USRE30199E - Oxidation hair dyes based upon tetraaminopyrimidine developers - Google Patents
Oxidation hair dyes based upon tetraaminopyrimidine developers Download PDFInfo
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- USRE30199E USRE30199E US05/953,688 US95368878A USRE30199E US RE30199 E USRE30199 E US RE30199E US 95368878 A US95368878 A US 95368878A US RE30199 E USRE30199 E US RE30199E
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- pyrimidine
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- amino
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/4953—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil
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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
Definitions
- oxidation dyestuffs Of great importance for the dyeing of hair are the so-called oxidation dyestuffs because of their intensive colors and very good fastness. These dyestuffs are formed by the oxidative coupling of a developer component with a coupling component.
- the developers customarily used are nitrogenous bases, such as p-phenylenediamine derivatives, diaminopyridines, 4-aminopyrazolone derivatives or heterocyclic hydrazones.
- Useful as so-called coupling components are m-phenylenediamine derivatives, phenols, naphthols, resorcinol derivatives and pyrazolones.
- An object of the invention is to provide usable oxidation hair dyes containing suitable components which optimally satisfy the above requirements.
- Another object of the present invention is to provide an oxidation dyestuff combination of a coupling component and a developer component, which is based on tetraaminopyrimidines as the developer component.
- the present invention provides a composition and process for dyeing hair based upon an oxidation dyestuff combination of a coupling component and a developer component with tetraaminopyrimidines being the developer component, as well as novel tetraaminopyrimidines.
- the present invention is directed to an aqueous preparation for the dyeing of hair consisting essentially of (1) from 0.2% to 5% by weight of an oxidation dyestuff combination of a developer component, and a coupling component in substantially equimolar amounts, said developer component consisting essentially of (A) a tetraaminopyrimidine of the formula ##STR2## wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each selected from the group consisting of hydrogen, phenyl, alkyl having 1 to 4 carbon atoms, phenylalkyl having 7 to 10 atoms, phenylalkenyl having 7 to 10 carbon atoms,
- n is an integer from 1 to 4
- X is selected from the group consisting of hydroxyl, halogen and NR 7 R 8 -- in which R 7 and R 8 are each hydrogen or alkyl having 1 to 4 carbon atoms, and together with the nitrogen atom R 7 and R 8 from a member selected from the group consisting of a 5 to 6 membered heterocyclic ring optionally containing an additional nitrogen atom or oxygen atom,
- R 1 and R 2 , or R 3 and R 4 , or R 5 and R 6 together with the nitrogen atom form a five to six membered heterocyclic ring optionally containing another nitrogen or oxygen atom in the ring and (B) a water-soluble acid addition salt of (A); (2) from 0% to 5% by weight of a direct dyestuff; (3) from 0% to 30% by weight of a surfactant; (4) from 0% to 25% by weight of thickeners; and (5) the balance up to 100% by weight of water.
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, butyl, phenyl, benzyl and benzylidene, or --(CH 2 ) n --X
- R 1 and R 2 , or R 3 and R 4 , or R 5 and R 6 , together with the nitrogen atom form a substituent selected from the group consisting of hydroxyl, halogen and --NR 7 R 8 in which R 7 and R 8 are each hydrogen or alkyl having 1 to 4 carbon atoms.
- the compounds according to the invention When the compounds according to the invention are used as developer components, they react with the known couplers generally used in oxidation hair dyestuffs to give very intensive, varying shades which previously heretofore could not be effected with these known couplers and these developers known so far. Thus, the compounds of the invention considerably increase the possibilities for utilizing oxidation hair dyes. Furthermore, the tetraaminopyrimidines according to the invention are distinguished by very good fastness of the dyeings effects with them, by good water-solubility, by good storage stability, and by excellent toxicological as well as dermatological unobjectionableness.
- tetraaminopyrimidines which are to be used as developer components according to the invention can be used either as such or in form of their water-soluble acid addition salts with non-toxic inorganic acids or organic acids, such as for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.
- novel tetraaminopyrimidines are 5-amino-2,4,6-tris(methylamino)-pyrimidine, 2,4,5-triamino-6-(di-n-propylamino)-pyrimidine and 2,4,5-triamino-6-morpholino-pyrimidine, or a water-solution acid addition salt thereof.
- the starting material generally is a 2,4,6-aminopyrimidine, into which the 5-amino group is introduced by nitrosation and subsequent reduction. It is also possible to start from the correspondingly substituted triaminoalkylmercaptopyrimides and to replace the alkylmercapto group with an amino group. The latter method is especially suitable for the introduction of substituted amino groups into the 2-, 4-, or 6-positions of the pyrimidine ring.
- Suitable examples of developer components to be used according to the invention are, for example: 2,4,5,6-tetraamino-pyrimidine, 4,5-diamino-2,6-bis-(methylamino)-pyrimidine,
- the coupling components include 1-phenyl-pyrazol-5-ones, aromatic amines, aromatic alcohols, preferably m-aminophenols, 1,3-diamino-4-nitrobenzenes, 1,4-diamino-2-nitrobenzenes and pyrazolidine-diones.
- Examples of coupling components include 1-phenylpyrazol-5-one derivatives of the formula ##STR3## wherein D represents lower alkyl such as methyl, NH 2 --,--NH--CO--D 1 or --NH--CO--NH--D 1 or NH--CS--NH--D 1 and D 1 denotes a hydrocarbon radical with 1 to 12 carbon atoms or a heterocylic radical, and preferably D 1 is alkyl having 1 to 6 carbon atoms such as methyl, ethyl, isopropyl, n-propyl, n-butyl; phenyl; halopenyl such as p-chlorophenyl; alkylphenyl having from 7 to 12 carbon atoms such as p-methylphenyl, p-ethylphenyl, o-propylphenyl; alkoxyphenyl, having from 7 to 12 carbon atoms such as o-methoxyphenyl p-
- Another coupling component for the hair dyes is based on aromatic amines and/or aromatic alcohols, preferably a compound having the formula
- Ar represents an aromatic nucleus, preferably consisting of naphthylene, hydroxynaphthylene, aminonaphthylene, phenylene, aminophenylene, hydroxyphenylene, toluylene, alkoxyphenylene having from 7 to 10 carbon atoms and quinolylene;
- E represents hydrogen, hydroxyl, or amino, dialkylamino having from 1 to 4 carbon atoms in the alkyls; and
- F represents hydroxyl, amino or dialkylamino having from 1 to 4 carbon atoms in the alkyls.
- Suitable coupling components include aromatic amines and diamines, phenols, naphthols and aminophenols.
- the metacompounds are preferably used in the case of the diamines, aminophenols and phenols.
- diamines those in which the hydrogen atoms of the amino groups are substituted by lower alkyl residues (C 1 -C 4 ) may also be used.
- X is an electrophilic substituent and A 2 is a member selected from the group consisting of hydrogen, alkyl of 1 to 10 carbon atoms, hydroxyalkyl of 1 to 10 carbon atoms; N,N-dialkyl-aminoalkyl of 3 to 18 carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxy and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, hal
- An electrophilic substituents X the radicals containing a carbonyl, such as carboxyl, alkoxycarbonyl, and acyl, or a nitrile, or carbonyl containing radicals further substituted with halogen, the sulfo group and the nitro group, are considered.
- X is preferably a nitrile, acyl, or alkoxycarbonyl group.
- Examples of X include carboxyl, cyano, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo, cycloalkylcarbonyl of 6 to 10 carbon atoms, alkoxylcarbonyl of 2 to 10 carbon atoms, cycloalkoxycarbonyl of 6 to 10 carbon atoms, phenylalkoxycarbonyl of 8 to 16 carbon atoms, furoyl, and thenoyl.
- Further coupling components include pyrazolidinediones such as 1-phenyl-3,5-pyrazolidine dione.
- m-aminophenols have the formula ##STR6## wherein Z and Y are each selected from the group consisting of hydrogen, halogen, hydroxyl, amino, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each of the alkyls; R 9 is selected from the group consisting of alkyl having 1 to 10 carbon atoms, phenyl optionally substituted, benzyl, methylenecyanamido, propionamido, ureido, thioureido, oxalyl ester having 1 to 4 carbon atoms in the alcohol moiety, M--(CH 2 ) m --in which
- the coupling component is selected from the group consisting of (a) m-aminophenol of the formula ##STR7## wherein Z and Y are each selected from the group consisting of hydrogen, halogen, hydroxyl, amino, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each of the alkyls;
- R 9 is selected from the group consisting of alkyl having 1 to 10 carbon atoms, hydroxyalkyl having 1 to 10 carbon atoms, phenyl, anilino, hydroxyphenyl, benzyl, methylenecyanamido, propionamido, ureido, thioureido, oxalyl ester of an alcohol having 1 to 4 carbon atoms,
- m is an integer from 1 to 4 and M is selected from the group consisting of hydroxyl, halogen, and --NR 11 R 12 , in which R 11 and R 12 are each hydrogen or alkyl having 1 to 4 carbon atoms and wherein R 10 is selected from the group consisting of hydrogen and R 9 ,
- R 9 and R 10 can together with the nitrogen atom form a member selected from the group consisting of a five- or six-membered heterocyclic ring optionally containing in the ring oxygen or nitrogen and
- a particularly preferred subgenus of said coupling component is
- Z and Y are each selected from the group consisting of hydrogen, methyl, methoxy, amino, chloro, and hydroxyl;
- R 9 is selected from the group consisting of methyl, ethyl, octyl, propyl, hydroxyethyl, phenyl, benzyl, anilino, hydroxyphenyl, ureido, thioureido, methylene-cyanamido, and diethylaminoethyl,
- R 10 is selected from the group consisting of hydrogen and R 9 ,
- R 9 and R 10 together with the nitrogen atom form a member selected from the group consisting of pyrrolidino, morpholino, and piperidino.
- the m-aminophenol derivatives to be employed as blue-coupling component can be used either as such or in form of their water-soluble acid addition salts with inorganic or organic acids, such as for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid and citric acid.
- inorganic or organic acids such as for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid and citric acid.
- Suitable examples of blue-coupling components to be employed according to the invention are as follows:
- novel m-aminophenols are as follows: 3-(diethylamino)-4-methoxy-phenol, 5-(ethylamino)-2-methyl-phenol and 5-(diethylamino)-2-methyl-phenol, as well as water-soluble acid addition salts thereof.
- substantially equimolar quantities of the developer components are used based on the coupling components employed. Although an equimolar amount is preferred, it is possible to use more or less than molar amounts.
- the developer component and the coupling component may be used as pure ingredients or as mixtures. Not only can the developer component consist of mixtures of the tetraaminopyrimidines to be used according to the invention, but the coupling component can also consist of mixtures of the above-named coupling components.
- the hair coloring preparations according to the invention can contain admixtures of other customary developing components and, if necessary, can also contain the customary direct dyestuffs in case the latter are needed for obtaining certain shades. From 0% to 5% direct dyestuffs may be employed.
- the oxidative coupling i.e., the development of the dye can in principle be effected by atmospheric oxygen.
- chemical oxidizing agents are especially hydrogen peroxide or its products of addition to urea, melamine and sodium borate, as well as mixtures of such hydrogen peroxide addition products with potassium peroxydisulfate.
- the tetraaminopyrimidines according to the invention When used as developer components, they have the advantage that the oxidative coupling with atmospheric oxygen readily produces highly satisfactory hair dyeing results. Thus, damage to the hair by the oxidizing agents, otherwise employed for oxidative coupling, can be prevented.
- the hair dyes according to the invention are incorporated into suitable aqueous cosmetic preparations, such as creams, emulsions, gels or simple solutions and immediately before application to the hair, one of the above-named oxidizing agents is added.
- suitable aqueous cosmetic preparations such as creams, emulsions, gels or simple solutions
- coupling and developing components in amounts of from 0.2% to 5% by weight, preferably from 1% to 3% by weight.
- the dye components are mixed with the additional ingredients customarily used in such preparations.
- additional ingredients are, for example, wetting agents or emulsifiers of the anionic or nonionic type, such as alkylbenzenesulfonates, higher fatty alcohol sulfates, higher alkylsulfonates, higher fatty acid alkanolamides, ethoxylated fatty alcohols; thickeners such as methyl cellulose, starch, higher fatty alcohols, paraffin oil and higher fatty acids.
- perfumes and hair-conditioning and grooming agents such as panthothenic acid and cholesterol may be included.
- Effective amounts of the above-named additives are those customarily employed for this purpose. Effective amounts of wetting agents range from 0.5% to 30% by weight, preferably from 1% to 15% by weight; and for thickeners, an effective amount ranges from 0.1% to 25% by weight, preferably from 1% to 15% by weight, based in each case on the total weight of the preparation. As a lower limit for the above additives, a zero percent lower limit is possible, if none of the additive is utilized.
- the hair coloring preparations according to the invention can be applied in a weakly acid medium, a neutral medium or especially, in an alkaline medium, preferably at a pH of 8 to 10, regardless whether a solution, an emulsion, a cream, or a gel is employed.
- These preparations are applied at a temperature which usually ranges from 15° C. to 40° C. and preferably is room temperature.
- the hair coloring preparation is removed from the hair to be dyed, by rinsing. Then the hair is washed with a mild shampoo, and finally is dried.
- the shades obtainable by use of the hair coloring preparations according to the invention have the advantage of providing an extraordinary variations which extend from ash blond to dark brown and green to violet.
- the properties of the hair colors produced are excellent as far as fastness to light and washing are concerned, as well as good resistance to abrasion is concerned; and the hair dyes once fixed can be easily removed by means of reducing agents.
- 2,4,6-tris(methylamino)-pyrimidine was prepared according to Winkelmann, J. Pract. Chem. 115, 292 (1927) and 5.5 gm of this compound were dissolved in 50 ml water. The solution was adjusted to a pH of 4 by means of sodium acetate and was then heated to 80° C.; and a solution of 1.4 gm of NaNO 2 in 5 ml of H 2 O was added to form a red solution. At 60° C., sodium dithionite was added until the solution became yellow. Dilute H 2 SO 4 was added to the yellow solution; and the precipitate was vacuum filtered. The yield was 55%; and the melting point was 215° C.
- 2,4-Diamino-6-chloropyrimidine was prepared according to Roth et al, J. Amer. Chem. Soc. 72, 1914 (1950). To 15 gm of this compound in 130 ml of ethanol, there was added 50 gm of di-n-propylamine, and the mixture was heated in an autoclave at 200° C. for three hours (at an initial gauge pressure of 10 atm. of N 2 ). After the autoclave had cooled and had been opened, the reaction mixture was cooled in an ice-salt bath to precipitate dipropylamine hydrochloride. After filtration, the mother liquor was considerably concentrated to give a residue of about 30 ml, whereby 18 gm or 82.9% of theory of crude raw product precipitated. This product was used as such for subsequent synthesis.
- 2,4-diamino-6-chloropyrimidine was prepared according to Roth et al, J. Amer. Chem. Soc. 72, 1914 (1950).
- Melting Point the compound sintered at 230° slow decomposition from 255° C. on.
- test compound used was 2-dimethylamino-4,5,6-triamino-pyrimidine sulfate which was compared with known compounds, p-phenylenediamine and p-toluylenediamine sulfate. The following results were obtained.
- mice of the CF/W 68-strain were used for the tests of general tolerance.
- the average weight of the test animals was 22 gm.
- the substances to be tested were administered by means of a stomach tube, whereby increasing dosages were used once.
- Ten mice were employed per dose.
- the volume of application was constant and was 0.2 cm 3 /10 gm body weight.
- the animals were observed for a period of eight days. After the test results had been calculated according to the method of Litchfield-Wilcoxon, J. Pharm. Exptl. Ther. 96, 99-108(1949), the following LD 50 -values were obtained.
Abstract
An aqueous hair dye preparation comprising an oxidation dyestuff combination of a coupling component and a developer component consisting of a tetraaminopyrimidine derivative or a water-soluble acid addition salt thereof, as well as a process for dyeing hair by utilizing this oxidation dyestuff combination.
Description
Of great importance for the dyeing of hair are the so-called oxidation dyestuffs because of their intensive colors and very good fastness. These dyestuffs are formed by the oxidative coupling of a developer component with a coupling component. The developers customarily used are nitrogenous bases, such as p-phenylenediamine derivatives, diaminopyridines, 4-aminopyrazolone derivatives or heterocyclic hydrazones. Useful as so-called coupling components are m-phenylenediamine derivatives, phenols, naphthols, resorcinol derivatives and pyrazolones.
Good oxidation dyestuff components for hair dyeing must fulfill all of the following requirements.
They have to be able to develop a sufficient intensity of the desired color shades when oxidatively coupled with the respective developer component or coupling component. Furthermore, they have to possess a capacity for being absorbed by human hair, which capacity ranges from sufficient to very good; and in addition, they should be unobjectionable from toxicological and dermatological viewpoints.
As developers, it is customary to use the class of compounds consisting of substituted or unsubstituted p-phenylenediamines. However, this class of compounds has the disadvantage that sensitivity reactions and subsequently severe allergies are caused in numerous persons. The developers which have been recently proposed for avoiding these dermatological disadvantages are not always fully satisfactory with respect to their technical application.
An object of the invention is to provide usable oxidation hair dyes containing suitable components which optimally satisfy the above requirements.
Another object of the present invention is to provide an oxidation dyestuff combination of a coupling component and a developer component, which is based on tetraaminopyrimidines as the developer component.
These and further objects of the present invention will become apparent as the description thereof proceeds.
The present invention provides a composition and process for dyeing hair based upon an oxidation dyestuff combination of a coupling component and a developer component with tetraaminopyrimidines being the developer component, as well as novel tetraaminopyrimidines. It has now been found that the abovespecified requirements can be fulfilled to an especially significant extent by the use of hair coloring preparations that are based on oxidation dyestuff combinations containing tetraaminopyrimidines of the formula ##STR1## and their inorganic or organic water-soluble acid addition salts as developers, and containing the couplers customarily used in oxidation hair dyes, in which R1 to R6 are each selected from the group consisting of hydrogen, alkyl having 1 to 4 carbon atoms, aryl, substituted aryl and --(CH2)n --X, in which n is an integer from 1 to 4, and X is selected from the group consisting of hydroxy, halogen and --NR7 R8 wherein R7 and R8 are selected from the group consisting of hydrogen and alkyl having 1 to 4 carbon atoms and can form with the nitrogen atom a heterocyclic ring which may contain one additional nitrogen atom or an oxygen atom. In the above formula, R1 to R6 likewise can designate an optionally substituted five-membered or six-membered heterocyclic ring containing one or two nitrogen atoms, or one nitrogen atom and one oxygen atom.
More particularly, the present invention is directed to an aqueous preparation for the dyeing of hair consisting essentially of (1) from 0.2% to 5% by weight of an oxidation dyestuff combination of a developer component, and a coupling component in substantially equimolar amounts, said developer component consisting essentially of (A) a tetraaminopyrimidine of the formula ##STR2## wherein R1, R2, R3, R4, R5 and R6 are each selected from the group consisting of hydrogen, phenyl, alkyl having 1 to 4 carbon atoms, phenylalkyl having 7 to 10 atoms, phenylalkenyl having 7 to 10 carbon atoms,
X--(CH.sub.2).sub.n --
wherein n is an integer from 1 to 4, and X is selected from the group consisting of hydroxyl, halogen and NR7 R8 -- in which R7 and R8 are each hydrogen or alkyl having 1 to 4 carbon atoms, and together with the nitrogen atom R7 and R8 from a member selected from the group consisting of a 5 to 6 membered heterocyclic ring optionally containing an additional nitrogen atom or oxygen atom,
and wherein R1 and R2, or R3 and R4, or R5 and R6, together with the nitrogen atom form a five to six membered heterocyclic ring optionally containing another nitrogen or oxygen atom in the ring and (B) a water-soluble acid addition salt of (A); (2) from 0% to 5% by weight of a direct dyestuff; (3) from 0% to 30% by weight of a surfactant; (4) from 0% to 25% by weight of thickeners; and (5) the balance up to 100% by weight of water.
A particularly preferred subgenus of the above-mentioned developer component is wherein R1, R2, R3, R4, R5 and R6 are each selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, butyl, phenyl, benzyl and benzylidene, or --(CH2)n --X
wherein R1 and R2, or R3 and R4, or R5 and R6, together with the nitrogen atom form a substituent selected from the group consisting of hydroxyl, halogen and --NR7 R8 in which R7 and R8 are each hydrogen or alkyl having 1 to 4 carbon atoms.
When the compounds according to the invention are used as developer components, they react with the known couplers generally used in oxidation hair dyestuffs to give very intensive, varying shades which previously heretofore could not be effected with these known couplers and these developers known so far. Thus, the compounds of the invention considerably increase the possibilities for utilizing oxidation hair dyes. Furthermore, the tetraaminopyrimidines according to the invention are distinguished by very good fastness of the dyeings effects with them, by good water-solubility, by good storage stability, and by excellent toxicological as well as dermatological unobjectionableness.
The tetraaminopyrimidines which are to be used as developer components according to the invention can be used either as such or in form of their water-soluble acid addition salts with non-toxic inorganic acids or organic acids, such as for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.
The preparation of most tetraaminopyrimidines to be used as developer components according to the invention is already known in the literature and can be taken from the monograph by D. J. Brown, in the series "Heterocyclic Compounds", Interscience Publishers, 1962, Vols. I and II, "The Pyrimidines". Only a few of the compounds used are novel substances, the preparation of which is separately described below.
Specific examples of the novel tetraaminopyrimidines according to the invention are 5-amino-2,4,6-tris(methylamino)-pyrimidine, 2,4,5-triamino-6-(di-n-propylamino)-pyrimidine and 2,4,5-triamino-6-morpholino-pyrimidine, or a water-solution acid addition salt thereof.
To synthesize the compounds to be used according to the invention, the starting material generally is a 2,4,6-aminopyrimidine, into which the 5-amino group is introduced by nitrosation and subsequent reduction. It is also possible to start from the correspondingly substituted triaminoalkylmercaptopyrimides and to replace the alkylmercapto group with an amino group. The latter method is especially suitable for the introduction of substituted amino groups into the 2-, 4-, or 6-positions of the pyrimidine ring. Suitable examples of developer components to be used according to the invention are, for example: 2,4,5,6-tetraamino-pyrimidine, 4,5-diamino-2,6-bis-(methylamino)-pyrimidine,
2,5-diamino-4,6-bis-(methylamino)-pyrimidine,
4,5-diamino-6-(butylamino)-2-(dimethylamino)-6-pyrimidine,
2,5-diamino-4-(diethylamino)-6-(methylamino)-pyrimidine,
4,5-diamino-6-(diethylamino)-(2-dimethylamino)-pyrimidine,
4,5-diamino-2-(diethylamino)-6-(methylamino)-pyrimidine,
4,5-diamino-2-(dimethylamino)-6-(ethylamino)-pyrimidine,
4,5-diamino-2-(dimethylamino)-6-(isopropylamino)-pyrimidine,
4,5-diamino-2-(dimethylamino)-6-(methylamino)-pyrimidine,
4,5-diamino-6-(dimethylamino)-2-(methylamino)-pyrimidine,
4,5-diamino-2-(dimethylamino)-6-(propylamino)-pyrimidine,
2,4,5-triamino-6-(dimethylamino)-pyrimidine,
4,5,6-triamino-2-(dimethylamino)-pyrimidine,
2,4,5-triamino-6-(methylamino)-pyrimidine,
4,5,6-triamino-2-(methylamino)-pyrimidine,
4,5-diamino-2-(dimethylamino)-6-piperidino-pyrimidine,
4,5-diamino-6-(methylamino)-2-piperidino-pyrimidine,
2,4,5-triamino-6-piperidino-pyrimidine,
2,4,5-triamino-6-anilino-pyrimidine,
2,4,5-triamino-6-(benzylamino)-pyrimidine,
2,4,5-triamino-6-(benzylideneamino)-pyrimidine,
4,5,6-triamino-2-piperidino-pyrimidine,
5-amino-2,4,6-tris-(methylamino)-pyrimidine,
2,4,5-triamino-6-(di-n-propylamino)-pyridine,
2,4,5-triamino-6-morpholino-pyrimidine,
2,.Badd..[.4.]..Baddend..Iadd.5.Iaddend.,6-triamino-4-(dimethylamino)-pyrimidine
4,5,6-triamino-2-morpholino-pyrimidine,
2,4,5-triamino-6-(β-hydroxyethyl-amino)-pyrimidine,
4,5,6-triamino-2-[(β-aminoethyl)amino]-pyrimidine,
2,5,6-triamino-4-[(β-methylamino)-ethylamino]pyrimidine,
2,5-diamino-4,6[bis-(γ-diethylamino)-propylamino]-pyrimidine,
4,5-diamino-6-[(.[.B.]..Iadd.β.Iaddend.-hydroxyethyl)-amino]-2-(methylamino)-pyrimidine,
5-amino-2,4,6-(triethylamino)-pyrimidine, and
5-amino-6-anilino-2,4-[bis-(β-hydroxyethyl)-amino]-pyrimidine.
Generally speaking, the coupling components include 1-phenyl-pyrazol-5-ones, aromatic amines, aromatic alcohols, preferably m-aminophenols, 1,3-diamino-4-nitrobenzenes, 1,4-diamino-2-nitrobenzenes and pyrazolidine-diones.
Examples of coupling components include 1-phenylpyrazol-5-one derivatives of the formula ##STR3## wherein D represents lower alkyl such as methyl, NH2 --,--NH--CO--D1 or --NH--CO--NH--D1 or NH--CS--NH--D1 and D1 denotes a hydrocarbon radical with 1 to 12 carbon atoms or a heterocylic radical, and preferably D1 is alkyl having 1 to 6 carbon atoms such as methyl, ethyl, isopropyl, n-propyl, n-butyl; phenyl; halopenyl such as p-chlorophenyl; alkylphenyl having from 7 to 12 carbon atoms such as p-methylphenyl, p-ethylphenyl, o-propylphenyl; alkoxyphenyl, having from 7 to 12 carbon atoms such as o-methoxyphenyl p-isopropoxyphenyl; dialkylaminophenyl having 1 to 4 carbon atoms in the alkyl such as p-dimethylaminophenyl; cyclohexyl; alkylcyclohexyl having from 7 to 12 carbon atoms such as methylcyclohexyl; pyridyl; and piperidyl.
Examples of readily available substituted 1-phenyl-3-aminopyrazol-5-ones are the following:
1-phenyl-3-amino-pyrazol-5-one,
1-phenyl-3-methyl-pyrazol-5-one,
1-phenyl-3-acetamido-pyrazol-5-one,
1-phenyl-3-benzamido-pyrazol-5-one,
1-phenyl-3-(3'-cyclohexylureido)-pyrazol-5-one,
1-phenyl-3-(3'-phenylureido)-pyrazol-5-one,
1-phenyl-3-(3'-p-chlorophenylureido)-pyrazol-5-one,
1-phenyl-3-(3'-ethyl-2'-thioureido)-pyrazol-5-one,
1-phenyl-3-(3'-n-butyl-2'-thioureido)-pyrazol-5-one,
1-phenyl-3-(3'-phenyl-2'-thioureido)-pyrazol-5-one,
1-phenyl-3-(3'methylureido)-pyrazol-5-one,
1-phenyl-3-(3'-ethylureido)-pyrazol-5-one,
1-phenyl-3-(3'-n-propylureido-pyrazole-5-one,
1-phenyl-3-(3'-isopropylureido)-pyrazol-5-one, and
1-phenyl-3-(3'-n-butylureido)-pyrazol-5-one.
Another coupling component for the hair dyes is based on aromatic amines and/or aromatic alcohols, preferably a compound having the formula
E--Ar--F
in which Ar represents an aromatic nucleus, preferably consisting of naphthylene, hydroxynaphthylene, aminonaphthylene, phenylene, aminophenylene, hydroxyphenylene, toluylene, alkoxyphenylene having from 7 to 10 carbon atoms and quinolylene; E represents hydrogen, hydroxyl, or amino, dialkylamino having from 1 to 4 carbon atoms in the alkyls; and F represents hydroxyl, amino or dialkylamino having from 1 to 4 carbon atoms in the alkyls.
Suitable coupling components include aromatic amines and diamines, phenols, naphthols and aminophenols. The metacompounds are preferably used in the case of the diamines, aminophenols and phenols. When diamines are used, those in which the hydrogen atoms of the amino groups are substituted by lower alkyl residues (C1 -C4) may also be used.
The following compounds are examples of the said coupling components:
m-cresol,
m-phenylenediamine,
o-cresol,
m-aminophenol,
anisidine,
2,4-diaminoanisole,
m-toluylenediamine,
resorcinol,
pyrogallol,
pyrocathechol,
resorcinol-monoethyl ether
resorcinol-monomethyl ether,
m-aminoresorcinol,
1,5-dihydroxynaphthalene,
1,6-dihydroxynaphthalene,
1,7-dihydroxynaphthalene,
2,7-dihydroxynaphthalene,
1,5-amino- or 1,8-amino-hydroxynaphthalene,
α-naphthol,
7-(dimethylamino)-4-hydroxy-1-methyl-2-quinoline,
8-hydroxyquinoline,
1,8-diaminonaphthalene,
2,6-dimethyl-phenol,
2,5-dimethyl-phenol,
3,4-dimethyl-phenol,
3,5-dimethyl-phenol,
5-amino-2-methyl-phenol,
hydroquinone,
4-aminophenol,
Other coupling compounds include
1,3-diamino-4-nitrobenzene derivatives of the formula ##STR4## and 1,4-diamino-2-nitrobenzene derivatives of the formula ##STR5## in which X is an electrophilic substituent and A2 is a member selected from the group consisting of hydrogen, alkyl of 1 to 10 carbon atoms, hydroxyalkyl of 1 to 10 carbon atoms; N,N-dialkyl-aminoalkyl of 3 to 18 carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxy and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo, and the activated methylene group --CO--CH2 --X, in which X is an electrophilic substituent.
An electrophilic substituents X, the radicals containing a carbonyl, such as carboxyl, alkoxycarbonyl, and acyl, or a nitrile, or carbonyl containing radicals further substituted with halogen, the sulfo group and the nitro group, are considered. X is preferably a nitrile, acyl, or alkoxycarbonyl group.
Examples of X include carboxyl, cyano, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo, cycloalkylcarbonyl of 6 to 10 carbon atoms, alkoxylcarbonyl of 2 to 10 carbon atoms, cycloalkoxycarbonyl of 6 to 10 carbon atoms, phenylalkoxycarbonyl of 8 to 16 carbon atoms, furoyl, and thenoyl.
Suitable examples for compounds of the above described diamino-nitrobenzenes are as follows:
1-amino-3-cyanoacetylamino-4-nitrobenzene,
1-benzoylacetylamino-3-amino-4-nitrobenzene,
1-methylamino-3-cyanoacetylamino-4-nitrobenzene,
1,3-di(cyanoacetylamino)-4-nitrobenzene,
1,3-Di(ω-ethoxycarbonyl-acetylamino)-4-nitrobenzene,
1-Amino-3(ω-ethoxycarbonyl-acetylamino)-4-nitrobenzene,
1-Acetylamino-3-cyanoacetylamino-4-nitrobenzene,
1-Amino-3-acetoacetylamino-4-nitrobenzene,
1-(ρ-Nitro-benzylacetylamino)-3-amino-4-nitrobenzene,
1-Trifluoro-acetoacetylamino-3-amino-4-nitrobenzene,
1-(2-Hydroxy-ethylamino)-3-cyanoacetylamino-4-nitrobenzene,
1-Amino-2-nitro-4-ω-cyanoacetylamino-benzene,
1-Amino-2-nitro-4-ω-benzoyl-acetylamino-benzene,
1,4-Dicyanoacetylamino-2-nitrobenzene,
1-Amino-2-nitro-4-ω-ethoxycarbonyl-acetylamino-benzene,
1,4-Bis-(ω-ethoxycarbonyl-acetylamino)-2-nitrobenzene,
1-Amino-2-nitro-4ω-benzoxycarbonyl-acetylamino-benzene,
1-Amino-2-nitro-4-(ρ-nitrobenzoyl-acetylamino)-benzene,
1-Amino-2-nitro-4-acetoacetylamino-benzene,
1-Amino-2-nitro-4-nitroacetoacetylamino-benzene,
1-Amino-2-nitro-4-trifluoroacetoacetylamino-benzene,
1-Amino-2-nitro-4-ω-butyryl-acetylamino-benzene,
1-Amino-2-nitro-4-ω-(β-Naphthoylacetylamino)-benzene,
1-Amino-2-nitro-4-cyclohexylcarbonyl-acetylamino-benzene,
1-Amino-2-nitro-4-Furoylacetylamino-benzene,
1-Amino-2-nitro-4-Thenoylacetylamino-benzene,
1,4-Bis-(ω-butoxycarbonyl-acetylamino)-benzene,
1,4-Bis-(ω-cyclohexyloxycarbonyl-acetylamino)-benzene.
Further coupling components include pyrazolidinediones such as 1-phenyl-3,5-pyrazolidine dione.
Specific examples of preferred coupling components to be used for the hair dyes according to the invention are as follows:
α-naphthol,
o-cresol,
m-cresol,
2,6-dimethylphenol,
2,5-dimethylphenol
3,4-dimethylphenol,
3,5-dimethylphenol
pyrocatechol,
pyrogallol
1,5-dihydroxy-naphthalene,
1,7-dihydroxy-naphthalene,
5-amino-2-methylphenol,
hydroquinone,
2,4-diaminoanisole,
m-toluylenediamine
4-aminophenol,
resorcinol,
resorcinol monomethyl ether m-phenylenediamine,
3-methyl-1-phenyl-pyrazolone-5,
3-amino-1-phenyl-pyrazolone-5,
1-phenyl-3,5-dione-pyrazolidine,
7-(dimethylamino)-4-hydroxy-1-methyl-quinolone-2,
1-amino-3-(acetacetylamino)-4-nitrobenzene,
1-amino-3-(cyanoacetylamino)-4-nitrobenzene.
In order to obtain shades which are as strong as possible and which correspond to natural hair colors to a large extent, it is very important to use a superior blue dye as shade component. In the preparation of natural looking shades with the aid of coupler components for producing blue dyes, there are, however, difficulties encountered with the customary blue-couplers even when the otherwise very satisfactory tetraaminopyrimidines are used as developers.
It has now been found that this drawback can be corrected when, in combination with the tetraaminopyrimidines employed as developers, the following m-aminophenols are used as the coupling components. These m-aminophenols have the formula ##STR6## wherein Z and Y are each selected from the group consisting of hydrogen, halogen, hydroxyl, amino, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each of the alkyls; R9 is selected from the group consisting of alkyl having 1 to 10 carbon atoms, phenyl optionally substituted, benzyl, methylenecyanamido, propionamido, ureido, thioureido, oxalyl ester having 1 to 4 carbon atoms in the alcohol moiety, M--(CH2)m --in which m is an integer from 1 to 4 and M is selected from the group consisting of hydroxyl, halogen, and--NR11 R12 in which R11 and R12 are each hydrogen or alkyl having 1 to 4 carbon atoms, and in which R9 and R10 can together with the nitrogen atom form an optionally substituted five- or six-membered heterocyclic ring which may contain an additional nitrogen atom or an oxygen atom, and R10 is selected from the group consisting of hydrogen and R9.
More particularly the coupling component is selected from the group consisting of (a) m-aminophenol of the formula ##STR7## wherein Z and Y are each selected from the group consisting of hydrogen, halogen, hydroxyl, amino, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each of the alkyls;
Wherein R9 is selected from the group consisting of alkyl having 1 to 10 carbon atoms, hydroxyalkyl having 1 to 10 carbon atoms, phenyl, anilino, hydroxyphenyl, benzyl, methylenecyanamido, propionamido, ureido, thioureido, oxalyl ester of an alcohol having 1 to 4 carbon atoms,
M--(CH.sub.2).sub.m --
wherein m is an integer from 1 to 4 and M is selected from the group consisting of hydroxyl, halogen, and --NR11 R12, in which R11 and R12 are each hydrogen or alkyl having 1 to 4 carbon atoms and wherein R10 is selected from the group consisting of hydrogen and R9,
wherein R9 and R10 can together with the nitrogen atom form a member selected from the group consisting of a five- or six-membered heterocyclic ring optionally containing in the ring oxygen or nitrogen and
b. a water-soluble acid addition salt of (a).
A particularly preferred subgenus of said coupling component is
wherein Z and Y are each selected from the group consisting of hydrogen, methyl, methoxy, amino, chloro, and hydroxyl;
wherein R9 is selected from the group consisting of methyl, ethyl, octyl, propyl, hydroxyethyl, phenyl, benzyl, anilino, hydroxyphenyl, ureido, thioureido, methylene-cyanamido, and diethylaminoethyl,
wherein R10 is selected from the group consisting of hydrogen and R9,
and wherein R9 and R10 together with the nitrogen atom form a member selected from the group consisting of pyrrolidino, morpholino, and piperidino.
The m-aminophenol derivatives to be employed as blue-coupling component can be used either as such or in form of their water-soluble acid addition salts with inorganic or organic acids, such as for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid and citric acid.
Suitable examples of blue-coupling components to be employed according to the invention are as follows:
3-(dimethylamino)-phenol,
3-(diethylamino)-phenol,
3-(dioctylamino)-phenol,
3-(ethylmethylamino)-phenol,
3-(ethylpropylamino)-phenol,
3-(phenylethylamino)-phenol,
3-(phenyloctylamino)-phenol,
3-(benzylamino)-phenol,
3-(ethylbenzylamino)-phenol,
3-anilinophenol,
3-(methylamino)-phenol,
3-(ethylamino)-phenol,
3-(octylamino)-phenol,
3-(ethylureidoamino)-phenol,
3-ureidophenol,
3-(phenylureidoamino)-phenol,
3-(β-hydroxyethyl amino)-phenol,
3-(N-β-hydroxyethyl-N-methyl-amino)-phenol,
3-(thioureidoamino)-phenol,
N-ethyl-N-(3-hydroxyphenyl)-urea,
3-(methylenecyanamido)-phenol,
3-((2-diethylamino)-ethyl)-amino)-phenol,
3-N-(2-diethylaminoethyl)-N-methyl-aminophenol,
3-pyrrolidinophenol,
3-morpholinophenol,
3-piperidinophenol,
5-(ethylamino)-2-methylphenol,
5-(diethylamino)-2-methylphenol
3-ethylamino)-4-methoxyphenol,
3-diethylamino)-4-methoxyphenol,
2-chloro-5-(dimethylamino)-phenol
3,5-dihydroxy-N,N-dimethylaniline,
2-amino-5-(diethylamino)-phenol,
6-chloro-3-(diethylamino)-5-hydroxy-toluene,
3-anilino-6-chloro-5-hydroxy-toluene,
5-methyl-3-piperidino-phenol, and
4-chloro-3-pyrrolidino-phenol.
The preparation of the m-aminophenol derivatives to be used as blue-coupling components is already known from the literature. See the article of F. Effenberger et al in Chem. Ber. 103, 1456-62, (1970) and British Pat. No. 974,343. The preparation of several novel derivatives which were not found in the literature is separately described below.
Specific examples of novel m-aminophenols are as follows: 3-(diethylamino)-4-methoxy-phenol, 5-(ethylamino)-2-methyl-phenol and 5-(diethylamino)-2-methyl-phenol, as well as water-soluble acid addition salts thereof.
In the hair coloring preparations according to the invention, substantially equimolar quantities of the developer components are used based on the coupling components employed. Although an equimolar amount is preferred, it is possible to use more or less than molar amounts. Furthermore, the developer component and the coupling component may be used as pure ingredients or as mixtures. Not only can the developer component consist of mixtures of the tetraaminopyrimidines to be used according to the invention, but the coupling component can also consist of mixtures of the above-named coupling components.
In addition, the hair coloring preparations according to the invention can contain admixtures of other customary developing components and, if necessary, can also contain the customary direct dyestuffs in case the latter are needed for obtaining certain shades. From 0% to 5% direct dyestuffs may be employed. As in the case of other oxidation hair dyes, the oxidative coupling, i.e., the development of the dye can in principle be effected by atmospheric oxygen. Moreover, it is preferred to use chemical oxidizing agents. Suitable examples are especially hydrogen peroxide or its products of addition to urea, melamine and sodium borate, as well as mixtures of such hydrogen peroxide addition products with potassium peroxydisulfate.
When the tetraaminopyrimidines according to the invention are used as developer components, they have the advantage that the oxidative coupling with atmospheric oxygen readily produces highly satisfactory hair dyeing results. Thus, damage to the hair by the oxidizing agents, otherwise employed for oxidative coupling, can be prevented.
In the situation that a bleaching of the hair is simultaneously desired, then the concurrent use of chemical oxidizing agents is necessary.
For application, the hair dyes according to the invention are incorporated into suitable aqueous cosmetic preparations, such as creams, emulsions, gels or simple solutions and immediately before application to the hair, one of the above-named oxidizing agents is added. These hair dyeing preparations contain coupling and developing components in amounts of from 0.2% to 5% by weight, preferably from 1% to 3% by weight.
For the preparation of creams, emulsions or gels, the dye components are mixed with the additional ingredients customarily used in such preparations. Such additional ingredients are, for example, wetting agents or emulsifiers of the anionic or nonionic type, such as alkylbenzenesulfonates, higher fatty alcohol sulfates, higher alkylsulfonates, higher fatty acid alkanolamides, ethoxylated fatty alcohols; thickeners such as methyl cellulose, starch, higher fatty alcohols, paraffin oil and higher fatty acids. Furthermore, perfumes and hair-conditioning and grooming agents, such as panthothenic acid and cholesterol may be included.
Effective amounts of the above-named additives are those customarily employed for this purpose. Effective amounts of wetting agents range from 0.5% to 30% by weight, preferably from 1% to 15% by weight; and for thickeners, an effective amount ranges from 0.1% to 25% by weight, preferably from 1% to 15% by weight, based in each case on the total weight of the preparation. As a lower limit for the above additives, a zero percent lower limit is possible, if none of the additive is utilized.
The hair coloring preparations according to the invention can be applied in a weakly acid medium, a neutral medium or especially, in an alkaline medium, preferably at a pH of 8 to 10, regardless whether a solution, an emulsion, a cream, or a gel is employed.
These preparations are applied at a temperature which usually ranges from 15° C. to 40° C. and preferably is room temperature.
After the preparation has been allowed to react for about 30 minutes, the hair coloring preparation is removed from the hair to be dyed, by rinsing. Then the hair is washed with a mild shampoo, and finally is dried.
When different developer and coupling components are used, the shades obtainable by use of the hair coloring preparations according to the invention have the advantage of providing an extraordinary variations which extend from ash blond to dark brown and green to violet. The properties of the hair colors produced are excellent as far as fastness to light and washing are concerned, as well as good resistance to abrasion is concerned; and the hair dyes once fixed can be easily removed by means of reducing agents.
The following examples are merely illustrative of the present invention without being deemed limitative in any manner thereof.
First, there are examples for the preparation of some novel tetraminopyrimidines which are utilized according to the invention, but have not been previously described in the literature.
2,4,6-tris(methylamino)-pyrimidine was prepared according to Winkelmann, J. Pract. Chem. 115, 292 (1927) and 5.5 gm of this compound were dissolved in 50 ml water. The solution was adjusted to a pH of 4 by means of sodium acetate and was then heated to 80° C.; and a solution of 1.4 gm of NaNO2 in 5 ml of H2 O was added to form a red solution. At 60° C., sodium dithionite was added until the solution became yellow. Dilute H2 SO4 was added to the yellow solution; and the precipitate was vacuum filtered. The yield was 55%; and the melting point was 215° C.
______________________________________
Elemental Analysis:
% C % H % N
______________________________________
Found: 26.6 6.4 26.6
Calculated: 26.6 8.3 27.7
______________________________________
2,4,5-Triamino-6-(di-n-propylamino)pyrimidine dihydrochloride was prepared stepwise as follows:
1. 2,4-Diamino-6-(di-n-propylamino)-pyrimidine
2,4-Diamino-6-chloropyrimidine was prepared according to Roth et al, J. Amer. Chem. Soc. 72, 1914 (1950). To 15 gm of this compound in 130 ml of ethanol, there was added 50 gm of di-n-propylamine, and the mixture was heated in an autoclave at 200° C. for three hours (at an initial gauge pressure of 10 atm. of N2). After the autoclave had cooled and had been opened, the reaction mixture was cooled in an ice-salt bath to precipitate dipropylamine hydrochloride. After filtration, the mother liquor was considerably concentrated to give a residue of about 30 ml, whereby 18 gm or 82.9% of theory of crude raw product precipitated. This product was used as such for subsequent synthesis.
2. 2,4-Diamino-6-(di-n-propylamino)-5nitrosopyrimidine
18 gm of the crude product 2,4-diamino-6-(di-n-propylamino)-pyrimidine was suspended in 25 ml of water; and glacial acetic acid was added until a pH of 4 was reached. After heating to 50° C. had resulted in solution of the substance, 5.5 gm of sodium nitrite in 10 ml of water were slowly added. After a short time, a raspberry red precipitate was deposited, vacuum filtered, and dried under vacuum at room temperature. The remainder weighed 9.4 gm which was 46% theory; and had a melting point of 206°-208° C.
______________________________________
Elemental Analysis:
% C % H % N
______________________________________
Found: 50.40 7.61 35.27
Calculated: 49.56 7.62 35.50
______________________________________
3. 2,4,5-Triamino-6-(di-n-propylamino)-pyrimidine Dihydrochloride
6.5 gm of 2,4-diamino-6-(di-n-propylamino)-5-nitrosopyrimidine in 150 ml of ethanol with 0.5 gm of catalyst (10% palladium-on-charcoal) were introduced into a pressure-tested hydrogenation vessel to be hydrogenated at room temperature in a catalytic apparatus of the shaker type. After H2 -absorption had terminated, the catalyst was removed by filtration; the solution was acidified with hydrochloric acid, and concentrated. The residue was 5.6 gm which was 78.8% of theory of brown crystals; melting point (decomp.) was 105° C. The mass spectrum showed the molecular mass to be 224 (calcd.: 224).
2,4,5-Triamino-6-morpholino-pyrimidine sulfate was prepared stepwise from the following compounds:
1. 2,4-Diamino-6-morpholinopyrimidine
2,4-diamino-6-chloropyrimidine was prepared according to Roth et al, J. Amer. Chem. Soc. 72, 1914 (1950). To 10 gm of this compound, (0.07 mol), 30 gm of morpholine (30 ml, 0.34 mol) were added; and while stirring, the mixture was heated to 100° C. within one hour. The mixture was kept at this temperature for 21/2 hours. Then, 10 ml of ethanol were added; and the mixture was stored in a refrigerator until morpholine hydrochloride had precipitated. After removal of this salt, the filtrate was concentrated to produce the crude product which was half oily, half crystalline residue. There was 5.9 gm which constituted 43.7% of theory; and this crude product was utilized for subsequent synthesis.
2. 2,4-Diamino-6-morpholine-5-nitroso-pyrimidine
5.9 gm of the crude 2,4-diamino-6-morpholino-pyrimidine (0.03 mol), were dissolved by heating in 25 ml of water; and glacial acetic acid was added until a pH of 4 was reached. Then the solution was heated to 80° C., and a solution of 2 gm of sodium nitrite in 5 ml of water was slowly added. After a short time, the nitroso compound was obtained as a raspberry red precipitate. Concentration and cooling produced a total yield of a 4.1 gm which was 60.3% of theory. The melting point was 231°-233° C.
______________________________________
Elemental Analysis:
% C % H % N
______________________________________
Found: 42.85 5.39 37.48
Calculated: 41.92 4.97 38.22
______________________________________
3. 2,4,5-Triamino-6-morpholino-pyrimidine Sulfate
2.5 gm of 2,4-diamino-6-morpholino-5-nitroso-pyrimidine was suspended in 15 ml of water, and 2 N HCl (5 ml) was added until the substance just dissolved. The mixture was heated to 50° C.; and sodium dithionite (Na2 S2 O4) was added until the violet color solution took on a yellow color. Then, the solution was filtered, cooled, and adjusted to a pH 2 by means of sulfuric acid (1:1). After a short time, the pyrimidine derivative precipitated as pyrimidine sulfate; the yield was 2.6 gm which was 76.4% of theory.
______________________________________
Elemental Analysis
(of the recrystallized compound):
% C % H % N
______________________________________
Found: 31.17 5.23 27.2
Calculated: 29.81 4.98 27.8
Melting Point: the compound sintered at 230°
slow decomposition from 255° C. on.
______________________________________
Melting Point: the compound sintered at 230° slow decomposition from 255° C. on.
The other tetraaminopyrimidines which were used in the following Examples were reported in the literature and were prepared by the synthesis indicated in the monograph of D. J. Brown, "The Pyrimidines" in the series of Heterocyclic Compounds, Interscience Publishers, 1962, Vols. I and II.
Several m-aminophenol derivatives which were used as blue-coupling components in the hair coloring preparations according to the invention are novel and are not found in the literature. Hence, their preparation is described in the following examples.
8.3 gm ethyl bromide were added to a solution of 10.5 gm of 3-amino-4-methoxyphenol in 50 ml of ethanol. The reaction mixture was refluxed for 24 hours. After the solution had cooled, it was diluted with 800 ml of water; and the pH was adjusted to slight alkalinity by the addition of sodium carbonate. The solution was repeatedly extracted with ether, and the combined extracts were dried over anhydrous sodium sulfate. After the precipitate had been filtered off, the residue was concentrated; and the remaining residue as dissolved in 50 ml of ethanol. Then, after 8.7 gm of ethyl bromide had been added, the alkylation and treatment of the product were repeated as described above with the exception that this time, the dried ether extract was only concentrated to a volume of about 300 ml and dry HCl gas was passed into the solution while it was being cooled with ice. The precipitate was vacuum filtered; the residue was dried, dissolved in ethanol, and treated with active charcoal. Addition of ether to the ethanolic solution resulted in the precipitation of the pure product, which had a melting point of 197°-198° C.
______________________________________
Elemental Analysis:
% C % H % N C1
______________________________________
Found: 57.1 7.8 6.03 15.3
Calculated: 56.3 7.8 5.4 14.6
______________________________________
Mass Spectrum: 195 (calcd.: 195).
88.6 gm of ethyl bromide were added to a solution of 50 gm of 5-amino-2-methylphenol in 250 ml of ethanol; and the mixture was refluxed for four hours. After the solution had cooled, it was diluted with 1.2 liters of water and was made weakly alkaline with sodium carbonate. After repeated extraction with ether, the ether extracts were dried and concentrated. The residue was recrystallized from ethanol, and had a melting point of 128° C. to 129° C.
______________________________________
Elemental Analysis:
% C % H % N
______________________________________
Found: 71.5 8.6 9.3
Calculated: 70.79 8.51 9.5
______________________________________
Mass Spectrum: 151 (calcd.: 151)
5 gm of 5-(ethylamino)-2-methylphenol were dissolved in 50 ml of ethanol, then alkylated analogously to the procedure described in Example 4 with 5,2 gm ethyl bromide, and worked up. The hydrochloride had a melting point of 192° C.
______________________________________
Elemental Analysis:
% C % H % N % Cl
______________________________________
Found: 61.3 8.4 6.5 16.5
Calculated: 62.9 8.8 6.8 15.9
______________________________________
Mass Spectrum: 179 (calcd.: 179)
The hair dyes according to the invention were applied in form of an aqueous preparation such as an emulsified cream. The emulsion contained
10 parts by weight of fatty alcohols having 12 to 18 carbon atoms,
10 parts by weight of fatty alcohol sulfate (sodium salt) having 12 to 18 carbon atoms and
75 parts by weight of water.
Into each emulsion, there was incorporated 0.01 mol of the tetraaminopyrimidines and couplers which are listed in the following Table I. Then, the pH-value of the emulsion was adjusted to 9.5 with ammonia, and the emulsion was made up to 100 parts by weight with water. The oxidative coupling was effected by using as an oxidizing agent either atmospheric oxygen, or a 1% hydrogen peroxide solution with the proviso that 10 parts by weight of hydrogen peroxide solution were added to 100 parts by weight of the emulsion. The respective dyeing cream, with or without additional oxidizing agent, was applied to human hair that was 90% gray and that had not been pretreated in a special manner. After the cream had remained on the hair for 30 minutes to complete the dyeing process, the hair was washed with a customary shampoo and then dried. The shades thereby obtained are also listed in the following Table I.
TABLE 1
__________________________________________________________________________
Shade obtained
With
Atmos- with
Example
Developer Coupler pheric O.sub.2
1% H.sub.2 O.sub.2
__________________________________________________________________________
7 2,4,5,6-Tetra-amino-
m-Phenylenediamine
olive olive
pyrimidine
8 2,4,5,6-Tetra-amino-
2,4-Diaminoanisole
dark green
dark green
pyrimidine
9 2,4,5,6-Tetra-amino-
m-diamino toluene
yellowish
yellowish
pyrimidine
brown brown
10 2,4,5,6-Tetra-amino-
m-aminophenol violet violet
pyrimidine brown brown
11 2,4,5,6-Tetra-amino-
Resorcinol strawberry
grayish
pyrimidine red red
12 2,4,5,6-Tetra-amino-
3-Amino-1-phenyl-
brownish
brownish
pyrimidine pyrazolone-5 orange orange
13 2,4,5,6-Tetra-amino-
3-Methyl-1-phenyl-
brownish
brownish
pyrimidine pyrazolone-5 red orange
14 2,4,5,6-Tetra-amino-
Resorcinol golden golden
pyrimidine monomethyl ether
brown brown
15 2,4,5,6-Tetra-amino-
Naphthol yellowish
yellowish
pyrimidine brown brown
16 2,4,5,6-Tetra-amino-
1,5-Dihydroxy-
havanna
havanna
pyrimidine Naphthalene brown brown
17 2,4,5,6-Tetra-amino-
1,7-Dihydroxy-
olive olive
pyrimidine Naphthalene brown brown
18 4-Dimethylamino-
m-Phenylenediamine
yellowish
yellowish
2,5,6-Triamino- brown brown
pyrimidine
19 4-Dimethylamino-
2,4-Diaminoanisole
olive olive
2,5,6-Triamino- yellow yellow
pyrimidine
20 4-Dimethylamino-
m-Diaminotoluene
yellowish
yellowish
2,5,6-Triamino- brown brown
pyrimidine
21 4-Dimethylamino-
m-Aminophenol burgundy
burgundy
2,5,6-Triamino- red red
pyrimidine
22 4-Dimethylamino-
Resorcinol brownish
brownish
2,5,6-Triamino- red red
pyrimidine
23 4-Dimethylamino-
3-Amino-1-Phenyl-
raspberry
raspberry
2,5,6-Triamino-
pyrazolone-5 red red
pyrimidine
24 4-Dimethylamino-
m-Phenylenediamine
olive olive
2,5,6-Triamino- brown brown
pyrimidine
25 2-Dimethylamino-
m-Phenylenediamine
dark dark
4,5,6-triamino- green green
pyrimidine
26 2-Dimethylamino-
2,4-Diaminoanisole
dark dark
4,5,6-triamino- green green
pyrimidine
27 2-Dimethylamino-
m-Diaminotoluene
olive- olive-
4,5,6-triamino- tinged tinged
pyrimidine yellow yellow
28 2-Dimethylamino-
m-Aminophenol grayish
dark
4,5,6-triamino- violet violet
pyrimidine
29 2-Dimethylamino-
Resorcinol reddish
reddish
4,5,6-triamino- violet violet
pyrimidine
30 2-Dimethylamino-
3-Amino-1-phenyl-
brick red
brick red
4,5,6-triamino-
pyrazolone-5
pyrimidine
31 2-Dimethylamino-
3-Methyl-1-phenyl-
lake red
grayish
4,5,6-triamino-
pyrazolone-5 orange
pyrimidine
32 2-Dimethylamino-
Naphthol hair olive
4,5,6-triamino- brown brown
pyrimidine
33 2-Dimethylamino-
3-acetoacetylamino-
yellowish
brass
4,5,6-triaminio-
1-amino-4-nitroben-
brown yellow
pyrimidine zene
34 2-Dimethylamino-
1-Phenyl-3,5-pyra-
brownish
gray red
4,5,6-triamino-
zolidine-dione
orange
pyrimidine
35 2-Dimethylamino-
o-Cresol brownish
ivory
4,5,6-triamino- orange
pyrimidine
36 2-Dimethylamino-
m-Cresol brownish
ivory
4,5,6-triamino- orange
pyrimidine
37 2-Dimethylamino-
2,5-Dimethylphenol
brownish
grayish
4,5,6-triamino- red green
pyrimidine
38 2-Dimethylamino-
3,4-Dimethylphenol
brownish
grayish
4,5,6-triamino- orange green
pyrimidine
39 2-Dimethylamino-
3,5-Dimethylphenol
brownish
grayish
4,5,6-triamino- orange orange
pyrimidine
40 2-Dimethylamino-
1,5-Dihydroxy-
brown brown
4,5,6-triamino-
Naphthalene
pyrimidine
41 2-Dimethylamino-
Pyrogallol chocolate
zinc
4,5,6-triamino- brown gray
pyrimidine
42 2-Dimethylamino-
Pyrocatechol reddish
fallow
4,5,6-triamino- brown
pyrimidine
43 2-Dimethylamino-
7-(Dimethylamino)-4-
grayish
golden
4,5,6-triamino-
hydroxy-1-methyl-2-
orange blond
pyrimidine quinolone
44 2-Dimethylamino-
5-Amino-2-methyl-
brown brown
4,5,6-triamino-
phenol
pyrimidine
45 2-Dimethylamino-
Hydroquinone brownish
golden
4,5,6-triamino- red blond
pyrimidine
46 2-Piperidino-
m-Phenylenediamine
dark dark
4,5,6-triamino- green green
pyrimidine
47 2-Piperidino-
m-Aminophenol dark dark
4,5,6-triamino- violet violet
pyrimidine
48 2-Piperidino-
Resorcinol grayish
grayish
4,5,6-triamino- ruby ruby
pyrimidine
49 2-Piperidino-
2,4-Diaminoanisole
dark dark
4,5,6-triamino- green green
pyrimidine
50 2-Piperidino-
m-Diaminotoluene
brownish
brownish
4,5,6-triamino- orange orange
pyrimidine
51 2-Piperidino-
3-Amino-1-phenyl-
tomato tomato
4,5,6-triamino-
pyrazolone-5- red red
pyrimidine
52 2-Morpholino-
m-Phenylenediamine
olive olive
4,5,6-triamino
pyrimidine
53 2-Morpholino-
m-Aminophenol dark dark
4,5,6-triamino- violet violet
pyrimidine
54 2-Morpholino-
Resorcinol grayish
grayish
4,5,6-triamino- ruby ruby
pyrimidine
55 2-Morpholino-
2,4-Diaminoanisole
dark dark
4,5,6-triamino- green green
pyrimidine
56 2-Morpholino-
m-Diaminotoluene
olive olive
4,5,6-triamino- brown brown
pyrimidine
57 2-Morpholino-
3-Amino-1-phenyl-
brownish
brownish
4,5,6-triamino-
pyrazolone-(5)
red red
pyrimidine
58 2-Methylamino-
m-Phenylenediamine
olive olive
4,5,6-triamino-
pyrimidine
59 2-Methylamino-
m-Aminophenol dark dark
4,5,6-triamino- purple violet
pyrimidine
60 2-Methylamino-
Resorcinol grayish
brownish
4,5,6-triamino- red violet
pyrimidine
61 2-Methylamino-
2,4-Diaminoanisole
dark dark
4,5,6-triamino- green green
pyrimidine
62 2-Methylamino-
m-Diaminotoluene
yellow yellow
4,5,6-triamino-
pyrimidine
63 2-Methylamino-
3-Amino-1-phenyl-
brownish
brownish
4,5,6-triamino-
pyrazolone-5 red red
pyrimidine
64 6-Morpholino-
m-Phenylenediamine
olive olive
2,4,5-triamino- brown brown
pyrimidine
65 6-Morpholino-
2,4-Diaminoanisole
grayish
olive
2,4,5-triamino- green
pyrimidine
66 6-Morpholino-
m-Diaminotoluene
golden brass
2,4,5-triamino- yellow yellow
pyrimidine
67 6-Morpholino-
m-Aminophenol grayish
grayish
2,4,5-triamino- ruby red
pyrimidine
68 6-Morpholino-
Resorcinol brownish
brownish
2,4,5-triamino- red red
pyrimidine
69 6-Morpholino-
3-Amino-1-phenyl-
2,4,5-triamino-
pyrazolone-5 dull red
dull red
pyrimidine
70 6-Piperidino-
m-Phenylenediamine
bamboo grayish
2,4,5-Triamino- yellow yellow
pyrimidine
71 6-Piperidino-
2,4-Diaminoanisole
olive olive
2,4,5-Triamino- brown
pyrimidine
72 6-Piperidino-
m-Aminophenol olive bamboo
2,4,5-Triamino- brown yellow
pyrimidine
73 6-Piperidino-
Resorcinol grayish
ivory
2,4,5-Triamino- red
pyrimidine
74 6-Piperidino-
m-Diaminotoluene
grayish
olive
2,4,5-Triamino- yellow brown
pyrimidine
75 6-Piperidino-
3-Amino-1-phenyl-
chamois
straw
2,4,6-Triamino-
pyrazolone-5 yellow yellow
pyrimidine
76 6-(Di-n-propylamino)-
m-Phenylenediamine
honey olive
2,4,5-triamino- yellow
pyrimidine
77 6-(Di-n-propylamino)-
2,4-Diaminoanisole
olive olive
2,4,5-triamino- green
pyrimidine
78 6-(Di-n-propylamino)-
m-Diaminotoluene
honey honey
2,4,5-triamino- yellow yellow
pyrimidine
79 6-(Di-n-propylamino)-
m-Aminophenol grayish
grayish
2,4,5-triamino- ruby ruby
pyrimidine
80 6-(Di-n-propylamino)-
Resorcinol brownish
brownish
2,4,5-triamino- red red
pyrimidine
81 6-(Di-n-propylamino)-
3-Amino-1-phenyl-
reddish
reddish
2,4,5-triamino-
pyrazolone-5- brown brown
pyrimidine
82 5-Amino-2,4,6-
m-Phenylenediamine
oak brown
olive
tris-(methylamino)-
pyrimidine
83 5-Amino-2,4,6-
2,4-Diaminoanisole
olive beaver
tris-(methylamino)- brown
pyrimidine
84 5-Amino-2,4,6-
m-diaminotoluene
brass olive
tris-(methylamino)- yellow
pyrimidine
85 5-Amino-2,4,6-
m-Aminophenol dark brown
tris-(methylamino)- ruby
pyrimidine
86 5-Amino-2,4,6-
Resorcinol grayish
dull
tris-(methylamino)- red red
pyrimidine
87 5-Amino-2,4,6-
3-Amino-1-phenyl
reddish
light
tris-(methylamino)-
pyrazolone-5 brown brown
pyrimidine
88 2-Dimethylamino-
3-(Diethylamino)-
blue blue
4,5,6-Triamino-
phenol black black
pyrimidine
89 2-Dimethylamino-
3-[(β-Hydroxyethyl)-
blue blue
4,5,6-Triamino-
amino]-phenol black black
pyrimidine
90 2-Dimethylamino-
3-[2-(Diethylamino)-
blue blue
4,5,6-Triamino-
ethyl-amino]-phenol
black black
pyrimidine
91 2-Dimethylamino-
3-Morpholino-phenol
dark dark
4,5,6-Triamino- violet violet
pyrimidine
92 2-Dimethylamino-
3-(Ethylpropylamino)
blue blue
4,5,6-Triamino-
phenol black black
pyrimidine
93 2-Dimethylamino-
3-(Butylamino)-phenol
blue blue
4,5,6-Triamino- black black
pyrimidine
94 2-Dimethylamino-
3-(Ethylamino)-phenol
blue blue
4,5,6-Triamino- black black
pyrimidine
95 2-Dimethylamino-
3-(Octylamino)-phenol
dark dark
4,5,6-Triamino- violet violet
pyrimidine
96 2-Dimethylamino-
3-Pyrrolidino-phenol
blue blue
4,5,6-Triamino- black black
pyrimidine
97 2-Dimethylamino-
3-Piperidino-phenol
dark dark
4,5,6-Triamino- blue blue
pyrimidine
98 2-Dimethylamino-
3-(Dimethylamino)-
dark dark
4,5,6-Triamino-
phenol blue blue
pyrimidine
99 2-Dimethylamino-
5-(Ethylamino)-2-
bluish bluish
4,5,6-Triamino-
methyl-phenol gray gray
pyrimidine
100 2-Dimethylamino-
2-Chloro-5-(dimethyl-
dark dark
amino)-phenol
amion)-phenol violet violet
pyrimidine
101 2-Dimethylamino-
3-Hydroxydiphenyl-
dark dark
4,5,6-Triamino-
amine blue blue
pyrimidine
102 2-Dimethylamino-
3-(Methylenecyana-
dark dark
4,5,6-Triamino-
mido)-phenol violet violet
pyrimidine
103 2-Dimethylamino-
2-bromo-5-(methylene-
blue blue
4,5,6-Triamino-
cyanamido)-phenol
black black
pyrimidine
104 2-Dimethylamino-
3-Tihoureido-phenol
brownish
dull
4,5,6-Triamino- gray violet
pyrimidine
105 2-Dimethylamino-
3-(Diethylamino)-4-
dark dark
4,5,6-Triamino-
methoxy-phenol
blue blue
pyrimidine
106 2-Dimethylamino-
5-(Diethylamino)-2-
dark dark
4,5,6-Triamino-
methyl-phenol blue blue
pyrimidine
107 2-Morpholino-
m-Dimethylamino-
dark dark
4,5,6-triamino-
phenol blue blue
pyrimidine
108 2-Morpholino-
3-Hydroxydiphenyl-
dark dark
4,5,6-triamino-
amine blue blue
pyrimidine
109 2-Morpholino-
3-(Octylamino)-
dark violet
4,5,6-triamino-
phenol violet blue
pyrimidine
110 2-Piperidino-
m-(Dimethylamino)-
dark dark
4,5,6-triamino-
phenol blue blue
pyrimidine
111 2-Piperidino-
m-(Octylamino)-
blue blue
4,5,6-triamino-
phenol violet violet
pyrimidine
112 2-Piperidino-
3-Hydroxydiphenyl-
dark dark
4,5,6-triamino-
amine blue blue
pyrimidine
113 2-Methylamino-
3-Hydroxydiphenyl-
violet blue
4,5,6-triamino-
amine blue violet
pyrimidine
114 2-Methylamino-
3-(Octylamino)-
deep deep
4,5,6-triamino-
phenol violet violet
pyrimidine
115 2-Methylamino-
m-(Dimethylamino)-
deep violet
4,5,6-triamino-
phenol violet blue
pyrimidine
116 2,4,5,6-Tetraamino-
m-(Dimethylamino)-
dark dark
pyrimidine phenol violet violet
117 2,4,5,6-Tetraamino-
m-(Diethylamino)-
dark dark
pyrimidine phenol violet violet
118 2,4,5,6-Tetraamino-
m-(Ethylamino)-
indigo indigo
pyrimidine phenol blue blue
119 2,4,5,6-Tetraamino-
m-(Ethylpropylamino)-
dark dark
pyrimidine phenol violet violet
120 2,4,5,6-Tetraamino-
m-[(β-Hydroxyethyl)-
dark dark
pyrimidine amino]-phenol violet violet
121 2,4,5,6-Tetraamino-
m-Piperidino-phenol
light light
pyrimidine violet violet
122 2,4,5,6-Tetraamino-
m-Pyrrolidino-
violet violet
pyrimidine phenol
123 2,4,5,6-Tetraamino-
3-Hydroxydiphenyl-
indigo indigo
pyrimidine amine blue blue
__________________________________________________________________________
The following tests were conducted to determine the toxicological and dermatological properties of tetraaminopyrimidines. The test compound used was 2-dimethylamino-4,5,6-triamino-pyrimidine sulfate which was compared with known compounds, p-phenylenediamine and p-toluylenediamine sulfate. The following results were obtained.
Male white mice of the CF/W 68-strain were used for the tests of general tolerance. The average weight of the test animals was 22 gm. The substances to be tested were administered by means of a stomach tube, whereby increasing dosages were used once. Ten mice were employed per dose. The volume of application was constant and was 0.2 cm3 /10 gm body weight. The animals were observed for a period of eight days. After the test results had been calculated according to the method of Litchfield-Wilcoxon, J. Pharm. Exptl. Ther. 96, 99-108(1949), the following LD50 -values were obtained.
______________________________________
2-dimethylamino-4,5,6-triamino-pyrimidine sulfate
555 mg/kg
p-Phenylendiamine 87 mg/kg
p-Diaminotoluene Sulfate 110 mg/kg
______________________________________
Distilled water was used as the solvent.
Groups of five animals were used for each preparation. Small quantities of the substances to be tested were applied in form of an aqueous 5% solution to the dorsal skin of each animal. A single daily application was continued for 14 days. During this period, and at the end of the test, none of the animals showed any reaction.
Groups of albino rabbits were employed for these tests of the local tolerance. Small quantities of the substances to be tested were employed as aqueous 5% preparations; and were once dripped into the conjunctival sac of one eye of each rabbit. The reactions of the mucous membranes of the eye were evaluated according to the point system of Draize, [Appraisal of the Safety of Chemicals in Foods, Drugs and Cosmetics. Assoc. of Food and Drug Officials of the U.S., pp. 49-52 (1959)]. This evaluation which was made 2, 6, 24 and 48 hours after the application and it showed that p-phenylenediamines leads to a low-grade redness and exudation of the conjuctiva which could not be detected 24 hours after the dripping in. The other two test compounds were tolerated without reaction.
This test of local tolerance was conducted according to Barail, [J. Society Cosmetic Chemists 11, 241 (1960)]. In this test, small quantities of the compounds to be tested were transcutaneously applied to the abdominal skin of white mice, whereby increasing concentration were used. After 24 hours, the test animals were sacrificed and the treated places of the skin were cut out and dried. The skin damages were evaluated according to a point system, in which the blood irrigation and other damages of the treated skin are taken into account. In this test, a larger animal group of ten mice was employed per preparation and per test concentration. Hence, finer differences with respect to local tolerance could be observed according to the above-described test procedure. The test results are reported in the following Table II. ##STR8##
It is evident from the above test results that (2-dimethylamino)-4,5,6-triamino-pyrimidine sulfate shows the best results of the tested developers with respect to general and local tolerance. Besides these good toxicological and dermatological properties, the tetraaminopyrimidines used .[.into.]. .Iadd.in .Iaddend.the hair coloring preparations according to the invention have the additional advantages that the color can readily be developed with atmospheric oxygen. These hair coloring preparations produce an extraordinary variation of shades which are distinguished by excellent fastness to light and washing, as well as by excellent resistance to abrasion, and they can easily be removed with reducing agents.
Although the present invention has been disclosed in connection with a few preferred embodiments thereof, variations and modifications may be resorted to by those skilled in the art without departing from the principles of the new invention. All of these variations and modifications are considered to be within the true spirit and scope of the present invention as disclosed in the foregoing description and defined by the appended claims.
Claims (9)
1. An aqueous preparation for the dyeing of hair consisting essentially of (1) from 0.2% to 5% by weight of an oxidation dyestuff combination of a developer component, and a coupling component in substantially equimolar amounts, said developer component consisting essentially of (A) a tetraaminopyrimidine of the formula ##STR9## wherein R1, R2, R3, R4, R5 and R6 are each selected from the group consisting of hydrogen, phenyl, 6-alkyl having 1 to 4 carbon atoms, phenylalkyl having 7 to 10 carbon atoms, phenylalkenyl having 7 to 10 carbon atoms,
X--(CH.sub.2).sub.n --
wherein n is an integer from 1 to 4, and X is selected from the group consisting of hydroxyl, halogen and NR7 R8 -- in which R7 and R8 are selected from the group consisting of hydrogen and alkyl having 1 to 4 carbon atoms, and together with the nitrogen atom R7 to R8 form a 5 to 6 membered heterocyclic ring optionally containing an additional nitrogen atom or an oxygen atom,
and wherein R1 and R2 or R3 and R4 or R5 and R6, together with the nitrogen atom form a 5 to 6 membered heterocyclic ring, optionally containing another nitrogen or oxygen atom in the ring or (B) a water-soluble acid addition salt of (A); (2) from 0% to 5% by weight of a direct dyestuff; (3) from 0% to 30% by weight of a surfactant; (4) from 0% to 25% by weight of a thickener; and (5) the balance up to 100% by weight of water.
2. The aqueous preparation of claim 1, wherein R1, R2, R3, R4, R5 and R6 are each selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, butyl, phenyl, benzyl, benzylidene; and --(CH2)n --X
wherein R1 and R2 or R3 and R4, or R5 and R6, together with the nitrogen atom form a substituent selected from the group consisting of piperidino and morpholino; and
wherein n is 1,2 or 3 and X is selected from the group consisting of hydroxyl, halogen and --NR7 R8 in which R7 and R8 are selected from the group consisting of hydrogen and alkyl having 1 to 4 carbon atoms.
3. The aqueous preparation of claim 1, wherein said coupling component is selected from the group consisting of (a) a 1-phenyl-pyrazol-5-one, (b) an aromatic amine (c) an aromatic alcohol, and (d) a pyrazolidinedione.
4. The aqueous preparation of claim 1, wherein there is from 1% to 3% by weight of said oxidation dyestuff combination.
5. The aqueous preparation of claim 1, wherein the developer component is selected from the group consisting of (A) 2,4,5,6-tetraamino-pyrimidine, 4-dimethylamino-2,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triamino-pyrimidine, 2-piperidino-4,5,6-triamino-pyrimidine, 2-morpholino-4,5,6-triamino-pyrimidine, 6-morpholino-2,4,5-triamino-pyrimidine, 6-piperidino-2,4,5-triamino-pyrimidine, 6-(di-n-propylamino)-2,4,5-triamino-pyrimidine, 5-amino-2,4,6-tris-(methylamino)-pyrimidine and 2-methylamino-4,5,6-triamino-pyrimidine and (B) a water soluble acid addition salt of (A).
6. The aqueous preparation of claim 1, wherein said coupling component is selected from the group consisting of (a) a m-aminophenol of the formula ##STR10## wherein Z and Y are each selected from the group consisting of hydrogen, halogen, hydroxyl, amino, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each of the alkyls;
wherein R9 is selected from the group consisting of alkyl having 1 to 10 carbon atoms, hydroxyalkyl having 1 to 10 carbon atoms, phenyl, anilino, hydroxyphenyl, benzyl, methylenecyanamido, propionamido, ureido, thioureido, oxalyl ester of an alcohol having 1 to 4 carbon atoms,
M--(CH.sub.2).sub.m --
wherein m is an integer from 1 to 4 and M is selected from the group consisting of hydroxyl, halogen, and --NR11 R12, in which R11 and R12 are selected from the group consisting of hydrogen and alkyl having 1 to 4 carbon atoms and wherein R10 is selected from the group consisting of hydrogen and R9,
wherein R9 and R10 can together with the nitrogen atom form a five to six membered heterocyclic ring optionally containing an additional nitrogen atom or an oxygen atom and
b. a water-soluble acid addition salt of (a).
7. The aqueous preparation of claim 6,
wherein Z and Y are each selected from the group consisting of hydrogen, methyl, methoxy, amino, chloro and hydroxyl;
wherein R9 is selected from the group consisting of methyl, ethyl, octyl, propyl, hydroxyethyl, phenyl, benzyl, anilino, hydroxyphenol, ureido, thioureido, methylenecyanamido and diethylaminoethyl,
wherein R10 is selected from the group consisting of hydrogen and R9,
and wherein R9 and R10 together with the nitrogen atom form a member selected from the group consisting of pyrrolidino, morpholino, and piperidino.
8. A process for the dyeing of human hair comprising applying to said hair at temperatures ranging substantially from 15° C. to 40° C. for a time sufficient to effect dyeing, an effective amount of the aqueous preparation of claim 1.
9. The process for the dyeing of human hair of claim 8, wherein said preparation also contains a chemical oxidizing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/953,688 USRE30199E (en) | 1973-11-29 | 1978-10-23 | Oxidation hair dyes based upon tetraaminopyrimidine developers |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2359399 | 1973-11-29 | ||
| DE19732359399 DE2359399C3 (en) | 1973-11-29 | 1973-11-29 | Hair dye |
| DE19742447017 DE2447017A1 (en) | 1974-10-02 | 1974-10-02 | Tetraaminopyrimidines as developers in oxidation hair dyes - esp. used with meta aminophenol couplers for blue shading dyes |
| DE2447017 | 1974-10-02 | ||
| US05/526,232 US4003699A (en) | 1974-11-22 | 1974-11-22 | Oxidation hair dyes based upon tetraaminopyrimidine developers |
| US05/953,688 USRE30199E (en) | 1973-11-29 | 1978-10-23 | Oxidation hair dyes based upon tetraaminopyrimidine developers |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/526,232 Reissue US4003699A (en) | 1973-11-29 | 1974-11-22 | Oxidation hair dyes based upon tetraaminopyrimidine developers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE30199E true USRE30199E (en) | 1980-01-29 |
Family
ID=27431769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/953,688 Expired - Lifetime USRE30199E (en) | 1973-11-29 | 1978-10-23 | Oxidation hair dyes based upon tetraaminopyrimidine developers |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE30199E (en) |
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| US4745652A (en) | 1986-08-18 | 1988-05-24 | Henkel Kommanditgesellschaft Auf Aktien | New tetra-aminopyrimidine derivatives and their use in hair-dyeing preparations |
| US5176716A (en) * | 1990-07-17 | 1993-01-05 | Goldwell Ag | Hair dye composition and its application method |
| WO1995001713A1 (en) * | 1993-07-07 | 1995-01-19 | Henkel Kommanditgesellschaft Auf Aktien | Dyes containing tetraaminopyrimidine and direct-dyeing agents |
| US6228130B1 (en) | 1998-11-03 | 2001-05-08 | Bristol-Myers Squibb Company | Primary intermediate in oxidative hair dyeing |
| US6342079B1 (en) | 2000-01-27 | 2002-01-29 | Bristol-Myers Squibb Company | Primary intermediate for use in oxidative hair dyeing |
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| US20040163186A1 (en) * | 2002-12-06 | 2004-08-26 | Frederic Simonet | Oxidation dye composition for keratin fibers, comprising at least one oxidation dye, at least one associative polymer, at least one nonionic cellulose-based compound not comprising a C8-C30 fatty chain, and at least one cationic polymer with a charge density of greater than 1 meq/g and not comprising a C8-C30 fatty chain |
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| US20040205906A1 (en) * | 2003-01-17 | 2004-10-21 | Laurent Vidal | Dyeing composition comprising an acylaminophenol coupler and use of this coupler for dyeing keratinous fibres |
| US20040205902A1 (en) * | 2002-12-06 | 2004-10-21 | Francois Cottard | Composition for the oxidation dyeing of keratin fibers, comprising at least one non-oxyalkenylated fatty alcohol, at least one oxidation dye, at least one associative polymer, and at least one amide of an alkanolamine and a C14-C30 fatty acid |
| US20040216242A1 (en) * | 2001-09-28 | 2004-11-04 | Sylvain Kravtchenko | Dyeing composition comprising a diaminopyrazole-type oxidation base a heterocyclic oxidation base and a coupling agent |
| US20040248961A1 (en) * | 2003-03-28 | 2004-12-09 | Laure Ramos | Para-phenylenediamine derivatives containing a disubstituted pyrrolidinyl group bearing a cationic radical, and use of the same for dyeing keratin fibers |
| US20040255402A1 (en) * | 2001-10-26 | 2004-12-23 | Georg Knuebel | Developer components and their use for dyeing keratinic fibers |
| US20050000038A1 (en) * | 2003-04-29 | 2005-01-06 | Marie-Pascale Audousset | Dye composition comprising 2-chloro-6-methyl-3-aminophenol, at least two oxidation bases chosen from para-phenylenediamine derivatives and at least one associative thickening polymer |
| US20050000039A1 (en) * | 2003-04-29 | 2005-01-06 | Marie-Pascale Audousset | Composition comprising at least one coupler chosen from 2-chloro-6-methyl-3-aminophenol and addition salts thereof, at least one oxidation base, and at least one associative polymer comprising at least one C8-C30 fatty chain |
| US20050000037A1 (en) * | 2003-04-29 | 2005-01-06 | Marie-Pascale Audousset | Dye composition comprising 2-chloro-6-methyl-3-aminophenol as coupler, para-aminophenol and 3-methyl-4-aminophenol as oxidation bases and at least one associative thickening polymer |
| US20050015897A1 (en) * | 2003-06-19 | 2005-01-27 | Marie-Pascale Audousset | Dye composition comprising at least one oxidation base chosen from 4,5-diamino-1-(beta-hydroxyethyl)-1H-pyrazole and 4,5-diamino-1-(beta-methoxyethyl)-1H-pyrazole and the addition salts thereof and at least one coupler chosen from 6-hydroxyindole and the addition salts thereof |
| US20050039271A1 (en) * | 2002-03-01 | 2005-02-24 | Schulze Zur Wiesche Erik | Colouring agents |
| US20050060814A1 (en) * | 2002-10-04 | 2005-03-24 | Laurent Vidal | Novel 6-alkoxy-2,3-diaminopyridine couplers in which the amino radical in position 2 is a monosubstituted amino radical, and use of these couplers for dyeing keratin fibres |
| US20050120494A1 (en) * | 2003-09-26 | 2005-06-09 | Laurent Vidal | Triazacyclononane derivatives substituted on at least one of the nitrogen atoms with a substituted or unsubstituted 4'-aminophenyl group, for dyeing keratin fibres |
| US20050125912A1 (en) * | 2001-12-21 | 2005-06-16 | Patricia Desenne | Dyeing composition for keratinous fibers comprising an oxyethylene rapeseed fatty acid amide |
| US20050150060A1 (en) * | 1997-10-03 | 2005-07-14 | L'oreal S.A. | Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibres |
| US20050172422A1 (en) * | 2004-01-07 | 2005-08-11 | Sylvain Kravtchenko | Dye composition comprising at least one direct dye of the azo-pyridinio-pyridone family and at least one different synthetic dye, and process |
| US20050188477A1 (en) * | 2004-01-28 | 2005-09-01 | Gregory Plos | Composition for dyeing keratin fibers, comprising at least one alcohol oxidase and at least one silicone chosen from amino silicones and oxyalkylenated silicones, and process using this composition |
| US20050188478A1 (en) * | 2004-01-28 | 2005-09-01 | Gregory Plos | Composition for dyeing keratin fibers, comprising at least one alcohol oxidase and at least one sugar-based nonionic surfactant, and a process using this composition |
| US20050204485A1 (en) * | 2004-01-28 | 2005-09-22 | Gregory Plos | Composition for dyeing keratin fibers, containing an alcohol oxidase and an anionic associative polymer, process using this composition |
| US20050235432A1 (en) * | 2004-01-28 | 2005-10-27 | Gregory Plos | Composition for dyeing keratin fibers, comprising at least one alcohol oxidase, at least one oxidation dye precursor, and at least one azo, methine or azomethine cationic direct dye, and process using this composition |
| US20050268406A1 (en) * | 2004-01-28 | 2005-12-08 | Gregory Plos | Compositions for dyeing keratin fibers, comprising at least one alcohol oxidase and at least one oxyalkylenated anionic surfactant, and processes using these compositions |
| US20060000032A1 (en) * | 2002-12-23 | 2006-01-05 | George Knuebel | Novel coupling components |
| US20060005322A1 (en) * | 2004-02-27 | 2006-01-12 | Stephane Sabelle | N-alkylhydroxylated secondary para-phenylenediamine compounds, composition for dyeing keratin fibers comprising the same, and dyeing processes using the composition |
| US20060005321A1 (en) * | 2004-02-27 | 2006-01-12 | Stephane Sabelle | Sulfur-containing secondary para-phenylenediamines dye compositions comprising such para-phenylenediamines, processes, and uses thereof |
| US20060005324A1 (en) * | 2004-06-23 | 2006-01-12 | Andrew Greaves | Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor |
| US20060005327A1 (en) * | 2004-06-23 | 2006-01-12 | Andrew Greaves | Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor |
| US20060005323A1 (en) * | 2004-02-27 | 2006-01-12 | Stephane Sabelle | N-heteroaryl secondary para-phenylenediamine, a dye composition comprising such a para-phenylenediamine, a process for preparing this composition and use thereof |
| US20060005320A1 (en) * | 2004-02-27 | 2006-01-12 | Stephane Sabelle | N-alkylheteroaryl secondary para-phenylenediamine and composition comprising such a para-phenylenediamine |
| US20060016025A1 (en) * | 2004-06-23 | 2006-01-26 | Andrew Greaves | Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor |
| US20060016023A1 (en) * | 2002-12-23 | 2006-01-26 | Georg Knuebel | Novel m-phenylenediamine derivatives as coupler components for the colouring of keratin fibres |
| US20060021162A1 (en) * | 2004-06-23 | 2006-02-02 | Andrew Greaves | Cationic diazo compound, compositions comprising at least one cationic diazo compound as a direct dye, a process for dyeing keratin fibers and device therefore |
| US20060026772A1 (en) * | 2004-02-27 | 2006-02-09 | L'oreal | N-alkylamino secondary para-phenylenediamine, composition for dyeing keratin fibers comprising such a para-phenylenediamine, processes using this composition and uses thereof |
| US20060026774A1 (en) * | 2004-02-17 | 2006-02-09 | Stephane Sabelle | Ortho-and/or meta-substituted N-alkylhydroxylated secondary para-phenylenediamine compounds, compositions for dyeing keratin fibers comprising such compounds, and processes of dyeing therewith |
| US20060037151A1 (en) * | 2004-06-23 | 2006-02-23 | L'oreal | Use of polycationic compounds in the dyeing of keratinous fibres |
| US20060052019A1 (en) * | 2004-09-03 | 2006-03-09 | Crook Robert L Jr | Papermakers felt having a point-bonded web layer formed of coarse fibers |
| US20060085923A1 (en) * | 2004-10-04 | 2006-04-27 | Alain Lagrange | Dye composition comprising a naphthoylene-benzimidazolium direct dye, process for dyeing keratin fibers and uses thereof |
| US20060112500A1 (en) * | 2004-11-03 | 2006-06-01 | Sylvain Kravtchenko | Use of organosilane compounds for dyeing keratin fibers |
| US20060149044A1 (en) * | 2004-12-15 | 2006-07-06 | Herve David | Dissymmetrical diazo compounds comprising 2-pyridinium group and a cationic or non-cationic linker, compositions comprising them, method for coloring, and device |
| US20060156489A1 (en) * | 2004-12-15 | 2006-07-20 | Herve David | Dyssymmetrical diazo compounds having at least one 4-pyridinium unit and a cationic or non-cationic linker, compositions comprising them, method of coloring, and device |
| US20060156478A1 (en) * | 2004-12-23 | 2006-07-20 | Boris Lalleman | Process for washing colored keratinous fibers with a composition comprising at least one nonionic surfactant and method for protecting the color |
| US20060156477A1 (en) * | 2004-12-15 | 2006-07-20 | Herve David | Symmetrical diazo compounds comprising 2-imidazolium groups and a non-cationic linke, compositions comprising them, method of coloring, and device |
| US20060156488A1 (en) * | 2004-12-15 | 2006-07-20 | Herve David | Symmetrical diazo compounds containing 2-pyridinium groups and a cationic or non-cationic linker, compositions comprising them, method of coloring, and device |
| US20060156490A1 (en) * | 2004-12-15 | 2006-07-20 | Herve David | Symmetrical diazo compounds comprising 2-imidazolium groups and a cationic linker, compositions comprising them, method of coloring, and device |
| US20060162098A1 (en) * | 2004-06-23 | 2006-07-27 | Alain Lagrange | Use of polycationic compounds for dyeing keratin fibres |
| US20060174422A1 (en) * | 2004-12-15 | 2006-08-10 | Herve David | Symmetrical diazo compounds comprising 4-pyridinium groups and a cationic or non-cationic linker, compositions comprising them, method for coloring, and device |
| US20060230546A1 (en) * | 2005-02-28 | 2006-10-19 | Eric Bone | Anhydrous composition in the form of a film comprising at least one film-forming polymer and at least one oxidation dye, preparation, and dyeing process |
| US20060236469A1 (en) * | 2005-02-28 | 2006-10-26 | Eric Bone | Anhydrous composition in the form of a film comprising a film-forming polymer and oxidizing agent, preparation and process for coloring keratinous fibers employing the anhydrous composition |
| US20060242771A1 (en) * | 2005-02-28 | 2006-11-02 | Eric Bone | Anhydrous composition in the form of a film comprising a film-forming polymer and a direct dye, preparation and dyeing process using the composition |
| US20060272104A1 (en) * | 2005-04-29 | 2006-12-07 | Alain Lagrange | Dye composition containing a particular cationic hydrazone direct dye, dyeing process, use and multi-compartment devices |
| US20060277693A1 (en) * | 2005-05-31 | 2006-12-14 | Jean-Baptiste Saunier | Composition for dyeing keratin fibers, comprising at least one diamino-N,N-dihydropyrazolone derivative, at least one coupler and at least one associative polyurethane polymer |
| US20060277692A1 (en) * | 2005-05-31 | 2006-12-14 | Jean-Baptiste Saunier | Composition for dyeing keratin fibers, comprising at least one diamino-N,N-dihydropyrazolone derivative, at least one coupler, and at least one surfactant |
| US20060277691A1 (en) * | 2005-05-31 | 2006-12-14 | Jean-Baptiste Saunier | Composition for dyeing keratin fibers, comprising a diamino-N,N-dihydropyrazolone compound, a coupler, and a polyol |
| US20070010663A1 (en) * | 2004-12-15 | 2007-01-11 | Herve David | Dissymmetrical diazo compounds containing having at least one 2-imidazolium unit and a cationic or non-cationic linker, compositions comprising them, method of coloring, and device |
| US20070011828A1 (en) * | 2005-06-29 | 2007-01-18 | Stephane Sabelle | Novel double para-phenylenediamines joined by a branched aliphatic group and method of dyeing keratin fibers |
| US20070011826A1 (en) * | 2005-06-29 | 2007-01-18 | Thierry Bordier | Novel double para-phenylenediamines joined by a linker arm substituted with one or more carboxylic radicals and/or derivatives and use in dyeing |
| US20070011824A1 (en) * | 2005-06-29 | 2007-01-18 | Stephane Sabelle | Double para-phenylenediamines joined by an aromatic group for dyeing keratin fibers |
| US20070074356A1 (en) * | 2005-09-29 | 2007-04-05 | Boris Lalleman | Process for the photoprotective treatment of artificially dyed keratin fibers by application of a liquid water/steam mixture |
| US20070079451A1 (en) * | 2005-08-11 | 2007-04-12 | Marie-Pascale Audousset | Composition for dyeing keratin fibers comprising at least one oxidation base and a polyoxyethylenated sorbitan ester |
| US20070136959A1 (en) * | 2005-11-09 | 2007-06-21 | Aziz Fadli | Composition for dyeing keratin fibers comprising at least one cationic 3-amino-pyrazolopyridine derivative, and methods of use thereof |
| US20070234487A1 (en) * | 2006-03-28 | 2007-10-11 | Alain Lagrange | Dye composition comprising at least one cationic hydrazone direct dye, dyeing process, and multi-compartment devices |
| US20080005853A1 (en) * | 2006-06-20 | 2008-01-10 | Francois Cottard | Process for the predictable dyeing of keratinous fibers comprising applying at least one composition comprising at least one diamino-N, N-dihydropyrazolone derivative and at least one composition chosen from fundamental and/or golden-highlights compositions |
| US20080016627A1 (en) * | 2006-06-20 | 2008-01-24 | Francois Cottard | Composition for dyeing of keratin fibers, comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, at least one oxidation base chosen from para-phenylenediamine and para-tolylenediamine, and a substituted meta-aminophenol |
| US20080016628A1 (en) * | 2006-06-20 | 2008-01-24 | Francois Cottard | Composition for dyeing keratin fibers, comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 6-chloro-2-methyl-5-aminophenol and a substituted meta-aminophenol |
| US20080052840A1 (en) * | 2006-05-22 | 2008-03-06 | Maxime De Boni | Use of an anionic hydrotrope for the colouring of keratinous fibres, composition comprising it and colouring processes employing it |
| US20080086824A1 (en) * | 2006-05-22 | 2008-04-17 | Maxime De Boni | Use of a cationic hydrotrope for the direct dyeing of keratinous fibres, composition comprising it and colouring processes employing it |
| US20080120792A1 (en) * | 2005-02-28 | 2008-05-29 | Gregory Plos | Dyeing of in Particular Human Keratin Materials by Dry Thermal Transfer of a Direct Azomethine Dye, Composition Comprising the Said Dye and its Method of Preparation |
| US7384432B2 (en) | 2004-02-27 | 2008-06-10 | L'oreal S.A. | Secondary para-phenylenediamines having a carboxyl group, dye compositions comprising the same, and dyeing processes using the compositions |
| US20080148496A1 (en) * | 2005-02-28 | 2008-06-26 | Gregory Plos | Dyeing of in Particular Human Keratin Materials by Dry Thermal Transfer of a Direct Dye, Composition Comprising the Said Dye and Its Method of Preparation |
| US20080163883A1 (en) * | 2006-11-30 | 2008-07-10 | Francois Cottard | Dye composition of acidic pH comprising 2,3-diamino-6, 7-dihydro-1H, 5H-pyrazolo[1,2-a]pyrazol-1-one, a coupler, a particular surfactant and an oxidizing agent and processes and kits using said composition |
| US20080168608A1 (en) * | 2005-02-28 | 2008-07-17 | Gregory Plos | Dyeing of in Particular Human Keratin Materials by Dry Thermal Transfer of a Direct Anthraquinone Dye, Composition Comprising the Said Dye and Its Method of Preparation |
| US7407517B2 (en) | 2005-08-23 | 2008-08-05 | L'oreal S.A. | Cationic azo dyes with julolidine units, dyeing composition containing them, method of dyeing |
| US20080216254A1 (en) * | 2005-08-11 | 2008-09-11 | Marie-Pascale Audousset | Process for coloring keratin fibers comprising treating the scalp with at least one sorbitan ester |
| US7435267B2 (en) | 2004-02-27 | 2008-10-14 | L'oreal S.A. | Secondary para-phenylenediamines bearing an alkoxy group, dye composition comprising them, processes therefor and uses thereof |
| US20080289121A1 (en) * | 2007-05-09 | 2008-11-27 | Jean-Baptiste Saunier | Method of coloring keratinous fibers comprising application of at least one aminopyrazolopyridine oxidation base in the absence of chemical oxidizing agents |
| US20080289122A1 (en) * | 2007-05-09 | 2008-11-27 | Jean-Baptiste Saunier | Dyeing compositions comprising at least one aminopyrazolopyridine oxidation base, at least one coupler and at least one C4-C30 polyol and methods and use thereof |
| US20090007347A1 (en) * | 2006-11-30 | 2009-01-08 | Francois Cottard | Dye composition of acidic pH comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, a para-phenylenediamine, a meta-aminophenol and an oxidizing agent, and processes for dyeing keratin fibers using the composition |
| US20090044348A1 (en) * | 2007-06-22 | 2009-02-19 | Aziz Fadli | Coloring composition comprising at least one azomethine compound with a pyrazolinone unit |
| US7582121B2 (en) | 2005-05-31 | 2009-09-01 | L'oreal S.A. | Composition for dyeing keratin fibers, comprising at least one diamino-N,N-dihydropyrazolone derivative, at least one coupler, and at least one heterocyclic direct dye |
| US7635394B2 (en) | 2005-11-09 | 2009-12-22 | L'oreal S.A. | Composition for the dyeing of keratin fibers comprising at least one 3-amino-pyrazolopyridine derivatives |
| US20100037909A1 (en) * | 2006-09-05 | 2010-02-18 | Henkel Ag & Co. Kgaa | Substances for dyeing keratinous fibers |
| US8366792B2 (en) | 2009-08-12 | 2013-02-05 | L'oreal | Dye composition comprising a heterocyclic oxidation base and an indole coupler |
| US8403999B2 (en) | 2009-12-22 | 2013-03-26 | L'oreal | Dyeing and/or bleaching composition comprising a polycondensate of ethylene oxide and propylene oxide |
| US8419807B2 (en) | 2009-10-13 | 2013-04-16 | L'oreal | Composition including a glyceride and an organophosphonic acid or one of the salts thereof, dyeing or colour-lightening method implementing same and devices |
| US8623100B2 (en) | 2010-12-17 | 2014-01-07 | L'oreal | 4-aminoindole derivatives and use thereof for the oxidation dyeing of keratin fibres |
| US8628586B2 (en) | 2010-12-07 | 2014-01-14 | L'oreal | Composition comprising an oxidation dye precursor, a polycondensate of ethylene oxide and propylene oxide and a cationic polymer with a charge density of greater than or equal to 4 meq./g |
| US8628587B2 (en) | 2010-12-07 | 2014-01-14 | L'oreal | Composition comprising an oxidation dye precursor, a polycondensate of ethylene oxide and propylene oxide, and a polyoxyalkylenated fatty acid |
| US8709101B2 (en) | 2010-12-07 | 2014-04-29 | L'oreal | Oxidation dye composition comprising a polycondensate of ethylene oxide and of propylene oxide, and an oxyethylenated fatty acid amide |
| US8784506B2 (en) | 2010-11-02 | 2014-07-22 | L'oreal | Dye composition having a low content of ammonia |
| US8790623B2 (en) | 2005-01-18 | 2014-07-29 | Il'Oreal | Composition for treating keratin fibers, comprising at least one aromatic alcohol, at least one aromatic carboxylic acid, and at least one protecting agent |
| US8808401B2 (en) | 2010-12-20 | 2014-08-19 | L'oreal | Hair dyeing process using an insoluble silicate, an aromatic compound and a hydroxylated aliphatic solvent |
| US8808400B2 (en) | 2011-01-10 | 2014-08-19 | L'oreal | Dyeing or lightening process using a composition rich in fatty substances comprising an alcohol having at least 20 carbons, compositions and device |
| US8814951B2 (en) | 2010-12-07 | 2014-08-26 | L'oreal | Oxidation dye composition comprising a polycondensate of ethylene oxide and of propylene oxide, and an unsaturated fatty alcohol |
| US8828099B2 (en) | 2011-01-10 | 2014-09-09 | L'oreal | Dyeing or lightening process using a composition rich in fatty substances comprising a solid alcohol and a solid ester, compositions and device |
| US8961620B2 (en) | 2011-01-10 | 2015-02-24 | L'oreal | Process for dyeing or lightening keratin fibres in two parts, using an oil-rich alkaline direct emulsion based on a solid nonionic surfactant with an HLB ranging from 1.5 to 10 |
| US9028562B2 (en) | 2011-04-29 | 2015-05-12 | L'oreal | Dye composition using a 2-hydroxynaphthalene, (acylamino)phenol or quinoline coupler in a fatty-substance-rich medium, dyeing process and device therefor |
| US9044412B2 (en) | 2011-07-05 | 2015-06-02 | L'oreal | Dye composition using a long-chain ether of an alkoxylated fatty alcohol and a cationic polymer, processes and devices using the same |
| US9060944B2 (en) | 2011-07-05 | 2015-06-23 | L'oreal | Cosmetic composition rich in fatty substances comprising a polyoxyalkylenated fatty alcohol ether and a direct dye and/or an oxidation dye, the dyeing method and the device |
| US9066890B2 (en) | 2011-07-05 | 2015-06-30 | L'oreal | Dye composition comprising an alkoxylated fatty alcohol ether and a fatty alcohol |
| US9078828B2 (en) | 2011-12-16 | 2015-07-14 | L'oreal | Cationic tetrahydropyrazolopyridines, dye composition comprising such oxidation bases, implementation process therefor and use thereof |
| US9107848B2 (en) | 2011-12-16 | 2015-08-18 | L'oreal | Coupler with cationic 7-amino-1,2,3,4-tetrahydroquinoline structure, dyeing composition comprising same, processes and uses |
| US9125834B2 (en) | 2010-12-17 | 2015-09-08 | L'oreal | Dye composition comprising a heterocyclic oxidation base and a 4-aminoindole coupler |
| US9192555B2 (en) | 2010-12-07 | 2015-11-24 | L'oreal | Oxidation dye composition comprising a polycondensate of ethylene oxide and of propylene oxide, and a non-oxyalkylenated glycerolated nonionic surfactant |
| US9220671B2 (en) | 2010-12-17 | 2015-12-29 | L'oreal | Dye composition comprising at least four dye precursors including at least one oxidation base and at least one coupler |
| US9226879B2 (en) | 2011-09-30 | 2016-01-05 | L'oreal | Foam dye composition comprising at least one particular oxyethylenated nonionic surfactant |
| US9226883B2 (en) | 2011-12-13 | 2016-01-05 | L'oreal | Particular azomethine direct dyes, dye composition comprising at least one such compound, implementation process therefore and use thereof |
| US9233057B2 (en) | 2011-12-13 | 2016-01-12 | L'oreal | Particular quinone direct dyes, dye composition comprising at least one such dye, implementation process therefor and use thereof |
| US9233060B2 (en) | 2011-12-16 | 2016-01-12 | L'oreal | Coupler with 7-amino-1,2,3,4-tetrahydroquinoline structure, dyeing composition comprising same, processes and uses |
| US9241886B2 (en) | 2011-04-29 | 2016-01-26 | L'oreal | Dye composition using a particular phenolic coupler in a medium rich in fatty substances, processes and devices |
| US9271910B2 (en) | 2011-09-15 | 2016-03-01 | L'oreal | Dye composition comprising a cationic para-aminophenol oxidation base |
| US9345653B2 (en) | 2012-07-02 | 2016-05-24 | L'oreal | Dye composition comprising a cationic meta-phenylenediamine |
| US9364404B2 (en) | 2012-08-17 | 2016-06-14 | L'oreal | Dye composition comprising a cationic O-alkyl-substituted meta-phenylenediamine derivative |
| US9370477B2 (en) | 2010-12-17 | 2016-06-21 | L'oreal | Dyeing composition comprising a fatty substance, a pyrazolopyridine oxidation base and a coupler |
| US9439844B2 (en) | 2011-12-13 | 2016-09-13 | L'oreal | Tri-aromatic azomethine direct dyes comprising at least one unit derived from resorcinol, dyeing composition, method and use |
| US9463148B2 (en) | 2011-09-30 | 2016-10-11 | L'oreal | Foam dye composition comprising a polycondensate of ethylene oxide and propylene oxide |
| US9474700B2 (en) | 2012-11-09 | 2016-10-25 | L'oreal | Methods for altering the color and appearance of hair |
| US9554977B2 (en) | 2011-12-13 | 2017-01-31 | L'oreal | Triaromatic azomethine direct dyes, dye composition comprising at least one such dye, method of implementation and use |
| US9566221B2 (en) | 2012-11-09 | 2017-02-14 | L'oreal | Methods for altering the color and appearance of hair |
| US9565916B2 (en) | 2011-11-09 | 2017-02-14 | L'oreal | Compositions and methods for altering the appearance of hair |
| US9565915B2 (en) | 2011-11-09 | 2017-02-14 | L'oreal | Compositions and methods for altering the appearance of hair |
| US9662290B2 (en) | 2012-04-24 | 2017-05-30 | L'oreal | Dyeing process using a mixture comprising a thickening polymer, obtained from an aerosol device, and device therefor |
| US9750678B2 (en) | 2014-12-19 | 2017-09-05 | L'oreal | Hair coloring compositions comprising latex polymers |
| US9789051B2 (en) | 2013-06-28 | 2017-10-17 | L'oreal | Compositions and methods for treating hair |
| US9789039B2 (en) | 2013-06-21 | 2017-10-17 | L'oreal | Oxidation dyeing process implementing a pretreatment based on a composition rich in fatty substances and on metal catalysts |
| US9789050B2 (en) | 2013-06-28 | 2017-10-17 | L'oreal | Compositions and methods for treating hair |
| US9789034B2 (en) | 2012-04-24 | 2017-10-17 | L'oreal | Dyeing process using a mixture obtained from an aerosol device comprising a liquid fatty, alcohol and surfactants |
| US9789040B2 (en) | 2013-06-21 | 2017-10-17 | L'oreal | Oxidation dyeing process using a composition rich in fatty substances which comprises metal catalysts and couplers |
| US9788627B2 (en) | 2013-06-28 | 2017-10-17 | L'oreal | Compositions and methods for treating hair |
| US9795555B2 (en) | 2013-06-28 | 2017-10-24 | L'oreal | Compositions and methods for treating hair |
| US9795556B2 (en) | 2013-06-28 | 2017-10-24 | L'oreal | Compositions and methods for treating hair |
| US9801808B2 (en) | 2014-12-19 | 2017-10-31 | Loreal | Hair styling compositions comprising latex polymers and wax dispersions |
| US9801804B2 (en) | 2013-06-28 | 2017-10-31 | L'oreal | Compositions and methods for treating hair |
| US9808409B2 (en) | 2012-03-30 | 2017-11-07 | L'oreal | Composition comprising (2,5-diaminophenyl)ethanol and a cellulose polymer or carboxylic anionic polymer in a medium rich in fatty substances, dyeing process and device |
| US9814668B2 (en) | 2014-12-19 | 2017-11-14 | L'oreal | Hair styling compositions comprising latex polymers |
| US9814669B2 (en) | 2014-12-19 | 2017-11-14 | L'oreal | Hair cosmetic composition containing latex polymers and a silicone-organic polymer compound |
| US9827185B2 (en) | 2012-08-02 | 2017-11-28 | L'oreal | Dyeing composition comprising at least one fatty substance, at least one oxidizing agent and at least one non-ionic, anionic and amphoteric surfactant |
| US9839600B2 (en) | 2013-06-28 | 2017-12-12 | L'oreal | Compositions and methods for treating hair |
| US9855198B2 (en) | 2012-04-24 | 2018-01-02 | L'oreal | Dyeing process using a mixture obtained from an aerosol device comprising a nonionic fatty amide, and device therefor |
| US9872822B2 (en) | 2013-06-21 | 2018-01-23 | L'oreal | Process for dyeing in the presence of oxidation bases comprising at least one sulfonic, sulfonamide, sulfone, amid or acid group and a metal catalyst, device and ready-to-use composition |
| US9884002B2 (en) | 2013-06-28 | 2018-02-06 | L'oreal | Compositions and methods for treating hair |
| US9884004B2 (en) | 2013-06-28 | 2018-02-06 | L'oreal | Compositions and methods for treating hair |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2350812A (en) * | 1942-11-21 | 1944-06-06 | Eastman Kodak Co | Diketopyrimidine coupler |
| US2355691A (en) * | 1942-11-21 | 1944-08-15 | Eastman Kodak Co | Pyrimidine couplers |
| US3359168A (en) * | 1966-08-03 | 1967-12-19 | Warner Lambert Pharmaceutical | Dyeing hair with 2, 3, 6-triaminopyridine and salts thereof |
| US3536436A (en) * | 1965-07-07 | 1970-10-27 | Hans Schwarzkopf | Hair dyeing composition and method |
-
1978
- 1978-10-23 US US05/953,688 patent/USRE30199E/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2350812A (en) * | 1942-11-21 | 1944-06-06 | Eastman Kodak Co | Diketopyrimidine coupler |
| US2355691A (en) * | 1942-11-21 | 1944-08-15 | Eastman Kodak Co | Pyrimidine couplers |
| US3536436A (en) * | 1965-07-07 | 1970-10-27 | Hans Schwarzkopf | Hair dyeing composition and method |
| US3359168A (en) * | 1966-08-03 | 1967-12-19 | Warner Lambert Pharmaceutical | Dyeing hair with 2, 3, 6-triaminopyridine and salts thereof |
Cited By (302)
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| US4575377A (en) | 1982-09-10 | 1986-03-11 | Henkel Kommanditgesellschaft Auf Aktien | Oxidation hair dyes comprising resorcinol derivatives as coupling components |
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| US7347879B2 (en) | 2004-02-27 | 2008-03-25 | L'Oreál, S.A. | Sulfur-containing secondary para-phenylenediamines dye compositions comprising such para-phenylenediamines, processes, and uses thereof |
| US20080069789A1 (en) * | 2004-02-27 | 2008-03-20 | L'oreal S.A. | N-alkylheteroaryl secondary para-phenylenediamine and composition comprising such a para-phenylenediamine |
| US7338536B2 (en) | 2004-02-27 | 2008-03-04 | L'oreal S. A. | N-alkylamino secondary para-phenylenediamine, composition for dyeing keratin fibers comprising such a para-phenylenediamine, processes using this composition and uses thereof |
| US7435267B2 (en) | 2004-02-27 | 2008-10-14 | L'oreal S.A. | Secondary para-phenylenediamines bearing an alkoxy group, dye composition comprising them, processes therefor and uses thereof |
| US7445645B2 (en) | 2004-02-27 | 2008-11-04 | L'oreal S.A. | Ortho-and/or meta-substituted N-alkylhydroxylated secondary para-phenylenediamine compounds, compositions for dyeing keratin fibers comprising such compounds, and processes of dyeing therewith |
| US20060005321A1 (en) * | 2004-02-27 | 2006-01-12 | Stephane Sabelle | Sulfur-containing secondary para-phenylenediamines dye compositions comprising such para-phenylenediamines, processes, and uses thereof |
| US7329288B2 (en) | 2004-02-27 | 2008-02-12 | L'oreal S.A. | N-heteroaryl secondary para-phenylenediamine, a dye composition comprising such a para-phenylenediamine, a process for preparing this composition and use thereof |
| US20060005323A1 (en) * | 2004-02-27 | 2006-01-12 | Stephane Sabelle | N-heteroaryl secondary para-phenylenediamine, a dye composition comprising such a para-phenylenediamine, a process for preparing this composition and use thereof |
| US20060005320A1 (en) * | 2004-02-27 | 2006-01-12 | Stephane Sabelle | N-alkylheteroaryl secondary para-phenylenediamine and composition comprising such a para-phenylenediamine |
| US20060026772A1 (en) * | 2004-02-27 | 2006-02-09 | L'oreal | N-alkylamino secondary para-phenylenediamine, composition for dyeing keratin fibers comprising such a para-phenylenediamine, processes using this composition and uses thereof |
| US20060005324A1 (en) * | 2004-06-23 | 2006-01-12 | Andrew Greaves | Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor |
| US7326259B2 (en) | 2004-06-23 | 2008-02-05 | L'oreal S.A. | Use of polycationic compounds in the dyeing of keratinous fibres |
| US20060162098A1 (en) * | 2004-06-23 | 2006-07-27 | Alain Lagrange | Use of polycationic compounds for dyeing keratin fibres |
| US20060016025A1 (en) * | 2004-06-23 | 2006-01-26 | Andrew Greaves | Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor |
| US20060005327A1 (en) * | 2004-06-23 | 2006-01-12 | Andrew Greaves | Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor |
| US7288122B2 (en) | 2004-06-23 | 2007-10-30 | L'oreal S.A. | Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor |
| US7285138B2 (en) | 2004-06-23 | 2007-10-23 | L'oreal, S.A. | Cationic diazo compound, compositions comprising at least one cationic diazo compound as a direct dye, a process for dyeing keratin fibers and device therefore |
| US7282069B2 (en) | 2004-06-23 | 2007-10-16 | L'oreal S.A. | Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor |
| US7208586B2 (en) | 2004-06-23 | 2007-04-24 | L'oreal S.A. | Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor |
| US20060037151A1 (en) * | 2004-06-23 | 2006-02-23 | L'oreal | Use of polycationic compounds in the dyeing of keratinous fibres |
| US20060021162A1 (en) * | 2004-06-23 | 2006-02-02 | Andrew Greaves | Cationic diazo compound, compositions comprising at least one cationic diazo compound as a direct dye, a process for dyeing keratin fibers and device therefore |
| US20060052019A1 (en) * | 2004-09-03 | 2006-03-09 | Crook Robert L Jr | Papermakers felt having a point-bonded web layer formed of coarse fibers |
| US20060085923A1 (en) * | 2004-10-04 | 2006-04-27 | Alain Lagrange | Dye composition comprising a naphthoylene-benzimidazolium direct dye, process for dyeing keratin fibers and uses thereof |
| US7354459B2 (en) | 2004-11-03 | 2008-04-08 | L'oreal S.A. | Use of organosilane compounds for dyeing keratin fibers |
| US20060112500A1 (en) * | 2004-11-03 | 2006-06-01 | Sylvain Kravtchenko | Use of organosilane compounds for dyeing keratin fibers |
| US20060149044A1 (en) * | 2004-12-15 | 2006-07-06 | Herve David | Dissymmetrical diazo compounds comprising 2-pyridinium group and a cationic or non-cationic linker, compositions comprising them, method for coloring, and device |
| US20060156489A1 (en) * | 2004-12-15 | 2006-07-20 | Herve David | Dyssymmetrical diazo compounds having at least one 4-pyridinium unit and a cationic or non-cationic linker, compositions comprising them, method of coloring, and device |
| US7396368B2 (en) | 2004-12-15 | 2008-07-08 | L'oreal S.A. | Symmetrical diazo compounds comprising 4-pyridinium groups and a cationic or non-cationic linker, compositions comprising them, method for coloring, and device |
| US20060156490A1 (en) * | 2004-12-15 | 2006-07-20 | Herve David | Symmetrical diazo compounds comprising 2-imidazolium groups and a cationic linker, compositions comprising them, method of coloring, and device |
| US20060174422A1 (en) * | 2004-12-15 | 2006-08-10 | Herve David | Symmetrical diazo compounds comprising 4-pyridinium groups and a cationic or non-cationic linker, compositions comprising them, method for coloring, and device |
| US7288639B2 (en) | 2004-12-15 | 2007-10-30 | L'oreal S.A. | Dyssymmetrical diazo compounds having at least one 4-pyridinium unit and a cationic or non-cationic linker, compositions comprising them, method of coloring, and device |
| US20060156488A1 (en) * | 2004-12-15 | 2006-07-20 | Herve David | Symmetrical diazo compounds containing 2-pyridinium groups and a cationic or non-cationic linker, compositions comprising them, method of coloring, and device |
| US20090062517A2 (en) * | 2004-12-15 | 2009-03-05 | L'oreal S.A. | Dissymmetrical Diazo Compounds Containing Having at Least One 2-imidazolium Unit and a Cationic or Non-cationic Linker, Compositions Comprising Them, Method of Coloring, and Device |
| US20060156477A1 (en) * | 2004-12-15 | 2006-07-20 | Herve David | Symmetrical diazo compounds comprising 2-imidazolium groups and a non-cationic linke, compositions comprising them, method of coloring, and device |
| US7351267B2 (en) | 2004-12-15 | 2008-04-01 | L'oreal S.A. | Symmetrical diazo compounds comprising 2-imidazolium groups and a non-cationic linke, compositions comprising them, method of coloring, and device |
| US7438728B2 (en) | 2004-12-15 | 2008-10-21 | L'oreal S.A. | Dissymmetrical diazo compounds comprising 2-pyridinium group and a cationic or non-cationic linker, compositions comprising them, method for coloring, and device |
| US20070010663A1 (en) * | 2004-12-15 | 2007-01-11 | Herve David | Dissymmetrical diazo compounds containing having at least one 2-imidazolium unit and a cationic or non-cationic linker, compositions comprising them, method of coloring, and device |
| US7247713B2 (en) | 2004-12-15 | 2007-07-24 | L'oreal, S.A. | Symmetrical diazo compounds containing 2-pyridinium groups and cationic or non-cationic linker, compositions comprising them, method of coloring, and device |
| US20060156478A1 (en) * | 2004-12-23 | 2006-07-20 | Boris Lalleman | Process for washing colored keratinous fibers with a composition comprising at least one nonionic surfactant and method for protecting the color |
| US7485155B2 (en) | 2004-12-23 | 2009-02-03 | L'oreal S.A. | Process for washing colored keratinous fibers with a composition comprising at least one nonionic surfactant and method for protecting the color |
| US8790623B2 (en) | 2005-01-18 | 2014-07-29 | Il'Oreal | Composition for treating keratin fibers, comprising at least one aromatic alcohol, at least one aromatic carboxylic acid, and at least one protecting agent |
| US20060230546A1 (en) * | 2005-02-28 | 2006-10-19 | Eric Bone | Anhydrous composition in the form of a film comprising at least one film-forming polymer and at least one oxidation dye, preparation, and dyeing process |
| US20060242771A1 (en) * | 2005-02-28 | 2006-11-02 | Eric Bone | Anhydrous composition in the form of a film comprising a film-forming polymer and a direct dye, preparation and dyeing process using the composition |
| US20060236469A1 (en) * | 2005-02-28 | 2006-10-26 | Eric Bone | Anhydrous composition in the form of a film comprising a film-forming polymer and oxidizing agent, preparation and process for coloring keratinous fibers employing the anhydrous composition |
| US20080168608A1 (en) * | 2005-02-28 | 2008-07-17 | Gregory Plos | Dyeing of in Particular Human Keratin Materials by Dry Thermal Transfer of a Direct Anthraquinone Dye, Composition Comprising the Said Dye and Its Method of Preparation |
| US7722680B2 (en) | 2005-02-28 | 2010-05-25 | L'oreal S.A. | Dyeing of human keratin materials by dry thermal transfer of a direct dye, composition comprising the said dye and its method of preparation |
| US20080148496A1 (en) * | 2005-02-28 | 2008-06-26 | Gregory Plos | Dyeing of in Particular Human Keratin Materials by Dry Thermal Transfer of a Direct Dye, Composition Comprising the Said Dye and Its Method of Preparation |
| US7651535B2 (en) | 2005-02-28 | 2010-01-26 | L'oreal S.A. | Dyeing of in particular human keratin materials by dry thermal transfer of a direct anthraquinone dye, composition comprising the said dye and its method of preparation |
| US20080120792A1 (en) * | 2005-02-28 | 2008-05-29 | Gregory Plos | Dyeing of in Particular Human Keratin Materials by Dry Thermal Transfer of a Direct Azomethine Dye, Composition Comprising the Said Dye and its Method of Preparation |
| US7645304B2 (en) | 2005-02-28 | 2010-01-12 | L'oreal S.A. | Dyeing of in particular human keratin materials by dry thermal transfer of a direct azomethine dye, composition comprising the said dye and its method of preparation |
| US20060272104A1 (en) * | 2005-04-29 | 2006-12-07 | Alain Lagrange | Dye composition containing a particular cationic hydrazone direct dye, dyeing process, use and multi-compartment devices |
| US7374581B2 (en) | 2005-04-29 | 2008-05-20 | L'oreal, S.A. | Dye composition containing a particular cationic hydrazone direct dye, dyeing process, use and multi-compartment devices |
| US20060277692A1 (en) * | 2005-05-31 | 2006-12-14 | Jean-Baptiste Saunier | Composition for dyeing keratin fibers, comprising at least one diamino-N,N-dihydropyrazolone derivative, at least one coupler, and at least one surfactant |
| US20060277693A1 (en) * | 2005-05-31 | 2006-12-14 | Jean-Baptiste Saunier | Composition for dyeing keratin fibers, comprising at least one diamino-N,N-dihydropyrazolone derivative, at least one coupler and at least one associative polyurethane polymer |
| US7582121B2 (en) | 2005-05-31 | 2009-09-01 | L'oreal S.A. | Composition for dyeing keratin fibers, comprising at least one diamino-N,N-dihydropyrazolone derivative, at least one coupler, and at least one heterocyclic direct dye |
| US7485156B2 (en) | 2005-05-31 | 2009-02-03 | L'oreal S.A. | Composition for dyeing keratin fibers, comprising at least one diamino-N,N-dihydropyrazolone derivative, at least one coupler and at least one associative polyurethane polymer |
| US7488356B2 (en) | 2005-05-31 | 2009-02-10 | L'oreal S.A. | Composition for dyeing keratin fibers, comprising at least one diamino-N,N-dihydropyrazolone derivative, at least one coupler, and at least one surfactant |
| US7488355B2 (en) | 2005-05-31 | 2009-02-10 | L'oreal S.A. | Composition for dyeing keratin fibers, comprising a diamino-N,N-dihydropyrazolone compound, a coupler, and a polyol |
| US20060277691A1 (en) * | 2005-05-31 | 2006-12-14 | Jean-Baptiste Saunier | Composition for dyeing keratin fibers, comprising a diamino-N,N-dihydropyrazolone compound, a coupler, and a polyol |
| US20070011826A1 (en) * | 2005-06-29 | 2007-01-18 | Thierry Bordier | Novel double para-phenylenediamines joined by a linker arm substituted with one or more carboxylic radicals and/or derivatives and use in dyeing |
| US20070011824A1 (en) * | 2005-06-29 | 2007-01-18 | Stephane Sabelle | Double para-phenylenediamines joined by an aromatic group for dyeing keratin fibers |
| US20070011828A1 (en) * | 2005-06-29 | 2007-01-18 | Stephane Sabelle | Novel double para-phenylenediamines joined by a branched aliphatic group and method of dyeing keratin fibers |
| US7422609B2 (en) | 2005-06-29 | 2008-09-09 | Oreal | Double para-phenylenediamines joined by an aromatic group for dyeing keratin fibers |
| US7413580B2 (en) | 2005-06-29 | 2008-08-19 | L'oreal S.A. | Double para-phenylenediamines joined by a linker arm substituted with one or more carboxylic radicals and/or derivatives and use in dyeing |
| US7442215B2 (en) | 2005-08-11 | 2008-10-28 | L'oreal S.A. | Process for coloring keratin fibers comprising treating the scalp with at least one sorbitan ester |
| US20080216254A1 (en) * | 2005-08-11 | 2008-09-11 | Marie-Pascale Audousset | Process for coloring keratin fibers comprising treating the scalp with at least one sorbitan ester |
| US7972387B2 (en) | 2005-08-11 | 2011-07-05 | L'oreal S.A. | Composition for dyeing keratin fibers comprising at least one oxidation base and a polyoxyethylenated sorbitan ester |
| US20070079451A1 (en) * | 2005-08-11 | 2007-04-12 | Marie-Pascale Audousset | Composition for dyeing keratin fibers comprising at least one oxidation base and a polyoxyethylenated sorbitan ester |
| US7407517B2 (en) | 2005-08-23 | 2008-08-05 | L'oreal S.A. | Cationic azo dyes with julolidine units, dyeing composition containing them, method of dyeing |
| US7998464B2 (en) | 2005-09-29 | 2011-08-16 | L'oreal S.A. | Process for the photoprotective treatment of artificially dyed keratin fibers by application of a liquid water/steam mixture |
| US20070074356A1 (en) * | 2005-09-29 | 2007-04-05 | Boris Lalleman | Process for the photoprotective treatment of artificially dyed keratin fibers by application of a liquid water/steam mixture |
| US20070136959A1 (en) * | 2005-11-09 | 2007-06-21 | Aziz Fadli | Composition for dyeing keratin fibers comprising at least one cationic 3-amino-pyrazolopyridine derivative, and methods of use thereof |
| US7635394B2 (en) | 2005-11-09 | 2009-12-22 | L'oreal S.A. | Composition for the dyeing of keratin fibers comprising at least one 3-amino-pyrazolopyridine derivatives |
| US7578855B2 (en) | 2005-11-09 | 2009-08-25 | L'ORéAL S.A. | Composition for dyeing keratin fibers comprising at least one cationic 3-amino-pyrazolopyridine derivative, and methods of use thereof |
| US7857864B2 (en) | 2005-11-09 | 2010-12-28 | L'oreal S.A. | Composition for the dyeing of keratin fibers comprising at least one 3-amino-pyrazolopyridine derivative |
| US7481847B2 (en) | 2006-03-28 | 2009-01-27 | L'oreal S.A. | Dye composition comprising at least one cationic hydrazone direct dye, dyeing process, and multi-compartment devices |
| US20070234487A1 (en) * | 2006-03-28 | 2007-10-11 | Alain Lagrange | Dye composition comprising at least one cationic hydrazone direct dye, dyeing process, and multi-compartment devices |
| US7678157B2 (en) | 2006-05-22 | 2010-03-16 | L'oreal S.A. | Use of an anionic hydrotrope for the colouring of keratinous fibres, composition comprising it and colouring processes employing it |
| US20080052840A1 (en) * | 2006-05-22 | 2008-03-06 | Maxime De Boni | Use of an anionic hydrotrope for the colouring of keratinous fibres, composition comprising it and colouring processes employing it |
| US20080086824A1 (en) * | 2006-05-22 | 2008-04-17 | Maxime De Boni | Use of a cationic hydrotrope for the direct dyeing of keratinous fibres, composition comprising it and colouring processes employing it |
| US7559956B2 (en) | 2006-05-22 | 2009-07-14 | L'oreal S.A. | Use of a cationic hydrotrope for the direct dyeing of keratinous fibres, composition comprising it and colouring processes employing it |
| US7651537B2 (en) | 2006-06-20 | 2010-01-26 | L'oreal S.A. | Composition for dyeing keratin fibers, comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 6-chloro-2-methyl-5-aminophenol and a substituted meta-aminophenol |
| US20080005853A1 (en) * | 2006-06-20 | 2008-01-10 | Francois Cottard | Process for the predictable dyeing of keratinous fibers comprising applying at least one composition comprising at least one diamino-N, N-dihydropyrazolone derivative and at least one composition chosen from fundamental and/or golden-highlights compositions |
| US20080016628A1 (en) * | 2006-06-20 | 2008-01-24 | Francois Cottard | Composition for dyeing keratin fibers, comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 6-chloro-2-methyl-5-aminophenol and a substituted meta-aminophenol |
| US7918900B2 (en) | 2006-06-20 | 2011-04-05 | L'oreal S.A. | Process for the predictable dyeing of keratinous fibers comprising applying at least one composition comprising at least one diamino-N, N-dihydropyrazolone derivative and at least one composition chosen from fundamental and/or golden-highlights compositions |
| US7651536B2 (en) | 2006-06-20 | 2010-01-26 | L'oreal S.A. | Composition for dyeing of keratin fibers, comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, at least one oxidation base chosen from para-phenylenediamine and para-tolylenediamine, and a substituted meta-aminophenol |
| US20080016627A1 (en) * | 2006-06-20 | 2008-01-24 | Francois Cottard | Composition for dyeing of keratin fibers, comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, at least one oxidation base chosen from para-phenylenediamine and para-tolylenediamine, and a substituted meta-aminophenol |
| US20100037909A1 (en) * | 2006-09-05 | 2010-02-18 | Henkel Ag & Co. Kgaa | Substances for dyeing keratinous fibers |
| US20090007347A1 (en) * | 2006-11-30 | 2009-01-08 | Francois Cottard | Dye composition of acidic pH comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, a para-phenylenediamine, a meta-aminophenol and an oxidizing agent, and processes for dyeing keratin fibers using the composition |
| US7766977B2 (en) | 2006-11-30 | 2010-08-03 | L'oreal S.A. | Dye composition of acidic pH comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, a para-phenylenediamine, a meta-aminophenol and an oxidizing agent, and processes for dyeing keratin fibers using the composition |
| US20080163883A1 (en) * | 2006-11-30 | 2008-07-10 | Francois Cottard | Dye composition of acidic pH comprising 2,3-diamino-6, 7-dihydro-1H, 5H-pyrazolo[1,2-a]pyrazol-1-one, a coupler, a particular surfactant and an oxidizing agent and processes and kits using said composition |
| US7651539B2 (en) | 2006-11-30 | 2010-01-26 | L'oreal S.A. | Dye composition of acidic pH comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, a coupler, a particular surfactant and an oxidizing agent and processes and kits using said composition |
| US7578856B2 (en) | 2007-05-09 | 2009-08-25 | L'oreal S.A. | Dyeing compositions comprising at least one aminopyrazolopyridine oxidation base, at least one coupler and at least one C4-C30 polyol and methods and use thereof |
| US20080289122A1 (en) * | 2007-05-09 | 2008-11-27 | Jean-Baptiste Saunier | Dyeing compositions comprising at least one aminopyrazolopyridine oxidation base, at least one coupler and at least one C4-C30 polyol and methods and use thereof |
| US20080289121A1 (en) * | 2007-05-09 | 2008-11-27 | Jean-Baptiste Saunier | Method of coloring keratinous fibers comprising application of at least one aminopyrazolopyridine oxidation base in the absence of chemical oxidizing agents |
| US7648536B2 (en) | 2007-05-09 | 2010-01-19 | L'oreal S.A. | Method of coloring keratinous fibers comprising application of at least one aminopyrazolopyridine oxidation base in the absence of chemical oxidizing agents |
| US20090044348A1 (en) * | 2007-06-22 | 2009-02-19 | Aziz Fadli | Coloring composition comprising at least one azomethine compound with a pyrazolinone unit |
| US7582123B2 (en) | 2007-06-22 | 2009-09-01 | L'oreal S.A. | Coloring composition comprising at least one azomethine compound with a pyrazolinone unit |
| US8366792B2 (en) | 2009-08-12 | 2013-02-05 | L'oreal | Dye composition comprising a heterocyclic oxidation base and an indole coupler |
| US8419807B2 (en) | 2009-10-13 | 2013-04-16 | L'oreal | Composition including a glyceride and an organophosphonic acid or one of the salts thereof, dyeing or colour-lightening method implementing same and devices |
| US8403999B2 (en) | 2009-12-22 | 2013-03-26 | L'oreal | Dyeing and/or bleaching composition comprising a polycondensate of ethylene oxide and propylene oxide |
| US8784506B2 (en) | 2010-11-02 | 2014-07-22 | L'oreal | Dye composition having a low content of ammonia |
| US11406578B2 (en) | 2010-11-25 | 2022-08-09 | L'oreal | Process for stripping keratin fibres using a composition comprising a sulfinic acid derivative and an acidic aqueous composition |
| US9192555B2 (en) | 2010-12-07 | 2015-11-24 | L'oreal | Oxidation dye composition comprising a polycondensate of ethylene oxide and of propylene oxide, and a non-oxyalkylenated glycerolated nonionic surfactant |
| US8628586B2 (en) | 2010-12-07 | 2014-01-14 | L'oreal | Composition comprising an oxidation dye precursor, a polycondensate of ethylene oxide and propylene oxide and a cationic polymer with a charge density of greater than or equal to 4 meq./g |
| US8628587B2 (en) | 2010-12-07 | 2014-01-14 | L'oreal | Composition comprising an oxidation dye precursor, a polycondensate of ethylene oxide and propylene oxide, and a polyoxyalkylenated fatty acid |
| US8814951B2 (en) | 2010-12-07 | 2014-08-26 | L'oreal | Oxidation dye composition comprising a polycondensate of ethylene oxide and of propylene oxide, and an unsaturated fatty alcohol |
| US8709101B2 (en) | 2010-12-07 | 2014-04-29 | L'oreal | Oxidation dye composition comprising a polycondensate of ethylene oxide and of propylene oxide, and an oxyethylenated fatty acid amide |
| US9370477B2 (en) | 2010-12-17 | 2016-06-21 | L'oreal | Dyeing composition comprising a fatty substance, a pyrazolopyridine oxidation base and a coupler |
| US8623100B2 (en) | 2010-12-17 | 2014-01-07 | L'oreal | 4-aminoindole derivatives and use thereof for the oxidation dyeing of keratin fibres |
| US9220671B2 (en) | 2010-12-17 | 2015-12-29 | L'oreal | Dye composition comprising at least four dye precursors including at least one oxidation base and at least one coupler |
| US9125834B2 (en) | 2010-12-17 | 2015-09-08 | L'oreal | Dye composition comprising a heterocyclic oxidation base and a 4-aminoindole coupler |
| US8808401B2 (en) | 2010-12-20 | 2014-08-19 | L'oreal | Hair dyeing process using an insoluble silicate, an aromatic compound and a hydroxylated aliphatic solvent |
| US8961620B2 (en) | 2011-01-10 | 2015-02-24 | L'oreal | Process for dyeing or lightening keratin fibres in two parts, using an oil-rich alkaline direct emulsion based on a solid nonionic surfactant with an HLB ranging from 1.5 to 10 |
| US10130568B2 (en) | 2011-01-10 | 2018-11-20 | L'oreal | Process for dyeing or lightening keratin fibres in two parts, using an oil-rich alkaline direct emulsion based on a solid nonionic surfactant with an HLB ranging from 1.5 to 10 |
| US8808400B2 (en) | 2011-01-10 | 2014-08-19 | L'oreal | Dyeing or lightening process using a composition rich in fatty substances comprising an alcohol having at least 20 carbons, compositions and device |
| US8828099B2 (en) | 2011-01-10 | 2014-09-09 | L'oreal | Dyeing or lightening process using a composition rich in fatty substances comprising a solid alcohol and a solid ester, compositions and device |
| US9028562B2 (en) | 2011-04-29 | 2015-05-12 | L'oreal | Dye composition using a 2-hydroxynaphthalene, (acylamino)phenol or quinoline coupler in a fatty-substance-rich medium, dyeing process and device therefor |
| US9993411B2 (en) | 2011-04-29 | 2018-06-12 | L'oreal | Dye composition using a phenol-derived coupler in a medium rich in fatty substances, processes and devices |
| US9241886B2 (en) | 2011-04-29 | 2016-01-26 | L'oreal | Dye composition using a particular phenolic coupler in a medium rich in fatty substances, processes and devices |
| US10863811B2 (en) | 2011-06-23 | 2020-12-15 | L'oreal | Process for treating keratin fibres with input of heat |
| US9060944B2 (en) | 2011-07-05 | 2015-06-23 | L'oreal | Cosmetic composition rich in fatty substances comprising a polyoxyalkylenated fatty alcohol ether and a direct dye and/or an oxidation dye, the dyeing method and the device |
| US9044412B2 (en) | 2011-07-05 | 2015-06-02 | L'oreal | Dye composition using a long-chain ether of an alkoxylated fatty alcohol and a cationic polymer, processes and devices using the same |
| US9066890B2 (en) | 2011-07-05 | 2015-06-30 | L'oreal | Dye composition comprising an alkoxylated fatty alcohol ether and a fatty alcohol |
| US9271910B2 (en) | 2011-09-15 | 2016-03-01 | L'oreal | Dye composition comprising a cationic para-aminophenol oxidation base |
| US9463148B2 (en) | 2011-09-30 | 2016-10-11 | L'oreal | Foam dye composition comprising a polycondensate of ethylene oxide and propylene oxide |
| US9226879B2 (en) | 2011-09-30 | 2016-01-05 | L'oreal | Foam dye composition comprising at least one particular oxyethylenated nonionic surfactant |
| US9578944B2 (en) | 2011-11-09 | 2017-02-28 | L'oreal | Compositions and methods for altering the appearance of hair |
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