12 g of a typical dye base (concentration after mixing with oxidant).
  • the typical dye base comprised an alkylethersulfate, an alkanol, 25% ammonia solution, an organic acid, ethylenediaminetetraacetic acid and water.
  • the dyeing solution was mixed with 2 g of 3% hydrogen peroxide.
  • the resulting dyeing formulation was applied to the hair and permitted to remain in contact with the hair for 10 or 20 minutes as indicated in Table 1.
  • the dyed hair was then rinsed with water, shampooed and rinsed again with water and dried with a hair dryer.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Emergency Medicine (AREA)
  • Cosmetics (AREA)

Abstract

A process and composition for the oxidative coloring of hair comprising reacting a primary intermediate with an iodo-containing organic coupler of the formula (I) wherein R?1, R2, R3 and R4¿ are each independently H, I, or a straight or branched chain C¿1?-C4 alkyl group optionally substituted with one or more substituents selected from OH, NH2, NHR?8, NH8, OR9¿, phenyl or a five- or six-membered heterocyclic ring containing one or two nitrogen atoms, an oxygen atom or a sulfur atom with the remainder of the ring being carbon atoms, or R?2 and R3 or R3 and R4¿ together with the carbon atoms to which they are attached may form a benzene ring or a pyridine ring which may optionally be substituted by one or more substituents selected from NH¿2?, optionally be substituted by one or more substituents selected from NH2, NHR?6, NR6R7¿, OH or OR6 with the proviso that from 1 to 3 of the R?1, R2, R3 and R4¿ substituent is I and at least one of the iodo substituents is in the ortho- or para- position to the R substituent; R is OH, NH¿2?, NHR?6 or NR6R7¿, and where R?2 and R3 or R3 and R4¿ form a benzene or pyridine ring R can be H. R?6 and R7¿ independently each being a branched or straight chain C¿1?-C4 alkyl group optionally substituted with one or more substituents selected from OH, NH2, NHR?8, NR8R9, OR8¿, phenyl, or a five- or six-membered heterocyclic ring containing one or two nitrogen atoms, an oxygen atom or a sulfur atom with the remainder of the ring being carbon atoms; and R?8 and R9¿ are each independently a straight or branched chain C¿1?-C4 alkyl group, optionally substituted with one or more substituents selected from OH, OCH3 and NH2.

Description

IODO-CONTAINING ORGANIC COUPLERS FOR USE IN OXIDATIVE HAIR DYEING
Field of the Invention
This invention relates to iodo-containing organic couplers for use in hair coloring compositions. The invention also relates to hair coloring compositions and processes utilizing these iodo-containing organic couplers.
Background of the Invention
Coloration of hair is a procedure which has been practiced from antiquity by a variety of methods. In modern times, the most extensively used method to color hair is by an oxidative dyeing process. The process utilizes one or more oxidative hair coloring agents in combination with one or more oxidizing agents.
Most commonly, a peroxy oxidizing agent is used in combination with one or more oxidative hair coloring agents. The chemical reaction involves colorless dye precursors of small molecular size capable of diffusing into hair that undergo coupling reactions inside the hair to produce dyes of larger molecular weight. These precursors are dye intermediates. In this procedure, a peroxide material, such as hydrogen peroxide, is employed to activate the small molecules of primary intermediates so that they react with couplers to form larger sized complexes in the hair shaft to color the hair in a variety of shades and colors.
It has been disclosed that inorganic iodide compounds, such as alkali metal, alkaline earth metal and ammonium iodide, can be employed as catalysts for speeding up the time for the oxidative dyeing of hair to provide mild and fast dyeing. In this regard, reference is made to the disclosures in US Patent No. 1 ,677,508, US Patent No. 5,180,397, US Patent No. 5,180,399, US Patent No. 5,540,738 and GB Patent Publication No. 2,205,329A.
However, what is lacking in the art and is solved by the present invention is the utilization of iodide compounds to provide the mild and fast dyeing advantages of the catalysis action of the inorganic iodide compounds and which also act as couplers to provide improved and stable hair dyeing color results, as well as improved wearing properties even when the dyed hair is subject to light and/or shampooing.
Summary of the Invention
This invention provides iodo-containing organic couplers that also act as oxidation catalysts for the oxidative dyeing of hair. Any suitable iodo-containing organic compound capable of acting as a dye coupler with at least one hair dye primary intermediate can be employed in this invention.
The invention further provides a process for coloring hair which comprises reacting a primary intermediate with an iodo-containing organic coupler in the presence of an oxidizing agent to produce an oxidative hair dye wherein iodide is liberated and the activity of the oxidizing agent is increased.
The invention also provides a hair coloring composition for dyeing human hair. Detailed Description of the Invention
The invention provides a hair coloring composition for dyeing human hair comprising, in a suitable carrier or vehicle, a hair dyeing effective amount of:
(a) a primary intermediate,
(b) a coupler comprising an iodo-containing organic coupler, and
(c) an oxidizing agent.
The iodo-containing organic couplers of this invention particularly comprise compounds of the formula
Figure imgf000004_0001
wherein R1, R2, R3 and R4 are each independently H, I, or a straight or branched chain Cι-C alkyl group optionally substituted with one or more substituents selected from OH, NH2, NHR8, NH8R9, OR8, phenyl, or a five- or six-membered heterocyclic ring containing one or two nitrogen atoms, an oxygen atom or a sulfur atom with the remainder of the ring being carbon atoms, or R2 and R3 or R3 and R4 together with the carbon atoms to which they are attached may form a benzene ring or a pyridine ring which may optionally be substituted by one or more substituents selected from NH2, NHR6, NR6R7, OH or OR6 with the proviso that from 1 to 3 of the R1, R2, R3 and R4 substituent is I and at least one of the iodo substituents is in the ortho- or para- position to the R substituent; R is OH, NH2, NHR6 or NR6R7, and where R2 and R3 or R3 and R4 form a benzene or pyridine ring R can be H.
R6 and R7 independently each being a branched or straight chain Cι-C alkyl group optionally substituted with one or more substituents selected from OH, NH2, NHR8, NR8R9, OR8, phenyl, or a five- or six- membered heterocyclic ring containing one or two nitrogen atoms, an oxygen atom or a sulfur atom with the remainder of the ring being carbon atoms; and
R8 and R9 are each independently a straight or branched chain Cι-C alkyl group, optionally substituted with one or more substituents selected from OH, OCH3 and NH2.
These iodo-containing organic couplers are used with primary intermediates, and optionally with other couplers, to provide an oxidative hair dyeing process and composition for dyeing hair, particularly human hair, in a wide variety of colors and shades which are stable over a relatively long period of time. The iodo-containing organic couplers of this invention provide for fast and mild dyeing of hair in a wide variety of colors or shades having good wash fastness and which do not undergo undesirable significant changes on exposure to light or shampooing. The effect of the iodo- containing organic couplers of this invention is particularly noticeable with primary intermediates that are more difficult to oxidize, such as for example 2- chloro-p-phenylenediamine.
The iodo-containing couplers of this invention appear to slowly develop iodine in or on the hair during the hair dyeing process and enhance the efficacy of the oxidizing agent within the hair shaft. Iodide in a position ortho- or para to an OH or NH2 group may be released from the coupler molecule during or after the coupling reaction with the (oxidized) primary intermediate. Subsequently, iodide may react with H2O2 inside the hair shaft to form iodine.
Iodine-containing couplers of this invention are particularly those of the formula
Figure imgf000006_0001
wherein R1, R2, R3 and R4 are each independently H, I, NH2, CH3 or R2 and R3 together with the carbon atoms to which they are attached form a benzene or pyridine ring, and R is OH or NH2, with the proviso that from 1 to 3 of the R1, R2, R3 and R4 substituents is I and at least one of the iodo substituents is in the ortho- or para- position to the R substituent.
Especially preferred iodine-containing couplers of this invention are 2-iodoresorcinol, 2,4-diiodoresorcinol, 2-methyl-4-iodoresorcinol, 2- methyl-4-iodo-5-aminophenol, 2,4-diiodo-5-aminophenol and 2,4,6-
Figure imgf000006_0002
triiodoresorcinol of the formulae
Iodine-containing couplers of this invention also include, for example, 1-iodo-2-hydroxynaphthαl and 5-iodo-6-hydroxyquinoline of the formulae
Figure imgf000007_0001
Iodo-containing organic couplers of this invention are either available or can be produced by iodination of precursors therefor employing conventional iodination procedures. Synthesis of such iodo-containing organic couplers is exemplified in the following Synthesis Examples 1 to 7.
SYNTHESIS EXAMPLE 1 Synthesis of 2-iodoresorcinol
To a mixture of resorcinol (1.1 g, 0.01 mol) in water (25 ml) containing 0.01 mol HCI was added with stirring an aqueous solution (50 ml) of KIO3 (0.33 eq) and Kl (0.67 eq) over a period of 1 hr. Stirring was continued for an additional 2 hr, and the mixture was then extracted with ethyl acetate, the organic layers were taken to dryness to give an oily residue that was crystallized with chloroform/light petroleum and left at 4°C overnight to complete separation of crystals. The material thus obtained was chromatographically homogenous.
TLC: chloroform-methanol 95:5 v/v Rf=0.73 UV (CH3OH) λmax, 275, 281 nm 1H-NMR δ 6.93 (1 H, t, J=6.0), 6.32 (2 H, d, J-6.0) EI-MS: m/z 236 (M)+
SYNTHESIS EXAMPLE 2 Synthesis of 2,4-diiodoresorcinol To a mixture of resorcinol (1.1 g, 0.01 mol) in water (25 ml) containing HCI (0.02 mol) was added under stirring over a period of 60 min a solution of KI03 (0.67 eq) and Kl (1.3 eq) in water (50 ml). Stirring was continued for 2 hr at room temperature, and eventually the mixture was extracted with ethyl acetate, the organic extracts were taken to dryness to give an oily residue that was treated with CCI at 80°C and then left overnight at 4°C. The light yellow solid thus obtained was filtered and proved to be chromatographically homogeneous.
TLC: chloroform-methanol 95:5 v/v Rf=0.81 UV (CH3OH) λmax, 283 nm 1H-NMR δ 7.4 (1 H, d, J=8.4), 6.2 (1 H, d, J-8.4) EI-MS: m/z 362 (M)+
SYNTHESIS EXAMPLE 3
Synthesis of 2-methyl-4-iodoresorcinol
To a mixture of 2-methylresorcinol (1.24 g, 0.01 mol) in water
(25 ml) containing 0.01 mol HCI was slowly added with stirring over a period of about 1 hr an aqueous solution (50 ml) of KIO3 (0.33 eq) and Kl (0.67 eq).
Stirring was continued for an additional 2 hr, and the solid that separated was collected by filtration to give sufficiently pure 2-methyl-4-iodoresorcinol.
TLC: chloroform-methanol 95:5 v/v Rf=0.69 UV (CH3OH) λmax, 210, 279 nm
1H-NMR δ 7.3 (1 H, d, J=8.4), 6.2 (1 H, d, J=8.4), 2.1 (3 H, s) EI-MS: m/z 250 (M)+
SYNTHESIS EXAMPLE 4 Synthesis of 1 -iodo-2-hydroxynaphthol To a mixture of β-naphtol (0.01 mol) in water (25 ml) containing
0.01 mol HCI was added with stirring over a period of about 1 hr an aqueous solution (50 ml) of KIO3 (0.33 eq) and Kl (0.67 eq). Stirring was continued for an additional 2 hr, and the solid that separated was collected to give chromatographically homogeneous 1-iodo-2-hydroxynaphthol.
TLC: chloroform-methanol 98:2 v/v Rf=0.63
UV (CH3OH) λmax, 230, 280, 292, 335 nm 1H-NMR δ 8.0 (1 H, d, J=8.6), 7.7 (2 H, d, J=8.6), 7.4 (1 H, dd, J=8.6), 7.3 (1 H, dd, J=8.6), 7.1 (1 H, d, J=8.4)
EI-MS: m/z 270 (M)+
SYNTHESIS EXAMPLE 5
Synthesis of 2-methyl-4-iodo-5-aminophenol
5-Amino-o-cresol (1.23 g, 0.01 mol) was iodinated in water (25 ml) with KIO3 (0.33 eq) and Kl (0.67 eq) essentially as described in Synthesis Example 4 to give sufficiently pure 2-methyl-4-iodo-5-aminophenol.
TLC: chloroform-methanol 9:1 v/v Rf=0.43 UV (CH3OH) λmax, 210, 296 nm 1H-NMR δ 7.2 (1 H, s), 6.3 (1 H, s), 2.1 (3H, s)
SYNTHESIS EXAMPLE 6 Synthesis of 5-iodo-6-hydroxyquinoline
6-Hydroxyquinoline (0.01 mol) in water (25 ml) was iodinated by a procedure essentially similar to that used for iodination of naphthol in Synthesis Example 4 to give eventually pure 5-iodo-6-hydroxyquinoline.
TLC: chloroform-methanol 95:5 v/v Rf=0.27
UV (CH3OH) λmax, 242, 292, 336 nm 1H-NMR δ 8.6 (1 H, d bd, J=4), 8.4 (1 H, d, J=8.0), 7.8 (1 H, d, J=9), 7.5 (1 H, dd, J=8.0, J=4), 7.4 (1 H, d, J=9)
SYNTHESIS EXAMPLE 7 Synthesis of 2,4-diiodo-5-aminophenol
m-Aminophenol (500 mg, 4.6 mmol) in water (25 ml) was treated with acetic acid until most of the compound is solubilized (pH about 3-4). 4.6 Mmol of solid iodine are then added portionwise within 90 min, and the stirring is left for an additional 30 min. The solid which separates is collected and washed until it becomes negative to the starch iodine test. The material thus obtained consisted of practically pure 2,4-diiodo-5-aminophenol.
TLC: chloroform-methanol 9:1 v/v Rf=0.89 UV (CH3OH) λmax, 217, 303 nm
1H-NMR δ 7.71 (1 H, s), 6.37 (1 H, s) EI-MS: m/z 361 (M)+
Hair coloring compositions and systems of this invention can contain the iodo-containing organic couplers of this invention as the sole coupler or can also contain other couplers in combination with primary intermediates.
For hair coloring compositions of this invention, there may be used one or more suitable primary intermediates in combination with the novel couplers of this invention. Suitable primary intermediates include, for example,
p-phenylenediamine derivatives such as: 2-methyl-p- phenylenediamine, p-phenylenediamine, 2-chIoro-p-phenylenediamine, N- phenyl-p-phenylenediamine, N-(2-methoxyethyl)-p-phenylenediamine, N,N- bis(2-hydroxyethyl)-p-phenylenediamine, 2-hydroxymethyl-p- phenylenediamine, 2-(1-hydroxyethyl)-p-phenylenediamine, 2-(2- hydroxyethyl)-p-phenylenediamine, 4,4'diamino-diphenylamine, 2,6-dimethyl- p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(2-hydroxypropyl)-p- phenylenediamine, 2-propyl-p-phenylenediamine, 1 ,3-bis[(N-hydroxyethyl)-N- (4-aminophenyl)amino]-2-propanol, 2-methyl-4-dimethylamino-aniline, 2- methoxy-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2-(1 ,2- dihydroxyethyl)-p-phenylenediamine and 2-thiophen-2-yl-benzene-1 ,4- diamine;
p-aminophenol derivatives such as: p-aminophenol, p- methylaminophenol, 3-methyl-4-aminophenol, 2-hydroxymethyl-4- aminophenol, 2-methyl-4-aminophenol, 2-(2'-hydroxyethylaminomethyl)-4- aminophenol, 2-methoxymethyl-4-aminophenol, 5-aminosalicylic acid and 1- (5-amino-2-hydroxyphenyl)-ethane-1 ,2-diol;
o-aminophenol derivatives such as: o-aminophenol, 2,4- diaminophenol, 5-methyl-2-aminophenol, 6-methyl-2-aminophenol, 2- ethylamino-p-cresol and 2-amino-5-acetaminophenol and 4-methyl-2- aminophenol; and
heterocyclic derivatives such as: 2,4,5,6-tetraaminopyrimidine,
4,5-diamino-1 -methylpyrazole, 2-dimethylamino-5-aminopyridine, 1 -(2- hydroxyethyl)-4,5-diaminopyrazole, 4-hydroxy-2,5,6-triaminopyrimidine, 2-(2- hydroxyethylamino)-6-methoxy-3-aminopyridine and 3-amino-2-methylamino- 6-methoxypyridine.
The primary intermediates can be employed in the form of a free base or in the form of an acid additive salt thereof, such as, for example, as a hydrochloride, a hydrobromide, a sulfate or the like.
Suitable optional additional couplers include, for example, phenols, resorcinol and naphthol derivatives such as: 1 ,7- dihydroxynaphthalene, resorcinol, 4-chlororesorcinol, 1 -naphthol, 2-methyI-1- naphthol, 1-acetoxy-2-methylnaphthalene, 1 ,5-dihydroxynaphthalene, 2,7- dihydroxynaphthalene, hydroquinone, 2-methylresorcinol, 1-hydroxy-6- aminonaphthalene-3-sulfonic acid, 2-isopropyl-5-methylphenol, 1 ,5-dihydroxy- 1 ,2,3,4-tetrahydronaphthalene, 2-chlororesorcinol, 2,3-dihydroxy-1 ,4- naphthoquinone and 1-naphthol-4-sulfonic acid, 1 ,2,3-trihydroxybenzene;
m-phenylenediamines such as: m-phenylenediamine, 2,4- diamino-phenoxyethanol, N,N-bis(2-hydroxyethyl)-m-phenylenediamine, 2,6- diaminotoluene, 2-N,N-bis(hydroxyethyl)-2,4-diaminophenetole, 1 ,3-bis(2,4- diaminophenoxy)propane, 1 -hydroxyethyl-2,4-diaminobenzene, 2-amino-4-(2- hydroxyethylamino)anisole, 4-(2-aminoethoxy)-1 ,3-diaminobenzene, 2,4- diaminophenoxyacetic acid, 4,6-bis(2-hydroxyethoxy)-m-phenylenediamine, 2,4-diamino-5-methylphenetole, 2,4-diamino-5-hydroxyethoxy-toluene, 2,4- dimethoxy-1 ,3-diaminobenzene and 2,6-bis(2-hydroxyethylamino)-toluene, 3- (2,4-diaminophenoxy)-1-propanol;
m-aminophenols such as: m-aminophenol, 2-hydroxy-4- (carbamoyl-methylamino)toluene, m-carbamoylmethylaminophenol, 6- hydroxybenzomorpholine, 2-hydroxy-4-aminotoluene, 2-hydroxy-4-(2- hydroxyethylamino)toluene, 4,6-dichIoro-m-amino-phenol, 2-methyl-m- aminophenol, 2-chloro-6-methyl-m-aminophenol, 2-(2-hydroxyethoxy)-5- aminophenol, 2-chloro-5-trifluoroethylaminophenol, 4-chloro-6-methyl-m- aminophenol, N-cyclopentyl-3-aminophenol, N-hydroxyethyl-4-methoxy-6- methyl-m-aminophenol and 5-amino-4-methoxy-2-methylphenol; and
heterocyclic derivatives such as: 1-phenyl-3-methyl-5- pyrazolone, 6-methoxy-8-aminoquinoline, 2,6-dihydroxy-4-methylpyridine, 5- hydroxy-1 ,4-benzodioxane, 3,4-methylenedioxyphenol, 4-(2- hydroxyethylamino)-1 ,2-methylenedioxybenzene, 2,6-dihydroxy-3,4- dimethylpyridine, 5-chloro-2,3-dihydroxypyridine, 3,5-diamino-2,6- dimethoxypyridine, 3,4-methylene-dioxyaniline, 2,6-bis(2-hydroxyethoxy)-3,5- diaminopyridine, 4-hydroxyindole, 3-amino-5-hydroxy-2,6-dimethoxypyridine, 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 7-hydroxyindole, 5-hydroxyindole, 2-bromo-4,5-methylenedioxyphenol, 6-hydroxyindole, 2- amino-3-hydroxypyridine, 2,6-diaminopyridine, 5-(3,5-diamino-2-pyridyloxy)- 1 ,3-dihydroxypentane, 3-(3,5-diamino-2-pyridyloxy)-2-hydroxypropanol and isatin.
Preferred primary intermediates include:
p-phenylenediamine derivatives such as: 2-methyl-p- phenylenediamine, p-phenylenediamine, N-(2-methoxyethyl)-p- phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(1- hydroxyethyl)-p-phenylenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, and 2-(1 ,2-dihydroxyethyl)-p-phenylenediamine;
p-aminophenol derivatives such as: p-aminophenol, p- methylaminophenol, 3-methyl-4-aminophenol, 2-methoxymethyl-4- aminophenol and 1-(5-amino-2-hydroxyphenyI)-ethane-1 ,2-diol;
o-aminophenol derivatives such as: o-aminophenol, 2- ethylamino-p-cresol, 5-methyl-2-aminophenol, 6-methyl-2-aminophenol and 2-amino-5-acetaminophenol, 4-methyl-2-aminophenol; and
heterocyclic derivatives such as: 2,4,5,6-tetraaminopyrimidine
4,5-diamino-1 -methylpyrazole, 1 -(2-hydroxyethyl)-4,5-diaminopyrazole, and 2-dimethylamino-5-aminopyridine.
Preferred optional additional couplers include:
phenols, resorcinol and naphthol derivatives such as: 2-methyl- 1 -naphthol, 1-acetoxy-2-methylnaphthalene, 1 ,7-dihydroxynaphthalene, resorcinol, 4-chlororesorcinol, 1-naphthol, 1 ,5-dihydroxynaphthalene, 2,7- dihydroxynaphthalene, hydroquinone, 2-methylresorcinol and 2-isopropyl-5- methylphenol;
m-phenylenediamines such as: m-phenylenediamine, 2,4- diamino-phenoxyethanol, 1 ,3-bis(2,4-diaminophenoxy)propane, 2-amino-4-(2- hydroxyethyIamino)anisole and 4,6-bis(2-hydroxyethoxy)-m- phenylenediamine, 3-(2,4-diaminophenoxy)-1 -propanol;
m-aminophenols such as: m-aminophenol, 6- hydroxybenzomorpholine, 2-hydroxy-4-aminotoluene, 2-hydroxy-4-(2- hydroxyethylamino)toluene and 2-methyl-m-aminophenol; and
heterocyclic derivatives such as: 1 -phenyl-3-methyl-5- pyrazolone, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 4- hydroxyindole, 5,6-dihydroxyindole, 7-hydroxyindole, 5-hydroxyindole, 6- hydroxyindole, isatin, 2,6-diaminopyridine and 2-amino-3-hydroxypyridine.
Most preferred primary intermediates include:
p-phenylenediamine derivatives such as: 2-methyl-p- phenylenediamine, p-phenylenediamine, N,N-bis(2-hydroxyethyl)-p- phenylenediamine, 2-(1-hydroxyethyl)-p-phenylenediamine and 2-(2- hydroxyethyl)-p-phenylenediamine;
p-aminophenol derivatives such as: p-aminophenol, p- methylaminophenol, 3-methyl-4-aminophenol and 1-(5-amino-2- hydroxyphenyl)-ethane-1 ,2-diol;
o-amino derivatives such as: o-aminophenol, 2-ethylamino-p- cresol, 5-methyl-2-aminophenol, 6-methyl-2-aminophenol and 2-amino-5- acetaminophenol; and heterocyclic derivatives such as: 2,4,5,6-tetraaminopyrimidine and 1 -(2-hydroxyethyl)-4,5-diaminopyrazole.
Most preferred optional additional couplers include:
phenols, resorcinol and naphthol derivatives such as: 2-methyl- 1 -naphthol, 1-acetoxy-2-methylnaphthalene, resorcinol, 4-chlororesorcinol, 1- naphthol and 2-methylresorcinol;
m-phenylenediamines such as: 2,4-diaminophenoxyethanol, 2- amino-4-(2-hydroxyethyIamino)anisole and 4,6-bis(2-hydroxyethoxy)-m- phenylenediamine and 3-(2,4-diaminophenoxy)-1-propanol;
m-aminophenols such as: m-aminophenol, 6- hydroxybenzomorpholine, 2-hydroxy-4-aminotoluene, 2-hydroxy-4-(2- hydroxyethylamino)toluene and 2-methyl-m-aminophenol; and
heterocyclic derivatives such as: 1 -phenyl-3-methyl-5- pyrazolone, 2-amino-3-hydroxypyridine and 6-hydroxyindole.
The hair coloring compositions and systems of this invention will contain the iodo-containing organic couplers of this invention, alone or in combination with other couplers, in an effective coloring amount, generally in an amount of from about 0.01 to about 2.5 weight percent. Other couplers, when present will be present in an amount up to about 2.5 weight percent. The primary intermediate(s) will generally be present in an amount of from about 0.01 to about 3.5 weight percent. The molar ratio of primary intermediate to coupler will generally range from about 5:1 to about 1 :5 and be employed in any suitable carrier or vehicle, generally an aqueous or hydroalcoholic solution, preferably an aqueous solution. The carrier or vehicle will generally comprise up to about 40 weight percent. The hair coloring compositions and systems of this invention may contain one or more cationic, anionic or amphoteric surface active agents, perfumes, antioxidants, sequestering agents, thickening agents, alkalizing or acidifying agents, and other dyeing agents.
Any suitable oxidizing agent, particularly a peroxide providing agent can be employed in the coloring compositions of this invention, preferably hydrogen peroxide (H2O2) or precursors therefor.
The iodo-containing organic coupler may be applied to hair in a pretreatment step prior to oxidative dyeing or may be present in a dyeing formulation. In the latter case, a composition of primary intermediate(s) and iodine-containing coupler(s) is generally prepared just immediately prior to the time of application to the hair since some of the iodo-containing organic coupler compounds are relatively unstable at the alkaline pH of a typical hair dye formulation. Then an oxidizing agent, such as H2O2, is admixed therewith until an essentially homogenous composition is obtained, which resulting formulation is applied to the hair to be dyed and permitted to remain in contact with the hair for a dyeing effective amount of time, generally for a period of from about 2 to 45, preferably about 2 to 30, minutes, after which the hair is rinsed, shampooed and dried.
In a further aspect of this invention of the iodo-containing coupler of this invention may first be applied to hair followed by subsequent application to the hair of an oxidant and at least one primary intermediate and optionally one or more other couplers in order to oxidatively dye hair.
The usefulness of the iodo-containing organic coupler compounds of this invention is illustrated and exemplified by, but not limited by, the following examples of the use of such iodo-containing organic coupler formulations and systems to dye untreated Piedmont hair. Examples 1 to 23
The following compositions, shown in Table 1 , were used for dyeing the Piedmont hair. The dyeing solution comprised 0.042 mmole primary intermediate and 0.042 mmole coupler in 12 g of a typical dye base (concentration after mixing with oxidant). The typical dye base comprised an alkylethersulfate, an alkanol, 25% ammonia solution, an organic acid, ethylenediaminetetraacetic acid and water. The dyeing solution was mixed with 2 g of 3% hydrogen peroxide. The resulting dyeing formulation was applied to the hair and permitted to remain in contact with the hair for 10 or 20 minutes as indicated in Table 1. The dyed hair was then rinsed with water, shampooed and rinsed again with water and dried with a hair dryer. After dyeing coloration results were measured using a Minolta spectrophotometer Chroma Meter 3700d reflectometer. The Minolta Chroma Meter 3700d spectrophotometer uses reflected light from a surface and gives results in terms of the CIE (International Commission on Illumination) tristimulus values. These values are subsequently transformed mathematically into the L* a* b* color space, wherein the magnitude of changes in hue and intensity of color correspond closely with those perceived by the human eye.
L*, being achromatic, ranges from black (L*=0) to white (L*=100); this term is called "metric lightness" and is a measure of how light or dark a color is, relative to a matching shade of gray. Hue is measured in terms of the chromaticity coordinates a* and b*, where a* indicates redness (a*>0) and b* indicates yellowness (b*>0). The values of a* and b* can be plotted with a* as the x-axis and b* as the y-axis to give quantitative color information: "metric chroma" is the length of a line from the origin (a*=0, b*=0) to the point of a sample reading, while metric hue angle is the angle between the a* axis and the metric chroma line. Metric chroma indicates the strength of a color response (i.e., the extent to which a color differs from its matching shade of gray). Metric hue angle quantifies hue in degrees, with larger values indicating more yellow hues and smaller values indicating more red (or less yellow) hues.
The results of the tests are set forth in the following Table 1. The baseline average values of L*, a* and b* for undyed, untreated Piedmont hair were L* 72.32, a* 2.0, b* 23.2.
Table 1
Figure imgf000018_0001
Example 24
The dyeing performance of an iodo coupler of this invention, namely 2,4-diiodo-resorcinol (Example 24), was compared to the dyeing performance of 4,6-dichloro-resorcinol (Comparative A) at identical dyeing conditions (same primary intermediate; all concentration molar equivalents) under the test conditions as described for Examples 1 to 23. Both couplers can liberate halogen ions during the oxidative dyeing; chloride ion in the case of 2,4-dichloro-resorcinol and iodide ion in the case of 2,4-diiodo-resorcinol. However, it was found that only the latter acts as a catalyst for the oxidation of the primary intermediate. The results of the testing are set forth in Table 2 where it is noted that the color obtained with the iodo-containing coupler is more intense (L* 41.2) than the color obtained with the chloro-containing coupler (L* 56.3).
Table 2
Figure imgf000019_0001
Example 25
The oxidative dyeing of untreated Piedmont hair with organic iodo-containing organic coupler formulations of this invention and the resulting fastness of the hair coloration to shampooing is illustrated in the data presented in following Table 3. For comparison, results for a similar comparative dyeing formulation employing sodium iodide catalyst instead of an organic iodo-containing coupler of this invention is presented in Comparative B. In these examples, Virgin Piedmont hair was dyed with a dyeing formulation comprising N,N-bis(hydroxyethyl)-p-phenylenediamine as the primary intermediate and 2-methyI resorcinol as the coupler. In both examples, a catalyst was also present during dyeing. This catalyst is 2,4,6- triiodo-resorcinol in Example 25 and inorganic sodium iodide in the Comparative B. The dye concentration was 5.72 mmole/100g and the catalyst concentration was 0.67 mmole/100g before mixing 1/1 (by weight) with 3% hydrogen peroxide.
The dyeing formulations were applied to the hair and permitted to remain in contact with the hair for 15 minutes. The dyed hair was then shampooed and rinsed with water and dried.
After drying the dyed hair coloration results were then measured using the Minolta 3700d spectrophotometer as described in Examples 1 to 23. The dyed hair was then shampooed for 60 minutes, rinsed with water and dried and the coloration results measured again to determine the fastness of the coloration to shampooing. The results are set forth in Table 3. The baseline average values of L*, a* and b* for undyed, untreated Piedmont hair were L* 72.32, a* 2.0 and b* 23.2.
Table 3
CIE Color Following CIE Color Following
Example Dyeing 60 min. Shampooing
L* a* b* L* a* b*
25 35.6 6.1 -0.8 37.7 5.6 2.1
Comparative
B 39.7 4.9 2.0 43.2 4.0 4.5
The results demonstrate that the formulations of this invention containing the iodo-containing organic couplers of this invention produce more intense coloration of the untreated Piedmont hair, and the dyed hair which is more colorfast after shampooing than a corresponding formulation containing an inorganic iodide catalyst of the prior art.
With the foregoing description of the invention, those skilled in the art will appreciate that modifications may be made to the invention without departing from the spirit thereof. Therefore, it is not intended that the scope of the invention be limited to the specific embodiments illustrated and described.

Claims

WE CLAIM:
1. A process for coloring hair comprising reacting a primary intermediate with an iodo-containing organic coupler in the presence of an oxidizing agent to produce an oxidative hair dye wherein iodide is liberated and the activity of the oxidizing agent is increased.
2. The process according to Claim 1 wherein the iodo-containing organic coupler comprises a compound of the formula
Figure imgf000022_0001
wherein R1, R2, R3 and R4 are each independently H, I, or a straight or branched chain C1-C4 alkyl group optionally substituted with one or more substituents selected from OH, NH2) NHR8, NH8R9, OR8, phenyl, or a five- or six- membered heterocyclic ring containing one or two nitrogen atoms, an oxygen atom or a sulfur atom with the remainder of the ring being carbon atoms, or R2 and R3 or R3 and R4 together with the carbon atoms to which they are attached may form a benzene ring or a pyridine ring which may optionally be substituted by one or more substituents selected from NH2, NHR6, NR6R7, OH or OR6 with the proviso that from 1 to 3 of the R1, R2, R3 and R4 substituent is I and at least one of the iodo substituents is in the ortho- or para- position to the R substituent;
R is OH, NH2, NHR6 or NR6R7, and where R2 and R3 or R3 and R4 form a benzene or pyridine ring R can be H. R6 and R7 independently each being a branched or straight chain C1-C4 alkyl group optionally substituted with one or more substituents selected from OH, NH2, NHR8, NR8R9, OR8, phenyl, or a five- or six-membered heterocyclic ring containing one or two nitrogen atoms, an oxygen atom or a sulfur atom with the remainder of the ring being carbon atoms; and
R8 and R9 are each independently a straight or branched chain C1-C4 alkyl group, optionally substituted with one or more substituents selected from OH, OCH3 and NH2.
3. The process according to Claim 1 wherein the primary intermediate is selected from the group consisting of 2-methyl-p-phenyIenediamine, p- phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(1 - hydroxyethyl)-p-phenylene-diamine, 2-(2-hydroxyethyl)-p- phenylenediamine, p-aminophenol, p-methylaminophenol, 3-methyl-4- aminophenol, 1-(5-amino-2-hydroxyphenyl)-ethane-1 ,2-diol, o- aminophenol, 2-ethylamino-p-cresol, 5-methyl-2-aminophenol, 6- methyl-2-aminophenol, 2-amino-5-acetaminophenol, 2,4,5,6- tetraamino-pyrimidine, 1 -(2-hydroxyethyl)-4,5-diaminopyrazole, 5,6- dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.
4. The process according to Claim 2 wherein the coupler is selected from the group consisting of 2-iodoresorcinol, 2,4-diiodoresorcinol, 2-methyl- 4-iodoresorcinol, 2-methyl-4-iodo-5-aminophenol, 2,4-diiodo-5- aminophenol and 2,4,6-triiodoresorcinol of the formulae
Figure imgf000024_0001
The process according to Claim 2 wherein the primary intermediate is selected from the group consisting of 2-methyl-p-phenylenediamine, p- phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(1- hydroxyethyl)-p-phenylene-diamine, 2-(2-hydroxyethyl)-p- phenylenediamine, p-aminophenol, p-methyl-aminophenol, 3-methyl-4- aminophenol, 1-(5-amino-2-hydroxyphenyl)-ethane-1 ,2-diol, o- aminophenol, 2-ethylamino-p-cresol, 5-methyl-2-aminophenol, 6- methyl-2-aminophenol, 2-amino-5-acetaminophenol, 2,4,5,6- tetraaminopyrimidine, 1 -(2-hydroxyethyl)-4,5-diaminopyrazole, 5,6- dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.
The process according to Claim 2 wherein Ri to R5 are each independently selected from the group consisting of I, OH, NH2, and CH3 or where Ri and R2 together with the carbon atoms to which they are attached form a benzene or pyridyl ring.
The process according to Claim 3 wherein the intermediate is selected from the group consisting of 2-methyl-p-phenylenediamine, p- phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(1- hydroxyethyl)-p-phenylenediamine, 2-(2-hydroxyethyl)-p- phenylenediamine, p-aminophenol, p-methylaminophenol, 3-methyl-4- aminophenol, 1-(5-amino-2-hydroxyphenyl)-ethane-1 ,2-diol, o- aminophenol, 2-ethylamino-p-cresol, 5-methyl-2-aminophenol, 6- methyl-2-aminophenol, 2-amino-5-acetaminophenol, 2,4,5,6- tetraaminopyrimidine, 1 -(2-hydroxyethyl)-4,5-diaminopyrazole, 5,6- dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.
8. The process according to Claim 4 wherein the coupler is selected from the group consisting of 2-iodoresorcinol, 2,4-diiodoresorcinol and 2- methyl-4-iodoresorcinol.
9. The process according to Claim 4 wherein the primary intermediate is selected from the group consisting of 2-methyl-p-phenylenediamine, p- phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(1 - hydroxyethyl)-p-phenylene-diamine, 2-(2-hydroxyethyl)-p- phenylenediamine, p-aminophenol, p-methyl-aminophenol, 3-methyl-4- aminophenol, 1-(5-amino-2-hydroxyphenyl)-ethane-1 ,2-diol, o- aminophenol, 2-ethylamino-p-cresol, 5-methyI-2-aminophenol, 6- methyl-2-aminophenol, 2-amino-5-acetaminophenol, 2,4,5,6- tetraaminopyrimidine, 1 -(2-hydroxyethyl)-4,5-diaminopyrazoIe, 5,6- dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.
10. The process according to Claim 5 wherein the primary intermediate is selected from the group consisting of 2-methyl-p-phenylenediamine, p- phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(1 - hydroxyethyl)-p-phenylene-diamine, 2-(2-hydroxyethyl)-p- phenylenediamine, p-aminophenol, p-methyl-aminophenol, 3-methyl-4- aminophenol, 1-(5-amino-2-hydroxyphenyl)-ethane-1 ,2-diol, o- aminophenol, 2-ethylamino-p-cresol, 5-methyl-2-aminophenol, 6- methyl-2-aminophenol, 2-amino-5-acetaminophenol, 2,4,5,6- tetraaminopyrimidine, 1 -(2-hydroxyethyl)-4,5-diaminopyrazole, 5,6- dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.
11. A hair coloring composition for dyeing human hair comprising, in a suitable carrier or vehicle, a composition comprising a hair-dyeing effective amount of:
(a) a primary intermediate,
(b) an iodo-containing organic coupler, and
(c) an oxidizing agent.
12. The composition according to Claim 11 wherein the iodo-containing organic coupler comprises a compound of the formula
Figure imgf000026_0001
wherein R1, R2, R3 and R4 are each independently H, I, or a straight or branched chain C1-C4 alkyl group optionally substituted with one or more substituents selected from OH, NH2, NHR8, NH8R9, OR8, phenyl, or a five- or six- membered heterocyclic ring containing one or two nitrogen atoms, an oxygen atom or a sulfur atom with the remainder of the ring being carbon atoms, or R2 and R3 or R3 and R4 together with the carbon atoms to which they are attached may form a benzene ring or a pyridine ring which may optionally be substituted by one or more substituents selected from NH2, NHR6, NR6R7, OH or OR6 with the proviso that from 1 to 3 of the R1, R2, R3 and R4 substituent is I and at least one of the iodo substituents is in the ortho- or para- position to the R substituent;
R is OH, NH2, NHR6 or NR6R7, and where R2 and R3 or R3 and R4 form a benzene or pyridine ring R can be H. R6 and R7 independently each being a branched or straight chain C1-C4 alkyl group optionally substituted with one or more substituents selected from OH, NH2, NHR8, NR8R9, OR8, phenyl, or a five- or six-membered heterocyclic ring containing one or two nitrogen atoms, an oxygen atom or a sulfur atom with the remainder of the ring being carbon atoms; and
R8 and R9 are each independently a straight or branched chain C1-C4 alkyl group, optionally substituted with one or more substituents selected from OH, OCH3 and NH2.
13. The composition according to Claim 12 wherein the primary intermediate is selected from the group consisting of 2-methyl-p- phenylenediamine, p-phenylenediamine, N,N-bis(2-hydroxyethyl)-p- phenylenediamine, 2-(1-hydroxyethyl)-p-phenylenediamine, 2-(2- hydroxyethyl)-p-phenylenediamine, p-aminophenol, p- methylaminophenol, 3-methyl-4-aminophenol, 1-(5-amino-2- hydroxyphenyl)-ethane-1 ,2-diol, o-aminophenol, 2-ethylamino-p-cresol, 5-methyl-2-aminophenol, 6-methyI-2-aminophenol, 2-amino-5- acetaminophenol, 2,4,5,6-tetraaminopyrimidine, 1 -(2-hydroxyethyl)-4,5- diaminopyrazole, 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.
14. The process according to Claim 13 wherein the coupler is selected from the group consisting of 2-iodoresorcinol, 2,4-diiodoresorcinol, 2- methyl-4-iodoresorcinol, 1-iodo-2-hydroxynaphthol, 2-methyl-4-iodo-5- aminophenol, 5-iodo-6-hydroxyquinoline, 2,4-diiodo-5-aminophenol and 2,4,6-triiodoresorcinol of the formulae
Figure imgf000028_0001
15. The process according to Claim 13 wherein the primary intermediate is selected from the group consisting of 2-methyl-p-phenylenediamine, p- phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(1 - hydroxyethyl)-p-phenylene-diamine, 2-(2-hydroxyethyl)-p- phenylenediamine, p-aminophenol, p-methyl-aminophenol, 3-methyl-4- aminophenol, 1-(5-amino-2-hydroxyphenyl)-ethane-1 ,2-diol, o- aminophenol, 2-ethylamino-p-cresol, 5-methyl-2-aminophenol, 6- methyl-2-aminophenol, 2-amino-5-acetaminophenol, 2,4,5,6- tetraaminopyrimidine, 1 -(2-hydroxyethyl)-4,5-diaminopyrazoIe, 5,6- dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.
16. The process according to Claim 13 wherein Ri to R5 are each independently selected from the group consisting of I, OH, NH2, and CH3 or where Ri and R2 together with the carbon atoms to which they are attached form a benzene or pyridyl ring.
17. The process according to Claim 14 wherein the intermediate is selected from the group consisting of 2-methyl-p-phenylenediamine, p- phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(1 - hydroxyethyl)-p-phenylenediamine, 2-(2-hydroxyethyl)-p- phenylenediamine, p-aminophenol, p-methylaminophenol, 3-methyl-4- aminophenol, 1-(5-amino-2-hydroxyphenyl)-ethane-1 ,2-diol, o- aminophenol, 2-ethylamino-p-cresol, 5-methyI-2-aminophenol, 6- methyl-2-aminophenol, 2-amino-5-acetaminophenol, 2,4,5,6- tetraaminopyrimidine, 1 -(2-hydroxyethyl)-4,5-diaminopyrazole, 5,6- dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.
18. The process according to Claim 15 wherein the coupler is selected from the group consisting of 2-iodoresorcinol, 2,4-diiodoresorcinol and 2-methyl-4-iodoresorcinol.
19. The process according to Claim 15 wherein the primary intermediate is selected from the group consisting of 2-methyl-p-phenylenediamine, p- phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(1- hydroxyethyl)-p-phenylene-diamine, 2-(2-hydroxyethyl)-p- phenylenediamine, p-aminophenol, p-methyl-aminophenol, 3-methyl-4- aminophenol, 1-(5-amino-2-hydroxyphenyl)-ethane-1 ,2-diol, o- aminophenol, 2-ethylamino-p-cresol, 5-methyl-2-aminophenol, 6- methyl-2-aminophenol, 2-amino-5-acetaminophenol, 2,4,5,6- tetraaminopyrimidine, 1-(2-hydroxyethyl)-4,5-diaminopyrazole, 5,6- dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.
20. The process according to Claim 16 wherein the primary intermediate is selected from the group consisting of 2-methyl-p-phenylenediamine, p- phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(1- hydroxyethyl)-p-phenylene-diamine, 2-(2-hydroxyethyl)-p- phenylenediamine, p-aminophenol, p-methyl-aminophenol, 3-methyl-4- aminophenol, 1-(5-amino-2-hydroxyphenyl)-ethane-1 ,2-diol, o- aminophenol, 2-ethylamino-p-cresol, 5-methyl-2-aminophenol, 6- methyl-2-aminophenol, 2-amino-5-acetaminophenol, 2,4,5,6- tetraaminopyrimidine, 1 -(2-hydroxyethyl)-4,5-diaminopyrazole, 5,6- dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.
21. An improved process for the oxidative coloration of hair comprising reacting a primary intermediate with a coupler in the presence of an oxidizing agent, the improvement comprising an iodo-containing organic coupler wherein iodide is liberated and the activity of the oxidizing agent is increased.
22. A process for the oxidative coloration of hair comprising applying an iodo-containing coupler to the hair followed by applying an oxidant, at least one primary intermediate and optionally one or more other couplers to the hair.
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