US3629330A - Components for hair dyeing compositions - Google Patents

Components for hair dyeing compositions Download PDF

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US3629330A
US3629330A US458443A US3629330DA US3629330A US 3629330 A US3629330 A US 3629330A US 458443 A US458443 A US 458443A US 3629330D A US3629330D A US 3629330DA US 3629330 A US3629330 A US 3629330A
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dye
hair
sodium
product
mixture
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Frederick Brody
Alexander Halasz
Milos S Bil
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P&G Hair Care Holding Inc
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Clairol Inc
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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
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/418—Amines containing nitro groups
    • 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
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C275/14—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/06—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms
    • C07C335/08—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of a saturated carbon skeleton

Definitions

  • ABSTRACT OF THE DISCLOSURE A group of N-substituted alkyl derivatives of nitroaminobenzenes which are characterized by the fact that the alkyl group carry further substituents such as --Oalkyl, NHCO-alkyl, NHCOhydroxyalkyl, NHCOaryl, NHSO -alkyl, NHSO aryl, NHCONH and SO alkyl; these are useful as dyes or dye intermediates that are particularly suitable for dyeing hair.
  • This invention relates to a novel group of alkyl derivatives of nitroaminobenzenes that are particularly suitable as dye intermediates or for dyeing keratinaceous materials. More particularly, it relates to said derivatives and compositions containing the same which may be used to dye living human hair on the head or as dye intermediates in preparing such dyes.
  • Nitrophenylenediamine derivatives have been suggested for use in the prior art as hair dyes. These, however, have been found in practice to offer many disadvantages. Nitrophenylenediamine dyes having no substituents on the amino nitrogens have only a yellow or orange shade. This is a disadvantage, since it is the red, blue and violet shades that are necessary for blending colors to arrive at natural looking shades.
  • the simple alkyl-substituted nitrophenylenediamine derivatives wherein only the simple alkyl substituents (e.g., methyl, ethyl) are on one or both amino nitrogens are insufficiently soluble or dispersible in Water.
  • some dyes of this class tend to sublime readily when exposed to heat (e.g., body heat or sunlight). The dyeings with these dyes, thus, become weaker and off-shade on wearing.
  • Y and Z are selected from the group consisting of NO and NR R at least one of said Y and Z being NO and wherein R R and R are selected from the group consisting of hydrogen, alkyl, hydroxyalkyl and the radical -alkyleneX, at least one of said R R and R being the radical --alkyleneX, in which the divalent radical alkylene may be straight chain or branched chain and may contain up to 4 carbon atoms; and X is selected from the group O-alkyl, -NHCOalkyl, NHCOhydroXyalkyl, NHCO-aryl, NHSO -alkyl, -NHSO aryl, NHCONH CN, SO NH droxyalkyl;
  • R is -alkylene-X. Although these have some use as dyes, they are principally useful as intermediates in preparing alkyl derivatives of nitrophenylenediamines.
  • compounds of Formula I which are especially suitable as dyes are those compounds in which one of Y and Z is NO and the other is -NR R wherein R and R have the same significance ascribed to them above.
  • R R or R in Formula I above is an alkyl radical, it may be of any carbon-chain length and may be either straight chain or branched chain. As a practical matter, however, the alkyl radical will rarely exceed 8 carbon atoms.
  • the alkyl radicals are lower alkyl radicals, and particularly alkyl radicals having from 1 to 4 carbon atoms.
  • the following specific alkyl radicals may be mentioned: methyl, ethyl, propyl, isopropyl, n-butyl, sec.- butyl, tert.-butyl, n-amyl, n-hexyl, and Z-ethylhexyl.
  • R R or R of Formula I are bydroxyalkyl radicals
  • the alkyl moiety of these radicals may be of any carbon-chain length and likewise may be either straight chain or branched chain. Again, however, as a practical matter, they will rarely exceed 8 carbon atoms, and preferably they will be lower alkyl groups containing from 1 to 4 carbon atoms.
  • hydroxyalkyl radicals will also vary. For the most part, there will be a maximum of 3 hydroxy groups.
  • hydroxyalkyl groups which are included within the definition of R R and R of Formula I above: hydroxymethyl, Z-hydroxyethyl, 3- hydroxypropyl, 2,3-dihydroxypropyl and 4-hydr-oxybutyl.
  • the aryl group may be unsubstituted or may contain any of a variety of substituents. Typical of the substituents that can be mentioned are lower alkyl, halogen, hydroxyalkyl, lower alkoxy, nitro, dialkylamino, carbamoyl, sulfamoyl, etc.
  • the substituents may occupy any position in the benzene nucleus.
  • the aryl radical is a naphthyl radical, the substituents may occupy any of the or or [3 positions.
  • this aryl radical is a hydrocarbon radical, and more particularly a phenyl radical or a lower alkyl substituted phenyl radical.
  • R R and R is the radical alkyleneNHCOaryl or -alkylene-- NHSO -aryl
  • aryl may be mentioned: phenyl, o-, m-, p-tolyl, m-chlorophenyl, mand p-anisyl, p-ethoxyphenyl, m-hydroxymethylphenyl, mnitrophenyl, p-dimethylaminophenyl, m-carbamoylmethyl, m-sulfamoylmethyl, l-naphthyl, Z-naphthyl, 3-hydroxy-2 naphthyl, 8-methoxy-1-naphthyl.
  • the compounds of the present invention may be prepared by various known methods which depend on the nature and position of the substituent --alkyleneX in Formula I.
  • R has the value alkyleneX in Formula 1
  • these compounds are generally prepared by first reacting 2,4-dinitrochl0robenzene with a suitable amine, NH -alkyleneX. This is accomplished by heating one mole of the former with one or more moles of the latter, in alcohol, aqueous alcohol, or an organic solvent containing an acid binder, such as sodium bicarbonate, sodium acetate, calcium carbonate or an additional mole of the amine, at reflux for periods ranging from /2 hour to 6 hours. This gives an N-substituted 2,4-dinitroaniline (Formula A below).
  • nitro groups is preferentially reduced to give either a Z-nitro-p-phenylenediamine or a 4-nitro-o-phenylenediamine, depending on the reduction method used.
  • the reduction is carried out essentially by the method of U-Sa Pat. 3,088,978,
  • R and R are alkyl or hydroxyalkyl groups by reaction with the appropriate alkyl or hydroxyalkyl halide, sulfate or tosylate or an alkylene oxide, for example, with ethyl iodide, dimethyl sulfate, methyl tosylate, ethylene chlorohydrin or ethylene oxide, by known methods.
  • Either one or two alkyl or hydroxylalkyl groups may be introduced by varying the proportion of the reagent used, the course of the reaction being conveniently followed by chromatogram, and stopped when the appropriate degree of substitution has been reached.
  • R and R may be different alkyl or hydroxyalkyl groups, which are introduced sequentially by reaction first with R -hal and then with R hal (hal being a halogen atom or its equivalent sulfate or tosylate group).
  • the dye When in the general Formula I, it is desired that R and/ or R; be the substituted alkyleneX, the dye may be conveniently prepared from a 2-nitro-p-phenylenediamine or a 4-nitro-o-phenylenediamine (e.g., Formula D below) in which R is already present. This is reacted with an appropriate X-alkylenehal, in which hal represents a chlorine, bromine or iodine atom. Depending on the reactivity of the Xalkylenehal and the number of X-alkylene groups to be introduced (whether one or two), one uses varying proportions of the reagent, from one mole to a large excess.
  • the reaction is carried out in an organic solvent or aqueous organic solvent at temperatures varying from room temperature to about C., and for times varying from 1 to 20 hours.
  • the solvent, temperature and time of reaction selected depend in part on the activity of the Xalkylenehal used.
  • highly reactive Xalkylenehal compounds such as chloroacetonitrile
  • a low boiling solvent such as ethanol
  • the Xalkylene-hal compounds of low activity such as chloroethyl ethyl ether
  • a high boiling solvent such as amyl alcohol
  • the extent of reaction is preferably followed by chromatogram in which can be seen the proportion of unreacted, monosubstituted and disubstituted com ponents, which can be distinguished by their colors.
  • the reaction is stopped at the desired stage, and the mixture worked up as usual. Significant amounts of unreacted starting material may be removed as the Schiffs base with benzaldehyde.
  • An alternate method for introducing alkylene-X groups is to react a nitrophenylenediamine (e.g., Formula D below) with a compound having an activated double bond.
  • the -X moiety generally is an electron attracting group which serves to activate the double bond.
  • reactants of this character include acrylonitrile, vinyl methyl ketone, and methyl vinyl sulfone.
  • the reaction is carried out by using equimolecular amounts of the two materials, in alcohol or aqueous alcohol containing a small amount of acetic acid as catalyst and heating to reflux for 3 to 10 hours. By this means only one alkyleneX will generally be introduced.
  • N-aminoalkyl-2,4-dinitroaniline which may be acylated and one of the nitro groups reduced and so forth, as described above.
  • NHCONH When X is a ureido group, NHCONH one may again prepare the aminoalkyl derivatives mentioned above, and either react them with potassium cyanate in a solvent or fuse them with urea for conversion of the free amino group to the ureido.
  • NHCSNH For introducing the thioureido group, NHCSNH one may react the aminoalkyl derivatives with carbon disulfide and caustic to form the dithiocarbonate; this is converted to the isothiocyanate (e.g., by reaction with ethyl chloroformate), and this in turn reacted with dry ammonia.
  • X is a sulfamoyl or a substituted sulfamoyl group
  • 2,4-dinitrochlorobenzene with an aminoalkanesulfonic acid (such as taurine), thereby obtaining an N-sulfoalkyl-2,4-dinitroaniline.
  • This may be converted by known methods, as with PCl to the N-ch10rosulfonylalkyl-2,4-dinitroaniline which by reaction with ammonia, an alkylamine or a hydroxyalkylamine forms the corresponding sulfamoylalkyl derivative of 2,4-dinitroaniline.
  • the dyes embodied in the present invention have many advantages over the prior art dyes utilized in this field. As compared with nitrophenylenediamine dyes having no substituents on the nitrogens, which are yellow or orange in shade, the dyes of this invention show a wide range of shade, from yellow to bluish violet.
  • the dyes of this invention are more soluble in water, or more readily dispersible. They can thus give more concentrated dye baths and therefore much stronger dyeings on hair.
  • the dyes of this character wherein only H or unsubstituted alkyl groups are bonded to nitrogen tend to sublime readily, when exposed to heat (e.g., body heat or sunlight) and thus to become weaker and olf-shade on wearing.
  • the dyes having ionizable substituents on the alkyl group i.e.
  • the dyes of this invention have much higher aifinity to hair without at the same time dyeing the hair unlevely, rubbing off, or staining the skin.
  • an acylated aminoalkyl side chain such as CH CH NHCOR or This is because dye aifinity and wet fastness depend on having an optimum of hydrophilic character.
  • a free hydroxy or amino group has more hydrophilic character than alkoxy or acylamido and could in fact be too hydrophilic for the purpose of dyeing hair.
  • a further disadvantage of the aminoalkyl radical is its high basicity which makes the dye more soluble in acidic media and less likely to go on hair therefrom. This disadvantage is removed in the case of all of the present acylamido derivatives, i.e., alkyl substituted by NHCOR, NHCOAr, NHSQ R, NHCONH NHCO R, NHCSNH
  • Another comparison may be made directly between the known sulfonic acid dyes (having (CH SO H) and the present sulfonarnide dyes (having SO NH SO NHR, or SO NRR).
  • the sulfonic dyes are anionic, with low general affinity when compared to the sulfonamides of this invention.
  • the dyes of the present invention can be employed to prepare basic, neutral or acidic dye compositions and because of their stability, may be used in conjunction with oxidation dyes. Furthermore, they may likewise be included in hair dyeing compositions which contain other direct dyeing dyes that also may or may not contain an oxidation dye.
  • direct dyeing dyes are known in the prior art which are useful for this purpose. They include other nitro dyes, azo dyes, anthraquinone dyes, etc. By way of illustration, any of the nitro dyes disclosed in the following U.S. patents may be used in conjunction with the present nitro dyes: 2,750,326; 2,750,327; 3,088,- 877; 3,088,878 and 3,088,978.
  • the dye compositions of this invention have in general the advantage that they are stable on storage. For example, when they are stored in the dark at 50 C. for a period of 3 months and then dyed on hair by methods described below, they show essentially no change in shade or strength of dyeing, as compared to the same compositions applied initially, before storage. Stability on storage is of great commercial importance, since dye compositions on the market are likely to be held on the shelf for periods up to several years, sometimes at high ambient temperatures.
  • the pH of the dye compositions of this invention can vary from about 2.5 to 11. In the acid range the pH of about 3.5 to 6 is suitable. It is preferred, however, that the compositions be in the alkaline range, and particu larly at a pH of about 7.5 to 10. Any selected waterdispersible, compatible, alkalizing agent (if it is desired to have the compositions in the alkaline range) can. be used to give the desired pH.
  • the quantity of the alkalizing agent employed can vary over a wide range depending on the dye and particular alkalizing agent employed and the desired pH. Illustratively, the alkalizing agent can vary from less than about 0.1% to about 10%, and preferably from about 0.25% to about 5% by weight of the composition.
  • the alkalizing agent is selected so that it will not interfere (i.e., is compatible) with the dye employed, and will not precipitate the dye or introduce any possibility of toxicity under the conditions of use, or injure the scalp at its ultimate concentration in the composition to be applied to the keratinaceous material.
  • a preliminary test of some selected alkalizing agent can be made to note its compatibility with the dye or to discover possibility of toxicity or injury.
  • Ammonium hydroxide because of its freedom from toxicity over a wide concentration range and its economy, is an acceptable alkalizing agent.
  • HoWever there can be used in place of, or together with, ammonia any other compatible ammonia derivative as an alkalizing agent, such as an alkylamine, such as ethylamine, dipropylamine, or triethylamine, an alkanediamine, such as 1,3-diaminopropane, an alkanolamine, such as ethanolamine or diethanolamine, a polyalkylenepolyarnine, such as diethylenetriamine, or a heterocyclic amine, such as morpholine.
  • an alkylamine such as ethylamine, dipropylamine, or triethylamine
  • an alkanediamine such as 1,3-diaminopropane
  • an alkanolamine such as ethanolamine or diethanolamine
  • a polyalkylenepolyarnine such as diethylenetriamine
  • any alkaline earth hydroxide for example, calcium hydroxide or magnesium hydroxide
  • the dissolved alkaline earth hydroxides are preferred over the alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, or carbonates, such as sodium carbonate and bicarbonate, any of which. can also be used so long as their ultimate concentration in the final dyeing solution is below that which might possibly irritate the scalp.
  • the alkalizing component of choice is a water-soluble organic amine of low volatility (B.P. higher than about C.) having less than about 12 carbon atoms, such as n-propylamine, isobutylamine, 2-ethylbutylamine, diethylamine, triethylamine.
  • alkalizing agent particularly suited as the alkalizing agent are the following: (A) primary aliphatic diamines, such as ethylenediamine; 1,2- diaminopropane; 1,3-diaminopropane; diethylenetriamine; triethylenetetramine; 2,2'-iminodipropy1amine; 3,3-iminodipropylamine; and bis-hexamethylenetriamine; (B) alkanolamines, such as ethanolamine; isopropanolamine; diethanolamine; di-isopropanolamine; triethanolamine; triisopropanolamine; N-methyldiethanolamine; diisopropylethanolamine; dimethylisopropanolamine; 2 amino- Z-methylpropane 1,3 diol; tris(hydroxymethyl)methylamine and the like, which may also have a phenyl substituent, e.g., N-(Z-hydroxyethyl)aniline; N-methyl-N- Z-
  • the pH of the composition may be adjusted with any inorganic or organic acid or acid salt which is compatible with the composition and will not introduce toxocity under its conditions of use, especially when acid compositions are desired.
  • acids or acid salts there can be mentioned: sulfuric, formic, acetic, lactic, citric or tartaric acid, or ammonium sulfate, sodium dihydrogen phosphate, or potassium bisulfate.
  • Water-soluble surface active agents can also be employed in the dyeing compositions utilized in this invention. These can be anionic, non-ionic or cationic. Illustrative of the various types of water-soluble surface active agents there can be mentioned: higher alkylbenzenesulfonates; alkylnaphthalenesulfonates; sulfonated esters of alcohols and polybasic acids; taurates; fatty alcohol sulfates; sulfates of branched chain or secondary alcohols; alkyl dimethylbenzyl ammonium chlorides; and the like.
  • lauryl sulfate polyoxyethylene lauryl ester; myristyl sulfate; glyceryl monostearate; sodium salt of palmitic methyl taurine; cetyl pyridinium chloride; lauryl sulfonate; myristyl sulfonate; lauric diethanolamide; polyoxyethylene stearate; stearyl dimethyl 'benzyl ammonium chloride; dodecyl benzene sodium sulfonate; nonyl naphthalene sodium sulfonate; dioctyl sodium sulfosuccinate; sodium N-methyl-N-oleoyl taurate; oleic acid ester of sodium isothionate; sodium dodecyl sulfate; the sodium salt of 3,9- diethyl tridaconol-6-sulfate and the like.
  • a thickening agent can also be incorporated in the present dyeing composition which may be one or several of those commonly used in hair dyeing, such as sodium ⁇ alginate or gum arabic, or cellulose derivatives, such as methylcellulose, or the sodium salt of carboxymethylcellulose, or acrylic polymers, such as polyacrylic acid sodium salt, or inorganic thickeners, such as bentonite.
  • the quantity of thickening agent can vary over a wide range, such as that of from about 0.1% to 20% and preferably from about 0.5% to 5% by weight.
  • Tinctorially effective quantities of the novel nitro dyes in the compositions of this invention can also vary over a wide range, such as that of about 0.01% to greater than about e.g., by weight of the composition, and preferably from about 0.01% to about 2% by weight.
  • the water content of the composition is ordinarily the major constituent and can vary over a wide range dependent in large measure on the quantity of other additives. Thus, the water content can be as little as 10%, and preferably from about 70% to 99%.
  • the dyeing compositions of this invention are preferably aqueous compositions.
  • aqueous composition is used herein in its usual generic sense as embracing any water-containing composition embodied in the invention. This includes true solutions of the dye in an aqueous medium, ether alone or in conjunction with other materials, which are also dissolved or dispersed in the aqueous medium.
  • aqueous composition also encompasses any mixture of dye With the aqueous medium either alone, or together with other ingredients.
  • the dye may be colloidally dispersed in the medium or may merely be intimately mixed therein.
  • aqueous medium includes any medium which contains water.
  • the aqueous medium may be an aqueous alkaline, aqueous neutral or aqueous acid medium.
  • the aqueous medium may comprise water and a solvent, e.g., ethanol. The latter may be employed as a common solvent to enhance the solution of the dye or some other organic material.
  • aqueous compositions of this invention may take many forms. Thus, they may be thin or thick flowable liquids, pastes, gels, etc.
  • any of the dyes, surface active agents, a-lkalies, thickening agents, acids and combinations thereof set forth above may be used in the proportions specified in the table immediately above.
  • the novel nitro dyes utilized in this invention are generally compatible with oxidation dyes. Accordingly, they can be used in oxidation dye compositions. Suitable compositions contain 15% ammonia, 23% hydrogen peroxide or urea peroxide; 0.005% to 2% oxidation dye components; 0.001% to 3% Compound I as defined above, as well as surfactants, thickeners, etc.
  • oxidation dye components can be utilized in formulating this composition: 0- phenylenediamine, m-phenylenediamine, p-phenylenediamine, p-toluenediamine, nitro-p-phenylenediamine, 4- nitro-o-phenylenediamine, p-aminodiphenylamine; 4,4- diaminodiphenylamine; 4,6 dinitro 2 aminophenol; 4- nitro-2-aminophenol; 2,4-diaminoanisole, hydroquinone,
  • resorcinol p-aminophenol
  • 1,2,4-trihydroxybenzene 1,2,4- triacetoxybenzene.
  • the dyeing compositions of this invention can be prepared by the conventional methods used in the hair dyeing art. Thus, they can be prepared by dissolving or suspending the dye in water in the desired concentration. Water miscible organic solvents can be employed to facilitate solution of the dye; in this event, the dye can be dissolved first in the solvent and then diluted with water. The dispersion of the various ingredients can also be facilitated by heating the composition at temperatures varying from 40 C. to 110 C., either before dilution with water or afterwards.
  • the dyeing compositions of this invention can be applied to hair by the conventional techniques used in the art.
  • the compositions when applied to living hair on the human head, can be applied to the hair with a brush, sponge, or other means of contact, such as dipping until the hair is properly saturated with the composition.
  • the reaction time or time of contact of the dyeing composition with the hair is not critical and can vary over a Wide range used in the hair dyeing art, such as periods of about 5 minutes to about 2 hours, and preferably from about 15 minutes to about minutes.
  • the dyeing temperature can vary over wide limits as is conventional in the art. Thus, the dyeing temperature can vary from about room temperature, e.g., about 20 C. to above about 60 C., and preferably from about 20 C. to about 45 C.
  • N-(Z-methoxyethyl)-2,4-dinitroaniline 150 ml. isopropanol 2.
  • platinum-on-charcoal was hydrogenated at atomospheric pressure until 3 molar equivalents of hydrogen were taken up. A precipitate was formed which was filtered off and treated with 600 ml. boiling water in order to dissolve the sulfate salt of the product. The hot slurry was filtered and the filtrate was cooled and made basic with ammonia. The product, which has the above structure, and which was in the form of reddish crystals, was filtered off. The yield was 3.3 g.
  • Example 9 IIIHCHQ l lHCH cH OCH
  • a mixture of 16.7 g. N -methyl-2-nitro-p-phenylenediamine, 10.0 g. sodium carbonate, 9.5 g. 2-chloroethyl methyl ether, and 150 ml. n-amyl alcohol was heated at reflux for 10 hours.
  • a test portion examined by paper chromatography showed the presence of reddish violet product and a significant amount of the starting primary amine N-methyl 2 nitro-p-phenylenediamine; however, no tertiary amine by-product was present.
  • the reaction mixture was steam-distilled and evaporated to dryness, and the residue dissolved in ml. ethanol.
  • Example 10 ITIHCH CH NHCOCH The 56.5 g. N-(Z-aminoethyl)-2,4-dinitroaniline in 300 ml. water, there was added 30 g. acetic anhydride. The mixture was heated at 80 C., cooled and then filtered. The filter cake obtained was then washed. There was recovered 58 g. of acetylated product of the above structure having a melting point 1747 C.
  • Example 12 1 IHCHzOHzNHC 00113
  • IHCHzOHzNHC 00113 A mixture of the dye, N -(2-acetamidoethyl)-2-nitro-pphenylenediamine, 2.5 molar equivalents of dimethyl sulfate, and 2 molar equivalents of sodium carbonate, in 50% aqueous alcohol, was heated at reflux until no further change was evident on a paper chromatogram. The alcohol was then distilled off, and the mixture cooled. The precipitated product, which has the structure formulated above, was filtered off, washed and dried.
  • Example 13 NHCHZCHZNHC 0 CH3
  • N -(2-acetamidoethy1)-2-nitro-p-phenylenediamine, 3.5 molar equivalents of ethyl iodide, and 2 molar equivalents of sodium carbonate, in 50% aqueous ethanol were heated in an autoclave at 8090 C. for about 14 hours.
  • the alcohol was then distilled off, and the product isolated by filtering and washing. It has the structure formulated above.
  • the precipitate which was the free base of the product, having the above formulated structure, was filtered off, washed with brine, and then with water. Yield, 12.0 g. of violet crystals, M.P. 62-64 0, having essentially a single colored component by paper chromatography.
  • Example 27 IYIHO Ha I IHCH OH NHC 0011
  • Example 28 1TIHCH CH CH NHC 00112011 N-(3-arninopropyl)-2,4-dinitroaniline was converted to the glycolyl derivative by reaction with 1.1 molar equivalent of glycolic acid in benzene solution in the presence of sodium bisulfate. The mixture was heated at reflux under a benzene-water separator, so that the water produced during the reaction was co-distilled with benzene as it was formed, and removed from the reaction mixture. Heating was continued until water no longer distilled ofl.
  • Example 29 BIIHCHZCHZCHZNHC OCH OH N-(3-glycolamidopropyl)-2,4-dinitroaniline was hydrogenated catalytically according to the procedure of Example 11 for reduction of the 4-nitro group.
  • Example 30 NHCH CH NHC o-@ To 56.5 g. of N(2-aminoethyl)-2,4-dinitroani1ine in 200 ml. of 5% aqueous NaOH was slowly added, while stirring, 40 g. of benzoyl chloride. The reaction mixture was then stirred for an additional two hours. The reaction product was filtered off and the filter cake was Washed well with water. 42 g. of the product, which has the above formulated structure, was obtained. On recrystallization from aqueous dimethylformamide, it had the melting point 188189 C.
  • Example 32 ITIHCH ClLNHCO-Q l uoH crr on A solution of 5.2 g. N -(Z-benzamidoethyl)-2-nitro-pphenylenediamine in ml. of ethanol was heated at reflux and ethylene oxide was passed in until a test portion was chromatographically homogeneous. The solvent was evaporated off giving a thick violet oil which did not crystallize on standing.
  • Example 34 Example 35 l ncmonzonmnoooom N-(El-benzamidopropyl)-2,4-dinitroaniline was hydrogenated by shaking 16.4 g. of the material in 200 ml. ethanol, containing 1 gram of 5% platinum-on-charcoal catalyst, and 100 ml. conc. HCl, at about 50 psi. hydrogen, until three molar equivalents of hydrogen were absorbed. The reaction mixture was filtered to remove the catalyst, and the filtrate reduced to a volume of 25 ml. and set in the cold. After some time a precipitate of 1 g. of the hydrochloride of the above formulated product was obtained as yellow crystals of M.P. 222-225 C.
  • the mother liquor contained considerably more of the product, as shown chromatographically, and this could be recovered in less pure form, and as the free base by basification of the liquor.
  • N -(2-hydroxyethyl)-2 nitro-p-phenylenediamine 75 ml. isopropanol 20 175 ml. water 61.2 g. 2-bromoethylamine hydrobromide neutralized wtih sodium carbonate to slight alkalinity was added dropwise at 75 C. to C., over a period of 20 minutes, 6.0 g. sodium hydroxide in the form of a 25% solution. Refiuxing was continued for one-half hour. Then the alcohol was distilled 01?, and the mixture salted at room temperature and acidified with hydrochloric acid. The light brown precipitate which formed was filtered off, and washed with a little water.
  • Example 38 IITHOH CH CH NHS 020E! A mixture of 24 g. N-(3-aminopropyl)-2,4-dinitroaniline, 11.4 g. methanesulfonyl chloride, 9 g. sodium bicarbonate, and ml. ethanol was heated at reflux for 4 /2 hours. The product, which precipitated on cooling, was filtered off, washed with hot water and dried. Yield, 11.5 g.; M.P. after recrystallization from ethanol, 162- 165 C.
  • Example 40 The dye, N -(3-methylsulfonamidopropyl) 2 nitro-pphenylenediamine, was hydroxyethylated by bubbling ethylene oxide through a solution of the dye in ethanol, at reflux temperature. When sufficient ethylene oxide had been bubbled in, as determined chromatographically by the appearance of a maximum of a bluish violet spot, the reaction mixture was taken to dryness. The residue was recrystallized from aqueous dimethylformamide, and appeared as dark violet crystals; it has the above designated structure.
  • Example 41 To a solution of 21 g. N-(3-methylsulfonamidopropyl)-2,4-dinitroaniline in 150 ml. ethanol was added a polysulfide solution prepared from 14.7 g. sodium sulfide and 3.9 g. sulfur dissolved in 45 ml. water. The addition was carried out at 7080 C. over a period of onehalf hour, and heating was continued for an additional one-half hour. The reaction mixture was then poured on ice, and the precipitate collected by filtration, washed with water and dried. It was recrystallized from ethanol; yield, 11.6 g.; M.P. 157-160 C.
  • Example 42 NH C Ha I IHOHZCHZNHSOZCEQ N -methylN -(2-aminoethyl) 2 nitro-p-phenylenediamine was treated with methanesulfonyl chloride according to the procedure of Example 38. There was obtained a bluish red product, N -methyl-N -(Z-methylsulfonamidoethyl) -2-nitro-p-phenylenediamine.
  • Example 43 NBC H3
  • Example 46 A mixture of 22.6 g. N-(Z-aminoethyl)-2,4-dinitroaniline, 17.7 g. benzenesulfonyl chloride, 10 g. sodium bicarbonate, and 100 ml. ethanol was heated at reflux for 5 hours. After cooling, the product, having the above formulated structure, was filtered off and washed with water. Yield, 15.6 g.; M.P. 159-160 C.
  • Example 48 IfHCHgCHgNHS 0311 I KGH OH OI-D N -(2 benzenesulfonamidoethyl)-2-nitro-p-phenylenediamine was subjected to hydroxyethylation following the procedure of Example 15, in which a hot ethanolic solution of the starting material is treated with ethylene oxide. When the reaction was essentially complete, as shown by a paper chromatogram, the solvent was evaporated off. The residue of reddish violet dye consisted essentially of the compound of the above formulated structure, and was used directly in dyeing experiments as described below.
  • N(3-aminopropyl)2,4-dinitroaniline 70 g. urea was heated for 5 hours at 150 165 C. Water was added to the reaction mixture to dissolve the excess urea and the reaction mixture was filtered. 12 g. of the product was obtained; M.P. 186-9 C.
  • Example 51 ITIHCH CH CH NHC ONH Into a solution of 4 g. N -(3-ureidopropyl)-2-nitro-pphenylenediamine in ethanol at reflux was bubbled ethylene oxide until a test portion chromatographed on paper showed essentially a single violet band. On evaporation to dryness there was obtained a violet viscous product which was used directly in. the dyeing of hair, described below.
  • Example 53 IITHCH CH NHC ONH 1503 A mixture of N-(Z-aminoethyl)-2,4-dinitroaniline and 5 molar equivalents of urea was fused at l50160 C. for 5 hours. The excess urea was then extracted with water, and the product was filtered, thoroughly washed and dried. It was used as such in the next synthetic step.
  • the hydrochloride of the product did not crystallize out of the reaction mixture.
  • the mixed amines were chromatographed on a column of silica gel, using chloroformmethanol 9:1 for developement. The red band was cut out of the column and the product extracted therefrom. It appeared as dark red crystals and had the above designated structure.
  • N-(Z-aminoethyl)-2,4-dinitroaniline was treated with one molar equivalent of ethyl chloroformate in pyridine solution by stirring the mixture of components at room temperature for about one hour. The reaction mixture was then drowned in water and the precipitated product N (2 carbethoxyaminoethyl) 2,4 dinitroaniline, filtered off, washed and dried.
  • Example 58 IIIHCHZCHQNHC OgCgHi
  • the compound, N-(Z carbethoxyaminoethyl)-2,4-dinitroaniline was hydrogenated according to the procedure of Example 24.
  • the hydrochloride of the product having the above formulated structure was recovered as yellow crystals, and was used directly in the dyeing experiments described below.
  • Example 59 111K 0 H3O H SO Na To a solution of 62.5 g. taurine and 4.2 g. sodium bicarbonate in 400 ml. water heated at reflux was added slowly 101 g. 2,4 dinitrochlorobenzene. Heating was continued for an additional 3 hours. After cooling, the precipitated crystals were filtered 01f, pressed dry and recrystallized from hot water containing a small amount (about 1%) of sodium hydroxide. The product is N-(Z- sulfoethyl)-2,4-dinitroaniline.
  • Example 62 NHCHzCHzSOzNHz
  • Example 6 3 111110 HzGHzS OzNHz M TQZ
  • the dye, N (2 sulfamoylethyl) 2 nitro-p-phenylenediamine was treated with 2.5 molar equivalents of dimethyl sulfate and 2 molar equivalents of sodium carbonate in 50% aqueous ethanol.
  • the mixture was heated at reflux until no further change was observed in the 27 chromatogram. After distillation of most of the alcohol, the product was recovered by filtration; it was washed and dried.
  • the dark violet product was used as such for the dyeing of hair, as described below.
  • Example 64 IIIHCHzCHzSOzNHCHa The procedure of Example 60 was followed except that in place of ammonia there was used an excess of 40% aqueous methylamine. The product was N-[Z-(methylsulfamoyl) ethyl] -2,4dinitroaniline.
  • Example 65 IIIHCH O H S O NHC H3
  • the procedure of Example 62 was followed except that the dinitroaniline derivative used was N-[2- (methylsulfamoyl)ethyl]-2,4-dinitroaniline.
  • the product was the hydrochloride of the dye of the above formulated structure. 9
  • This salt was used directly in the subsequent hair dyeing experiments, described below.
  • Example 66 IIIHCH CILS OZNIEI CHZO H 0 11
  • the procedure of Example 60 was followed except that in place of ammonia there was used an excess of 50% aqueous ethanolamine.
  • the product was N- [2-(2-hydroxyethylsulfamoyl)ethyl]-2,4-dinitroaniline and was used in the next example.
  • Example 67 IYIHCH CH S O NHCH GH OH I IHg
  • the procedure of Example 62 was followed except that the dinitroaniline derivative used was N-[2-(2-hydroxyethylsulfamoyl)ethyl]-2,4-dinitroaniline.
  • the product was the hydrochloride of the dye having the above formulated structure. The yellow hydrochloride product was used in the later hair dyeing experiments.
  • Example 68 IIIHCHZCHQS O N(CH3)g
  • the procedure of Example 60 was followed, except that in place of ammonia there was used an excess of 25% aqueous dimethylamine.
  • the product was N-[2-(dimethylsulfamoyl)ethyl]-2,4-dinitroaniline. It was used in the following example.
  • Example 69 IITHCH CH S O N(CH CH OH) 1 102 The procedure of Example 60 was followed, except that in place of ammonia there was used 25% aqueous diethanolamine. The product was N-[Z-(bis-Z-hydroxyethylsulfamoyl)ethyl]-2,4-dinitroaniline.
  • Example 71 lfrroH oH so NwH oH om
  • the compound, N-[2-(bis-Z-hydroxyethylsulfamoyl)- ethyl] -2,4-dinitroaniline was hydrogenated according to the procedure of Example 62. There was obtained the hydrochloride of the base whose structure is formulated above. It was used in this form for the dyeing of hair, as described below.
  • Example 71A ITIHCH GH SO N OH CH OH NO
  • the procedure of Example 60 was followed except that in place of ammonia there was used 25 aqueous 2- methylaminoethanol.
  • the product was N-[2(N-methyl-N- 2-hydroxyethylsulfamoyl) ethyl] -2,4-dinitroaniline.
  • the compound N-[2(N-methyl-N-Z-hydroxyethylsulfamoyl)ethyl]-2,4-dinitroaniline was hydrogenated according to the procedure of Example 62. There was obtained the hydrochloride of the base whose structure is formulated above. It was used in this form for the dyeing of hair, as described below.
  • Example 73 Nnon on so om
  • Example 74 I vHOHQ NHCHZCHZC OCH3
  • a solution of N -methyl-2-nitro-p-phenylenediamine and 5 g. methyl vinyl ketone in 100 ml. ethanol was heated at reflux for 5 hours.
  • the chromatogram at this point showed a single, violet component to be present.
  • the reaction mixture was clarified, and concentrated to 75 ml.
  • the product which had the above formulated structure, crystallized out. There was obtained 5 g. of red crystals of M.P. 120123 C., which was essentially pure by chromatogram.
  • the dye, N -methyl-N-(3-oxobutyl)-2-nitro-p-phenylenediamine (product of Example 74) was hydroxyethylated by treatment with ethylene oxide according to the procedure of Example 15, except that methanol was used as the solvent instead of ethanol.
  • the reaction mixture was chromatographed on a silica gel column, developing with a methanolchloroform 1:9 mixture.
  • the product, having the structure formulated above, was recovered from the bluish violet band found on the column, and was used for the dyeing of hair as described below.
  • Example 76 a I MCH CI-LCOCHQ A mixture of 15.3 g. Z-nitro-p-phenylenediamine, 14 g. methyl vinyl ketone, and 150 ml. ethanol was heated at reflux for 8 hours. Afterwards it was allowed to cool over night, and the crystalline precipitate filtered off. These crystals showed a single, violet band when examined chromatographically. They were recrystallized from ethanol, giving 15 g. violet crystals, M.P. -7 C.
  • Example 77 ITTHCHzGHzOH The hydrochloride of N -(2-hydroxyethyl)-2-nitro-p phenylenediamine was treated with 4 molar equivalents of methyl vinyl ketone in alcohol under reflux. When the reaction was essentially complete, the mixture was concentrated to a small volume and, on cooling, the product which has the structure designated above, precipitated out, and was filtered off. The purple crystals were used to dye hair as described in later examples.
  • Example 78 NHC H3
  • Example 81 A mixture of:
  • Example 83 NHCHZCHZOH HOCH CH NCH CH CN
  • a mixture of 4.38 g. of the dye, N -(2-hydroxyethyl)- N -(2-cyanoethyl)-2-nitro-p-phenylenediamine, 6.04 g. 2- chloroethanol, 2.5 g. calcium carbonate and 24 ml. water, containing catalytic amounts of iodine and cuprous chloride was heated at reflux for 12 hours. The reaction mixture was then acidified, clarified, diluted with three volumes of water, and made alkaline. Upon cooling, the product precipitated, and was collected by filtration; M.P. 1 11-1 13 C.
  • Dye-amount to be specified Isopropanol0.5 ml.
  • Thickening agentamount to be specified Water-to 100 ml.
  • Acid agentto give specified pH of 7 or lower
  • the dye was wet with isopropanol, and the other ingredients added with stirring and warming below 50 C. to give a uniform dispersion. Hair was dyed with this composition as in Procedure A.
  • PROCEDURE C Dyeing hair from peroxide bath The following composition was prepared:
  • a 30-ml. portion of this composition was mixed with 30 ml. of 6% hydrogen peroxide and the mixture poured on natural gray and bleached hair and allowed to remain there for 40 minutes at 30 C. The hair was then rinsed with clear water, shampooed and dried.
  • Example 86 The product of Example 2 was dyed on hair according to Procedure A, using 0.25 g. dye, 3.0 g. N-phenyldiethanolamine (as alkaline agent), 3.0 g. sodium N-coconut acid N-methyl taurate (as surfactant), and 3.0 g. hydroxyethylcellulose (as thickener), the pH being adjusted to 9.5. Both gray and bleached hair were dyed in strong level orange shades fast to shampooing. When this composition was stored for 3 months at 50 C. and again dyed on hair, the deyings were fully equivalent to the initial dyeings in shade and strength.
  • Example 87 The product of Example 3 was dyed on hair accord ing to Procedure A, using 0.3 g. dye, 3.0 g. diethylenetriamine (alkaline agent), 4.0 g. lauric diethanolamide (surfactant) and 3.0 g. methylcellulose (thickener), the pH being adjusted to 8.5. A red dyeing of good strength was obtained, somewhat stronger on the bleached than on the gray hair, and both fast to shampooing. When the above composition was stored at 50 C. for 3 months and then again dyed on hair, the dyeings were similar in shade and strength to the initial dyeings.
  • Example 88 The product of Example 8 was dyed on hair according to Procedure A, using 0.15 g. dye, 4.0 g. ethanolamine (alkaline agents), 2.0 g. sodium dodecylbenzenesulfonate, and 3.0 g. sodium carboxymethylcellulose, the final pH being 8.0. Both gray and bleached hair were dyed similar shades of bluish violet having good fastness to shampooing and rubbing. The dye composition was also stored at 50 C. for 3 months and thereafter dyed hair identically to the initial dyeing in shade and strength.
  • Procedure B When Procedure B was used with the same dye, using 0.4 g. dye, 2.0 g. ethyleneglycolmonostearate, 2.0 g. methylcellulose, and lactic acid to pH 5.5, the bleached hair was dyed strongly and the gray hair moderately, in level bluish violet shades, fast to shampooing.
  • Example 89 The dye which is the product of Example 14 was applied according to Procedure A, using 0.2 g. dye, 3.0 g. isopropanolamine as the alkaline agent, 4.0 g. coconut acid monoethanolamide (surfactant), 3.0 g. hydroxyethylcellulose, and citric acid to pH 7.5.
  • the dyeings were strong orange shades, similar on both kinds of hair, and fast to shampooing and rubbing. When the pH was adjusted to 9.5, the dyeings were similar.
  • Example 90 The product of Example 17 was dyed according to Procedure A, using 0.1 g. dye, 4.0 g. triethanolamine (alkali), 0.75 g. sodium N methyl-N-oleoyltaurate (surfactant) and 3.0 g. sodium carboxymethylcellulose, and adjusting the pH to 10. A heavy red shade on both kinds of hair was obtained which was only slightly reduced after 3 shampooings. The dye composition was stable on storage at 50 C. for 3 months; thereafter it dyed hair in the same shade and strength as initially.
  • alkali triethanolamine
  • surfactant 0.75 g. sodium N methyl-N-oleoyltaurate
  • 3.0 g. sodium carboxymethylcellulose 3.0 g. sodium carboxymethylcellulose
  • Procedure C was followed with 0.1 g. of the same dye and gave a red dyeing somewhat weaker than the dyeing mentioned in the first paragraph, but still moderately strong and uniform on both kinds of hair.
  • Example 91 The dye product of Example 24 was dyed according to Procedure A: 0.2 g. dye was combined with 3 g. ethanolamine (alkali), 3 g. sodium N-coconut acid N-methyl taurate (surfactant) and 2 g. methylcellulose, at pH 8.5. The dyeings were strong reds on both gray and bleached hair, fast to shampooing and rubbing. When, by Procedure A, 0.2 g. dye was combined with 4 g. 3,3'-imino dipropylamine, 2 g. sodium lauryl sulfate and 3 g. methylcellulose at pH 9.5, very similar dyeings were obtained. Again, by Procedure A, for 0.2 g. dye, using 9 g.
  • the same dye was applied by Procedure B, in the following compositions: (a) 0.25 g. dye, 3 g. polyethoxylatednonylphenol, 3 g. methylcellulose, and sulfuric acid added to pH 5; (b) 0.25 g. dye, 0.5 g. ethyleneglycol monostearate, 2 g. dicoco dimethyl ammonium chloride, 1 g. cetyl stearyl alcohol, and citric acid added to pH 7. Red dyeings were obtained in both kinds of hair, of same shade, and almost as strong, as the first dyeing above obtained by Procedure A. The dyeings were fast to shampooing and rubbing.
  • Example 92 The dye product of Example 32 was dyed by Procedure A, using 0.25 g. dye, 2.0 g. N-phenyldiethanolamine (alkali), 3.0 g. coconut diethanolamide (surfactant) and 1.0 g. co-polymer of acrylic acid and allylsucrose (thickener) the pH being set at 9.0. The color on hair was bluish violet, the affinity being high on gray hair and very high on bleached. Shampoo fastness was excellent. The dye bath stored at 50 C., for 3 months, gave no change in shade and strength of dyeing thereafter.
  • alkali N-phenyldiethanolamine
  • surfactant 3.0 g. coconut diethanolamide
  • 1.0 g. co-polymer of acrylic acid and allylsucrose (thickener) the pH being set at 9.0.
  • the dye bath stored at 50 C.,
  • Example 93 The dye product of Example 41 was applied to hair by Procedure A, using 0.15 g. dye, 3.5 g. 1,3-diaminopropane (as alkaline agent), 1.0 g. sodium lignosulfonate (surfactant), and 3.0 g. hydroxyethylcellulose (thickener and setting the pH at 8.0. Both gray and bleached hair were dyed equally strong shades of orange, very fast to successive shampooings. The dye bath was stable on 3 months storage at 50 C.
  • this dye 0.2 g., with 2.0 g. polyethoxylated octyl phenol and 2.0 g. hydroxyethylcellulose at a pH of 6.5 effected by addition of formic acid, gave equal uniform orange dyeings of the two kinds of hair fast to shampooing.
  • Example 94 The product of Example 50 was dyed by Procedure A using 0.1 g. dye, 2.0 g. 3,3'-imino-dipropylamine (as alkaline agent), 3.0 g. mixed fatty acids diethanolamide (as surfactant), and 2.0 g. sodium alginate (as thickener), the pH being adjusted to 9.0.
  • the gray and bleached hair were both dyed a similar, level red shade of good strength, which was fast to successive shampoos.
  • the dye compositions remained unchanged after three months storage at 50 C., after which time it dyed hair in the same shade and strength as initially.
  • Procedure A was again followed with this dye, using 0.1 g. dye, 1.5 g. diethylenetriamine (alkaline agent), 2.0 g. N-lauryl myristyl beta-aminopropionic acid (surfactant), and 1.0 g. methylcellulose, at a pH of 8.0.
  • the dyeings were similar to those above.
  • Example The dye product of Example 61 was applied to hair by Procedure A, using 0.2 g. dye, 1.5 g. ethylenediamine (alkaline agent), 0.75 g. sodium lauryl sulfate surfactant), and 2.5 g. sodium carboxymethylcellulose, at a pH of 9.5. A strong level orange dyeing was obtained on both kinds of hair, fast to shampooing and rubbing.
  • Example 96 The product of Example 62 was dyed variously according to- Procedure A, using 0.25 g. dye.
  • the alkaline agent was 0.5 g. triethanolamine
  • the surfactant was 2.0 g. sodium N-oleoyl-N-methyltaurate
  • the thickening agent was 3.0 g. sodium carboxymethylcellulose, the pH being adjusted to 7.5.
  • 2.0 g. N-phenyldiethanolamine 2.5 g. polyoxyethylene lauric ester, and 3.0 g. sodium carboxymethylcellulose; and the pH was 8.5.
  • very similar red dyeings were obtained, of about the same shade and strength on the two kinds of hair, and fast to shampooing.
  • Example 97 The dye product of Example 74 was applied to hair by Procedure A using 0.15 g. dye, 3.0 g. diisopropanolamine, 3.0 g. lauric diethanolamide, and 3.0 g. methylcellulose, at pH 8.5. An excellent maroon dyeing was obtained of high strength and levelness, fast to three successive shampooings. When in this procedure there was used 2.0 g. 1,3-diaminopropane, 3.0 g. glyceryl stearate and 3.0 g. methylcellulose, at pH 9.0, the dyeings were essentially similar in shade, strength and fastness. When the above dye compositions were stored at 50 C. for 3 months and then dyed on hair again, the dyeings were similar to the initial dyeings in shade and strength.
  • the dye was also applied by Procedure B using 0.15 g. dye, 2.0 g. ethylene glycol monostearate, and lactic acid added to give pH 5.0.
  • the bleached hair was dyed strongly maroon, the gray hair being dyed a similar but weaker shade.
  • the same procedure was followed using the following ingredients: 1.0 g. polyethoxylated coconut fatty acid amide, 3.0 g. di-coco dimethyl ammonium chloride, 2.0 g. hydroxyethylcellulose, and citric acid to give pH 6.5. Moderately strong maroon dyeings were obtained, with the bleached hair being dyed stronger than the gray.
  • Example 98 The product of Example 76 was dyed on hair by Pro cedure A, using 0.2 dye and the following adjuvants: 2.5 g. diethylenetriamine, 2.0 g. polyoxyethylene lauric ester and 3.0 g. gum arabic; the pH was adjusted to 8.5. The hair was colored strongly violet, similarly on gray as on bleached hair, and the shampoo fastness was very good. Almost as strong a violet dyeing was obtained by using the following adjuvants: 3.0 g. ethanolamine, 3.0 g. coco- 37 nut fatty acid diethanolamide, and 3.0 g. sodium carboxymethylcellulose, at pH 8.5. Somewhat weaker violet dyeings, but still very level and fast to shampooing, were obtained with the following: 30 g. triisopropanolamine, 3.0 g. coconut fatty acid diethanolamide and 3.0 g. sodium carboxymethylcellulose, at pH 8.0.
  • Example 99 The dye product of Example 81 was applied by Procedure A using 0.15 g. dye and several combinations of adjuvants, as follows:
  • the dyeings were all strong level maroon shades, similar in shade and strength on both kinds of hair.
  • the dyeings (1) above were particularly heavy, as compared to (2), (3) and (4) which were all essentially alike.
  • Example 100 The product of Example 82 was dyed on hair by Procedure A, using 0.15 g. dye and the following combinations of adjuvants:
  • the dyeings were a purple shade of very good strength, which were fast to three successive shampooings.
  • the dyeings were in moderately strong purple shades, fast to shampooing and rubbing.
  • the same dye was also applied by Procedure C and gave moderately strong purple dyeings.
  • the dye was shown to be completely stable in the peroxide composition, since when it was dyed by Procedure C but without peroxide (substituting an equal volume of water), it gave the same shade and strength as when dyed with peroxide.
  • sucrose copolymer nonylphenol. sucrose copolymer.
  • methyl taurate methylcellulose.

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Cited By (56)

* Cited by examiner, † Cited by third party
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DE2340219A1 (de) * 1972-08-09 1974-02-21 Bristol Myers Co Haarfaerbe- und konditionierungsmittel
US3804586A (en) * 1967-05-16 1974-04-16 Oreal Dyeing hair with aqueous solution of nitro p-phenylenediamines and composition therefor
US3836326A (en) * 1970-11-18 1974-09-17 Gillette Co Dyeing hair with nitro-substituted phenylene compounds
US3909190A (en) * 1972-08-21 1975-09-30 Henkel & Cie Gmbh Hair dyeing process and composition containing {60 -cyano-methanesulfonamido-nitrobenzene derivatives
US3930792A (en) * 1972-08-09 1976-01-06 Clairol Incorporated Hair dyeing and conditioning compositions
US3944612A (en) * 1967-11-02 1976-03-16 Clairol Incorporated 4-Fluoro-3-nitro anilines
US4060544A (en) * 1972-12-27 1977-11-29 Gaf Corporation N-2-[N-(keto-tert-alkyl carbamyl)alkyl]phenylamines
DE3534369A1 (de) * 1984-09-27 1986-04-03 Oreal Faerbemittel fuer keratinfasern, das mindestens ein n-substituiertes 2-nitro-p-phenylendiamin enthaelt, und faerbeverfahren fuer keratinfasern
US4629467A (en) * 1984-01-26 1986-12-16 Wella Aktiengesellschaft Use of p-ureidoalkylamino-nitrobenzene derivatives in hair dyeing compositions and new p-ureidoalkylamino-nitrobenzene derivatives
US4637821A (en) * 1981-10-08 1987-01-20 L'oreal Tinctorial composition for keratin fibres, based on nitrated benzene dyestuffs
JPH01132512A (ja) * 1987-10-15 1989-05-25 Unilever Nv ヘアトリートメント製品
US4900869A (en) * 1985-12-05 1990-02-13 Aktiengesellschaft Wella Process for the production of 4-[ethyl-(2'-hydroxyethyl)-amino]-1-[(2'-hydroxyethyl)-amino]-2-nitrobenzene
US4992589A (en) * 1984-07-20 1991-02-12 Hoechst Aktiengesellschaft Substituted phenyl hydroxyethyl sulfones, and process for their preparation
US5041143A (en) * 1984-10-09 1991-08-20 L'oreal N,N'-disubstituted nitro-para-phenylenediamines, and dyeing compositions containing the same
US5387716A (en) * 1991-12-20 1995-02-07 Cassella Aktiengesellschaft N4-substituted 1-alkoxy-2-acylamino-4-aminobenzenes, process for their preparation and their use
US5496377A (en) * 1993-12-22 1996-03-05 L'oreal Process for the direct dyeing of keratinous fibres using water vapor
US6441045B1 (en) * 1997-12-08 2002-08-27 Bernardo Birnbaum Disinfectant composition
US20040102616A1 (en) * 2001-04-26 2004-05-27 Gunter-Rudolf Schroder Novel reactive dyes and use thereof for dyeing substrates containing nucleophilic groups
US20050097684A1 (en) * 2003-11-12 2005-05-12 Saroja Narasimhan Methods, compositions, and kits for coloring hair
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US7901464B2 (en) 2007-12-21 2011-03-08 L'oreal S.A. Process for lightening direct dyeing or oxidation dyeing in the presence of at least one organic amine, device therefor and anhydrous composition
US7927382B2 (en) 2008-12-19 2011-04-19 L'oreal S.A. Ready-to-use composition for the oxidation dyeing of keratin fibers comprising at least one fatty substance, at least one oxidation chosen from 4,5-diaminopyrazoles and acid addition salts thereof, at least one additional dye precursor other than the at least one oxidation base, at least one oxidizing agent, and optionally at least one alkaline agent, and processes and kits therewith
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US20110158925A1 (en) * 2009-12-22 2011-06-30 Jean-Marc Ascione Dyeing or lightening compositions comprising at least one fatty substance and at least one amphoteric polymer
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IT941503B (it) 1973-03-10
GB1150445A (en) 1969-04-30
FR1517715A (fr) 1968-03-22
DE1693051B2 (de) 1977-09-01
DE1693051C3 (de) 1978-05-24
DE1693051A1 (de) 1971-04-15
CH475006A (de) 1969-07-15
SE347431B (cs) 1972-08-07

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