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Publication numberUS3909190 A
Publication typeGrant
Publication dateSep 30, 1975
Filing dateAug 16, 1973
Priority dateAug 21, 1972
Also published asDE2241015A1
Publication numberUS 3909190 A, US 3909190A, US-A-3909190, US3909190 A, US3909190A
InventorsFerdi Saygin
Original AssigneeHenkel & Cie Gmbh
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hair dyeing process and composition containing {60 -cyano-methanesulfonamido-nitrobenzene derivatives
US 3909190 A
Abstract
Hair dyeing processes and compositions containing alpha -cyano-methanesulfonamido-nitrobenzene compounds having the formula YNH-SO2-CH2-CN where Y represents hydrogen, chlorine, bromine or an alkoxy having 1 to 4 carbon atoms and Z represents NH2 or OH, and wherein the processes of dyeing hair use these compounds directly or in combination with couplers for oxidation dyeing.
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United States Patent [191 Saygin 1451 Sept. 30, 1975 [75] Inventor: Ferdi Saygin, Dusseldorf, Germany [73] Assignee: Henkel & Cie G.m.b.I-I., Dusseldorf,

Germany [22] Filed: Aug. 16, 1973 [21] Appl. No.: 388,728

[301 Foreign Application Priority Data Aug. 21, 1972 Germany 2241015 [52] U.S. C1. 8710.1; 8/10; 8/10.2; 8/11; 8/32; 260/465 E; 424/70 1511 Int'. C1. A6lK 7/13 [58] Field of Search 260/465 E; 8/102, 10, 8/101, 11, 32; 96/100 [56] References Cited UNITED STATES PATENTS 2,441,491 5/1948 Kendall et a1 96/100 X 3,388,148 6/1968 Altman 8/10.] X 3,629,330 12/1971 Brody et a1. 8/101 X 3,649,160 3/1972 Kalopissis et a1 8/10..2 3,702,861 11/1972 Howe .I 260/465 E 3,781,323 12/1973 Wagner ct a1 1. 260/465 E Primary Examiner-Albert T. Meyers Assistant ExaminerVera C Clarke Attorney, Agent, or FirmHammond & Littell 5 7 ABSTRACT Hair dyeing processes and compositions containing a-cyano-methanesulfonamido-nitrobenzene compounds having the formula where Y represents hydrogen, chlorine, bromine or an alkoxy having 1 to 4 carbon atoms and Z represents N11 or OH, and wherein the processes of dyeing hair use these compounds directly or in combination with couplers for oxidation dyeing.

8 Claims, No Drawings I HAIR DYEING PROCESS AND COMPOSITION CONTAINING v a-CYANO-METHANESULFONAMIDO- NITROBENZENE DERIVATIVES wherein Y is a member selected from the group consist- 5 OBJECTS OF THE INVENTION An object of the present invention is the develop ment of an a-cyano-methanesulfonamido-nitrobenzene compound having the formula NH,-SO CH CN wherein Y is a member selected from the group consisting of hydrogen, chloro, bromo, and alkoxy having 1 to 4 carbon atoms, and Z is a member selected from the group consisting of amino and hydroxyl.

Another object of the invention is the development of an aqueous preparation for the direct dyeing of human hair consisting essentially of 1) from 0.1% to 5% by weight of the above a-cyano-methanesulfonamido-nitrobenzene compounds; (2) from 0% to 30% by weight of a surfactant; (3) from 0% to 25% by weight of a thickener; and (4) from 40% to 99.9% by weight of water.

A further object of the invention is the development of an aqueous preparation for the dyeing of human 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 coupling component consisting essentially of the above wcyano-methanesulfonamido-nitrobenzene compounds; (2) from 0% to 30% by weight of a surfactant; (3) from O to 25% by weight of a thickener; and (4) from 40% to 99.8% by weight of water.

A yet further object of the inventionis the development of a process for dyeing human hair consisting essentially of applyingto said hair at temperatures ranging from about 150 to 40C for a time sufficient to effect dyeing, an effective amount of either of the above aqueous preparations.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION The present invention provides novel oz-cyanomethanesulfonamido-nitrobenzene compounds having the formula Examples of compounds of the described type are:.-

2-amino-3-( cx-cy'ano-methanesulfonamido l -nitrobenzene, 1 2-amino-4-( a-cyano-methanesulfonamido 1 -nitrobenzene, 1-amino-4-( a-cyano-methanesulfonamido )-2-nitro benzene,

methanesulfonamido)-3-nitro-benzene, l-amino-5-( a-cyano-m'ethanesulfonamido ).-4-

methoxy-2-nitro-benzene, 2-amino-3-chloro-4-(a-cyanomethanesulfonamido l -nitro-be nzene, 1-amino-3-(a-cyano-methanesulfonamido )-2-nitrobenzene, 1-arnino-2-( a-cyano-methanesulfonamido )-4-nitrobenzene, 2-aminol a-cyano-methanesulfonamido )-4-nitrobenzene, l-amino-5-brOmo-2-(a-cyanome'thanesulfonamido )-4-nitrO-benzene, l-amino-2-( a-cyano-methanesulfonamido )-3-nitrobenzene, l-amino-3-( oz-cyano-methanesulfonamido )-5-nitrobenzene, l-amino-2-chloro*3-(a-cyanomethanesulfonamido )-5-nitro-benzene, l-amino-2-butOxy-4-(a-cyanomethanesulfonamido )-5-nitro-benzene, 4-amino-2-( a-cyano-methanesulfonamido l -nitrobenzene, 2-aminol -ethoxy-4-( a-cyanomethanesulfonamido)-5-nitro-benzene, 2-( a-cyano-memthanesulfonamido )-4-nitro-phenol, 2-(a-cyano-methanesulfonamido )-6-nitro-phenol 4-chloro-2-( a-cyano-methanesulfonamido)-6-nitrophenol, 2-(oz-cyano-methanesulfonamido )-3-methoxy-6- nitro-phenol, 6-chloro-2-( a-cyano-methanesulfonamido)-4-nitrophenol, 2-(a-cyano-methanesulfonamido)-5-nitrO-phenol, 4-bromo-S-( a-cyano-methanesulfonamido )'2-nitrophenol, 4-(a-cyano-methanesulfonamido)-2-nit'rophenol, 3-( a-cyano-methanesulfonamido )-2-nitrO-phenol, 2-(a-cyano-methanesulfonamido)-5-nitro-phenol, 2-(a-cyano-methanesulfonamido)-3-methoxy-5- nitro-phenol, 5-chloro-2-(a-cyano-methanesulfonamido)-4-nitrophenol, 2-(a-cyano-methanesulfonamido)-3-nitro-phenol, 5-butoxy-2-(a-cyano-methanesulfonamido)-3-nitrophenol, 3-(oz-cyano-methanesulfonamido)-5-nitro-phenol,

2-bromo-4-( a-cyano-methanesulfonamido )-3-nitrophenol, 2-ethoxy-5-(oz-cyano-methanesulfonamido)-4-nitrophenol. The compounds in accordance with the invention may be produced by reacting the corresponding nitroamino-phenols or diamino-nitro-benzenes, substituted if required, wiith the stoichiometric quantity of chlorosulfonyl acetonitrile required for the monosubstitution of an amino group. Advantageously, reaction is effected in the presence of a solvent such as aliphatic hydrocarbons, benzene, chlorobenzene, tetrahydrofuran, in such a manner that the chlorosulfonyl acetonitrile dissolved in the particular solvent is added to the nitroamino-phenols or diamino-nitrobenzenes drop by drop while cooling with ice. After the said substances have been added, the reaction mixture is maintained for a few hours at room temperature under agitation and is subsequently poured into water and the reaction product, obtained in the form of an oil or in solid form, is separated. The a-cyano-methanensulfonamidonitrobenzene reaction products can be purified by recrystallization from ethanol.

The compounds in accordance with the invention are valuable hair dyes. They may be used as direct dyes which produce yellows of various tints. Compared with the starting substances used for their production, which are known as direct dyestuffs, they are characterized by better absorption and fastness properties, and also provide widely differing tints.

Furthermore, the compounds in accordance with the invention can be used as yellow couplers in oxidation dyes in combination with conventional developer substances, and the color tints obtainablecan be varied by means of the developer components, and the intensity of the oxidation can be varied through various tints of yellow to brown.

Consequently, a further object of the invention is the use of compounds of the general formula in which Y represents hydrogen, chlorine, bromine, or an alkoxy group having 1 to 4 carbon atoms, and Z represents an NH or OH-group in preparations for dyeing hair.

In another aspect, therefore, the invention provides an aqueous preparation for the direct dyeing of human hair consisting essentially of (1) from 0.1% to 5% by weight of the above a-cyano-methanesulfonamidonitrobenzene compounds; (2) from to 30%, preferably 0.5% to 30%, by weight of a surfactant; (3) from 0% to 25%, preferably 0.1% to 25%, by weight of a thickener; and (4) from 40% to 99.9%, preferably 40% to 99.3%, by weight of water; as well as an aqueous preparation for the dyeing of human hair consisting essentially of l 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 coupling component consisting essentially of the above a-cyano-methanesulfonamidonitrobenzene compounds; (2) from 0% to 30%, preferably 0.5% to 30%, by weight of a surfactant; (3) from O to 25%, preferably 0. 1% to 25%, by weight of a thickener; and (4) from 40% to 99.8%, preferably 40% to 99.3%, by weight of water.

Either of the above preparations can be used in the process for dyeing human hair consisting essentially of applying to said hair at temperatures ranging from about 15 to 40C for a time sufficient to effect dyeing, an effective amount of either of the above aqueous preparations.

A particular embodiment of this subject of the invention relates to the use of compounds of the abovementioned formulas in combination with conventional developer substances in preparation for the oxidative dyeing of hair.

In this instance, suitable developer substances are the compounds which are normally used for this purpose. The most important examples are primary aromatic amines having a further functional group in the paraposition, or else a 4-aminopyraz0lone.

Preferred 4-aminopyrazolones are compounds of the generic formula wherein R and R are hydrogen or an organic radical having 1 to 10 carbon atoms.

The organic radical R, can be an alkyl having 1 to 10 carbon atoms, an aryl, such as phenyl, hydroxyphenyl, sulfonylphenyl, sulfonamidophenyl, aminophenyl, lower alkylolphenyl, lower alkylphenyl, lower alkylaminophenyl and di-lower alkylaminophenyl where the alkyls and alkylols have 1 to 4 carbon atoms, or a heterrocyclic radical, such as the pyridyl. Functional groups may be present, particularly on the aryl, as indicated above, such as OH, NH NHCH N(CH or halogen atoms, i.e., fluorine, iodine, bromine, and particularly chlorine. Furthermore, the following groups may be present as organic radicals: COOH, COOR', CONH CONHR', CONR'R", wherein R and R are alkyl or hydroxyalkyl having 1 to 4 carbon atoms.

The organic radical R can be an alkyl having 1 to 10 carbons, an aryl, such as those mentioned above for R or a heterocyclic radical, such as the pyridyl. Functional groups may be present. Particularly, hydrocarbon radicals having 1 to 10 carbons are applicable containing as functional groups OH, NH COOH, CONH SO H and SO NH As aromatic radical, a phenyl is especially applicable. It may be substituted with alkyl or hydroxyalkyl groups having 1 to 4 carbons or other substituents, such as halogen, preferably Cl, NH OH, COOH, CONH- CONHR', CONR'R", SO H and SO NH It frequently is opportune to employ the 4- aminopyrazolone in the form of their water-soluble acid addition salts, such as the hydrochloride, sulfate or oxalate, because the resistance to atmospheric air is increased.

4- Aminopyrazolones which are suitable as develop- .ers in the process of the invention are as follows:

l-ethyl-4-aminopyrazolone l-n hexyl-4-aminopyrazolone l-n-decyl4-aminopyrazolone l-phenyl-4-arninopyrazolone l-( p-hydroxyphenyl )-4-aminopyrazolone l-(p-sulfonylphenyl )-4-aminopyrazolone 3-methyl-4-aminopyrazolone 3-i-propyl-4-aminopyrazolone 3-n-octyl-4-aminopyrazolone 3-phenyl-4-aminopyrazolone 3-(p-ethylphenyl)-4-aminopyrazolone B-(p-aminophenyl )-4-aminopyrazolone 3-(p-dimethylaminophenyl)-4-aminopyrazolone 3-( m-chloropheny] )-4-aminopyrazolone 3-(4-pyridyl)-4-aminopyrazolone 1-methyl-3-phenyl-4-aminopyrazolone l-ethyl-3-(o-hydroxyphenyl )-4-aminopyrazolone l-n-decyl-3-(p-methylaminophenyl)-4- aminopyrazolone l-phenyl-3-n butyl-4-aminopyrazolone l-(p-sulfonamidophenyl)-3-n-octy1-4- aminopyrazolone l-( p-sulfonamidophenyl)-3-phenyl-4- aminopyrazolone l p-ethylphenyl )-3-phenyl-4-aminopyrazolone l-(p-beta-hydroxyethylphenyl )-3-phenyl-4- aminopyrazolone l-(p-hydroxyphenyl )-3-n-octyl-4-aminopyrazolone l-( p-hydroxyphenyl )-3-n-octyl-4-aminopyrazolone 1-( pcarboxyphenyl )-3-n-octyl-4-aminopyrazolone l-( p-carbamidophenyl)-3-n-octyl-4- aminopyrazolone 4-aminopyrazolone-3-carboxylic acid 4-aminopyrazolone-3-carboxylic acid-ethyl ester 4-aminopyrazolone-3-carboxylic acid-mbutyl ester 4-aminopyrazolone-3-carboxylic acid-methylamide 4-aminopyrazolone-3-carboxylic acidhydroxymethylamide 4-aminopyrazolone-3-carboxylic acid-di-nbutylamide acid-ethyl-betaacid-n- 1-n-butyl-4-aminopyrazolone-3-carboxylic acidmethyl ester l-n-hexyl 4-aminopyrazolone-3-carboxylic acidethyl ester l-n-heptyl-4-aminopyrazolone-3-carboxylic acid l-n-decyl-4-aminopyrazolone-3-carboxylic acid-di-npropylamide l-n-decyl-4-aminopyrazolone-3-carboxylic beta-hydroxyethyl ester l-phenyl-4-aminopyrazolone-3-carboxylic acid l-phenyl-4-aminopyrazolone-3-carboxylic acid-ethyl ester acidl-phenyl-4-aminopyrazolone-3-carboxylic acid-B- hydroxyethyl ester 1-phenyl-4-aminopyrazolone-3-carboxylic acidamide acidacidtional group in para-position are, e.g., pphenylenediamine, p-toluylenediamine, pdiaminoanisole, p-methylaminoaniline, pethylaminoaniline, p-aminodiphenylamine, pdimethyaminoaniline, p-diethylaminoaniline, p-dibeta-hydroxyethylaminoaniline, p-aminophenol, p-

diaminoanisole, or compounds of the kind named which additionally contain one or more functional groups such as OH, NR NHR', NR'R, where R and R" again are lower alkyls or hydroxyalkyls having 1 to 4 carbon atoms.

Preferably, these aromatic biand polyfunctional amines have the formula wherein Y is a member selected from the group consisting of OH, NH NHR', NR'R and NHC l-l and Z is a member selected from the group consisting of H, R, Y and OR, where again R and R are alkyls or hydroxyalkyls having 1 to 4 carbon atoms.

Further suitable developers include diamino pyridine and its derivatives, for example 2,5-diamino-pyridine, and heterocyclic hydrazone derivatives, for example pyridone hydrazones such as l-ethyl-pyridone-Z- hydrazone.

The coupling components according to the invention are suitably used in substantially equimolar quantities with respect to the developers used. However, it is also possible to employ the coupling component in a certain excess over the stoichiometric amount or in a certain lesser quantity than the stoichiometric amount. Both the coupling components and the developers may be mixtures of compounds of the above-mentioned kind.

The oxidative coupling, that is, the development of the dyeing, may also be effected according to known procedures such as by the oxygen of the air. However, chemical oxidizing agents are suitably used, especially hydrogen peroxide orits adducts with urea, melamine and sodium borate, as well as mixtures of such hydrogen peroxide adducts with potassium peroxydisulfate.

The compounds according to the invention may be present in the form of aqueous preparations, such as solutions or emulsions. Such preparations should contain the direct'dye or the dyestuffs combination of coupling component and developer component in amounts of from 0.1% to by weight, preferably 0.1% to 2% by weight.

The compounds according to the invention may be applied in the form of creams or emulsions. For this purpose the direct dyes, or mixtures of oxidative dyestuffs combinations of developers and couplers may be mixed with the ingredients usually present in such preparations. Such ingredients include any anionic or nonionic wetting agents or detergents such as for example, alkylbenzenesulfonates, fatty alcohol sulfates, higher alkylsulfonates, higher fatty acid ethanolamides, or ethylene oxide adducts on higher fatty acids, higher fatty alcohols or alkylphenols. Further, such preparations may contain thickeners, as for example, methylcellu: lose, starch and also higher fatty alcohols, paraffin oil and fatty acids, as well as perfume oils or hair treatment agents, for example pantothenic acid and cholesterol,

The additives are utilized in the amounts effective for this purpose. An effective amount of a wetting agent or surfactant added is especially from 0.5% to 30% by weight; and an effective amount of a thickening agent added is from 0.1% to 25% by weight, calculated in each case on the total composition. The concentration of the direct dye or the dyestuffs combinations in such cream or emulsion preparations is from 0.1% to. 5% by weight preferably 0.2% to 2%, based upon the .total composition, depending on the purpose for which the agent is to be used. The application of the direct dye or dyestuffs combinations may be effected at temperatures between C and 40C preferably room temperature, in weakly acid, neutral or preferably alkaline medium.

The dyeings obtained have the advantages of a good light fastness, a good washing fastness and a good fastness to rubbing. A special advantage of the hair dyes according to the invention is that they may be used both in direct dyeing and as coupling components in oxidation dyestuffs to obtain yellow colorations.

The following examples are merely illustrative of the 3 present invention without being deemedlimitative in any manner thereof.

EXAMPLE 1 a v l-amino-b 2-( a-cyano-methanesulfonamido)-4-nitro-benzene 8 Melting point: 185 to 187C Analysis. Molecular Weight calculated for C H N O S.

Calculated: C 37.50%; H 3.12%; N 21.88%. Found: C 37.72%; H 2.86%; N 22.07%.

EXAMPLE 2 4-amino-2-( a-eyano-methanesulfonamido l -nitrobenzene calculated for EXAMPLE 3 1-amino'-4-( a-cyano-methanesulfonamido )-2-nitrobenzene 15.3 gm (0.1 mol) of 1,4-diamino-2-nitro-benzene dissolved in 200 ml of absolute tetrahydrofuran, and 14 gm (0.1 mol) of chlorosulfonyl acetonitrile dissolved in 50 ml of absolute tetrahydrofuran were reacted in the manner described in Example 1. The reaction product was recrystallized from ethanol. The precipitate filtered off was washed with a little ether and was subsequently recrystallized again from water.

Melting point: 157 to 162C. Analysis. Molecular weight C H N O S. I

Calculated: C 37.50%; H 3.12%; N 2l.88%. I Found: C 37.51%; H 2.79%, N 22.07%.

calculated for EXAMPLE 4 4-chloro-2-( a-cyano-methanesulfonamido)-6-nitrophenol '1 8.8 gm (0.1 mol) of 2-amino-4-chloro-6-nitrophenol suspended in ml of absolute tetrahydrofuran, and 14.0 gm (0.1 mol) of chlorosulfonyl acetonitrile dissolved in 50 m1 absolute tetrahydrofuran, were reacted in the same manner as described in Example 1.

The precipitate was recrystallized twice from ethanol.

Melting point: 174 to 177C Analysis, Molecular weight calculated for 'Calculated; C 32.93%; H 2.19%; H 14.41%.

Found: C 33 .5l%; H 2.06%; N 14.53%.

EXAMPLE 5 6-ch'lor'o- 2-("oz-cyano-methanesulfonamido )-4-nitrophenol 18.8 gm (0.1 mol) of 2-amino-6-chloro-4-nitrophenol suspended in 100 ml of absolute tetrahydrofuran, and 14.0 gm 0.1 mol) of chlorosulfonyl acetonitrile dissolved in 50 ml of absolute tetrahydrofuran, were reacted in the same manner as described in Exam- EXAMPLE 6 calculated for 2-( a-cyano-methanesulfonamido )-4-nitro-phenol 15.4 gm (0.1 mol) of 2-amino4-nitro-phenol dissolved in 100 ml of absolute tetrahydrofuran, and 14.0 gm (0.1 mol) of chlorosulfonyl acetonitrile dissolved in 50 ml of absolute tetrahydrofuran, were reacted in the l 5 EXAMPLE 7 4-( a-cyano-methanesulfonamido)-2-nitro-phenol 15.4 gm 1.0 mol) of 4-amino2-nitro-phenol dissolved in 100 ml of absolute tetrahydrofuran, and 14.0 gm (0.1 mol) of chlorosulfonyl acetonitrile dissolved in 50 ml of absolute tetrahydrofuran, were reacted in the same manner as described in Example 1. The precipitate was recrystallized from ethanol.

Melting point: 150 to 155C Analysis. Molecular weight calculated for CHHTNSOSS. 35

Calculated: C 37.36%; H 2.74%; N 16.34%. Found: C 37.71%; H 2.74%; N 16.29%.

EXAMPLE 8 2 parts by weight of 1-amino-2-(oz-cyano-methanesulfonamido)-4-nitro-benzene were incorporated in a cream base of the composition:

10 parts by weight of fatty alcohols C to C 10 parts by weight of fatty alcohol sulfate (commercial mixture C to C 75 parts by weight of water. and the pH value of the mixture was adjusted to 9.5 by adding ammonia. This emulsion was made up to 100 parts by weight with water. The dyeing cream thus obtained was applied to human hair which has turned grey naturally, and was allowed to act for 30 minutes at room temperature. The hair was subsequently washed and dried. The result was hair which had been dyed a deep yellow color.

EXAMPLES 9 to 14 Using the same procedure as stated in Example 8, but with the use of the dye components in Examples 2 to calculated for 20 7, listed in the following Table, the hair colors given in the same line were obtained.

Ex. Hair Color No. Dye component obtained 9 4-amino-2-(a-cyano-methanesulfonamido)-1-nitro-benzene olive yellow 10 1-amino-4-( a cyano-methanesulfonamido )-2-nitro-benzene topaz-yellow l l 4-ch1oro-2-(a-cyano-methanesulfonamido )-6-nitro-phenol l2 6-chloro-2-(a-cyano-methanesulfon pompeian yellow amido)-4-nitro-phenol honey yellow 1 3 2(a-cyano-methanesulfonamido )-4- nitro-phenol olive yellow 14 4-(a-cyano-methanesullonamido )-2- nitro-phenol ivory EXAMPLE 1 5 Equimolar quantities of 4-amino-1-phenyl-3-carbamoyl-pyazolone-S acting as a developer component, and 1-amino-2-(a-cyano-methanesulfonamido )-4-nitrobenzene acting as a coupler component, were emulsified in a cream base as described in Example 8. The molar concentrations are so calculated that, assuming 100% reaction upon the subsequent oxidative coupling reaction, 2 gm of dye are present in 100 gm of cream (corresponding to a 2% concentration of dye).

The emulsion was adjusted to a pH value of 9.5 by adding ammonia and was subsequently made up to 100 parts by weight with water. The dyeing cream thus obtained dyed human hair mustard brown to yellowist brown within 30 minutes by virtue of the action of the atmospheric oxygen or a 1% or 9% solution of hydrogen peroxide. The various tints of color were obtained in accordance with the oxidation. agents used (or their different concentrations).

EXAMPLES 16 to 52 Following the same procedure as in Example 15, but with the use of the developers and couplers given in the following Table as dye components (a) and (12), human hair which had turned grey naturally was dyed and the colors given in the last column were obtained (with atmospheric oxygen and a 1% and a 9% H 0 solution). The dye components were used in equimolar quantities. The total quantity of the dye to be formed was 2 gm in 100 gm of the cream base in each case, and the reaction time was 30 minutes at room temperature.

The developer components under a are abbreviated in the Table as follows:

4-amino-1-phenyl-3-carbamoyl-pyrazolone-5 A 4-amino-1-phenyl-3-ethoxycarbonyl-pyrazolone-5 B 4-amino-1H-3-ethoxycarbonyl-pyrazolone-5 C p-toluylene diamine D l-methy1-pyridone-Z-hydrazone E 1-methy1-quinolone-4-hydrazone F Ex- Dye components Tint of the dyed hair ample No. a) develb) coupler By air oxidation 1% H 0 solution 9% H 0 solution o er 16 B l-amino-2-( a cyanomethanesulfonamido) -4-nitro-benzene olive brown brass yellow reddish yellow 17 C ditto linoleum brown olive brown toffee brown 18 D ditto olive hrown nut brown hazelnut brown -Continued Ex- Dye components Tint of the dyed hair ample No. a) develb) coupler By air oxidation 1% H solution 9% H 0 solution oper 19 E ditto olive olive 20 F ditto yellowish brown yellowish brown light brown 21 A 4-amino-2-( a-cyanomethanesulfonamido) -l-nitro-benzene olive brown olive olive 22 B ditto olive brown honey yellow blonde 23 C ditto olive brown olive yellow olive yellow 24 D ditto olive brown dark brown linoleum brown 25 E ditto olive yellow olive green olive brown 26 F ditto olive yellow olive brown golden yellow 27 A l-amino-4-(a-cyanomethanesulfonamido) -2-nitro-benzene rust brown cocoa brown Titian red 28 B ditto cinnamon brown light brown autumn gold 29 C ditto brown cinammon brown autumn gold 30 D ditto autumn gold dark brown reddish brown 31 E l-amino-4-( a-cyanomethanesulfonamido) -2-nitro-benzene cognac brown dark brown dark brown 32 F ditto terra di Siena hazelnut brown dark brown 33 A Z-(a-cyano-methanesulfonamido) -4-chloro-6-nitrophenol somali brown fawn colored Titian red 34 B ditto brick red terra di Siena brownish orange 35 C ditto Titian red autumn gold reddish gold 36 D ditto brick red beaver brown umbra 37 E ditto brick red somali brown dark brown 38 F ditto reddish gold reddish gold autumn gold 39 A Z-(a-cyanomethanesulfonamidoJ--chloro- 4-nitro-phenol bronze brown bronze brown yellowish brown 40 B ditto olive brown olive brown dark yellow 4] C ditto yellowish brown olive brown dark yellow 42 D ditto olive brown rust brown yellowish brown 43 E ditto dark yellow yellow 44 A 2-( a-cyano-methanesulfonamido) -4-nitro-phenol olive brown brown bronze brown 45 ditto. khaki khaki greyish yellow 46 2(a-cyano-methanesulfonamido) -4-nitro-phenol clay colored honey yellow honey yellow 47 D ditto golden yellow rust brown linoleum brown 48 F ditto ochre yellow auburn 49 A 4-(a-cyano-methanesulfonamido) -2-nitro-phenol greyish brown greyish brown reddish grey 50 D ditto nougat brown nutria brown beaver brown 51 E ditto olive brown violet brown violet brown 52 F ditto Pompeian yellow brown brown group consisting of amino and hydroxyl; (2) from 0% The preceding specific embodiments are illustrative to 30% by weight of a surfactant selected from the of the practice of the invention. It is to be understood,

however, that other expedients known to those skilled 45 group consisting of an anionic wetting agent and a nonin the art, or disclosed herein, may be employed withionic wetting agent; (3) from 0% to 25% by weight of out departing from the spirit of the invention or the a thickener; and (4) from 40% to 99.9% by weight of scope of the appended claims. water.

I' claim: 2. The aqueous preparation of claim 1, wherein said 1. An aqueous preparation for the direct dyeing of 50 a-cyano-methanesulfonamido-nitrobenzene compound human hair consisting essentially of (1) from 0.1% to is selected from the group consisting of l-amino-2-(a- 5% by weight of an a-cyano-methanesulfonamidocyano-methanesulfonamido)-4-nitr0-benzene, 4- nitrobenzene compound having the formula amino-2-(a-cyano-methanesulfonamido)-l-nitro- 55 benzene, l-amino-4-( a-cyano-methanesulfonamido Z 2-nitro-benzene, 4-chloro-2-( a-cyano-methanesulfonamido )-6-nitro-phenol, 6-chloro-2-(a-cyanomethanesulfonamido )-4-nitro-phenol 2-'( a-cyano- Y NH SOCH CN methanesulfonamido)-4-nitro-phenol, and 4-(a-cyano I methanesulfonamido)-2-nitro-phenol.

3. A process for direct dyeing human hair consisting 2 essentially of applying to said hair at temperatures ranging from about 15C to 40C for a time sufficient to effect dyeing, an effective amount of the aqueous wherein Y is a member selected from the group consistpreparatons of clalm ing of hydrogen, chloro, bromo and alkoxy having 1 to 4 carbon atoms, and Z is a member selected from the 4. An aqueous preparation for the dyeing of human 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 coupling component consisting essentially of an a-cyano-methanesulfonamido-nitrobenzene compound having the formula wherein Y is a member selected from the group consisting of hydrogen, chloro, bromo and alkoxy having 1 to 4 carbon atoms, and Z is a member selected from the group consisting of amino and hydroxyl; (2) from to by weight of a surfactant selected from the group consisting of an anionic wetting agent and a nonionic wetting agent; (3) from O to 25% by weight of a thickener; and (4) from to 99.8% by weight of water.

5. The aqueous preparation of claim 4, wherein said a-cyano-methanesulfonamido-nitrobenzene compound is selected from the group consisting of l'-amino-2-( acyano-methanesulfonamido)-4-nitro-benzene, 4 amin- 0-2-( a-cyano-methanesulfonamido 1 -nitro-benzene, l-amino-4-( a-cyano-methanesulfonamido )-2-nitrobenzene, 4-chloro-2-(a-cyano-methanesulfonamido)- 6-nitro-phenol, 6-chloro-2-(a-cyano-methanesulfonamido)-4-nitro-phenol, Z-(a-cyano-methanesulfonamido)-4-nitro-phenol, and 4-(a-cyanomethanesulfonamido)-2-nitro-phenol.

6. The aqueous preparation of claim 4, wherein said developer component is selected from the group consisting of a 4-amino-pyrazolone, a water-soluble acid addition salt of said 4-amino-pyrazolone, an aromatic amine having at least one primary amino group and another functional group in the para-position, a diaminopyridine and a pyridone hydrazone.

7. The aqueous preparation of claim 4, wherein said developer component is selected from the group consisting of 4-aminol -phenyl-3-carbamoyl-pyrazolone-5 4-amino-1-phenyl-3-ethoxycarbonyl-pyrazolone-5, 4- aminolH-3-ethoxycarbonyl-pyrazolone-5, p-toluylene diamine, 1-methyl-pyridone-2-hydrazone and lmethyl-quinolone-4-hydrazone.

8. A process for dyeing human hair consisting essentially of applying to said hair at temperatures ranging from about 15 to 40C for a time sufficient to effect dyeing, an effective amount of the aqueous preparation of claim 4.

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4599450 *May 10, 1984Jul 8, 1986Hoechst AktiengesellschaftProcess for the preparation of acid nitro dyestuffs
US4980158 *Apr 4, 1989Dec 25, 1990Clairol IncorporatedNitroaniline dyes with a cyano substituent group
US5024673 *Oct 11, 1990Jun 18, 1991Clairol IncorporatedNitroaniline dyes with a cyano substituent group
US6503282 *Dec 16, 2000Jan 7, 2003Wella AktiengesellschaftComposition for coloring keratin fibers based on a developer-coupler combination characterized in that it contains as the coupler 3-(2,4-diaminophenoxy)-1-propanol and as the developer ring and having general formula (I)
US6537329 *Jan 21, 2000Mar 25, 2003L'oreal S.A.Intense colorations with a wide range of colours, excellent colorfastness
Classifications
U.S. Classification8/409, 8/410, 558/394, 8/408
International ClassificationC07C311/02, C07C311/00, C09B51/00
Cooperative ClassificationA61Q5/065, C09B51/00, A61K8/466
European ClassificationC09B51/00, A61Q5/06D, A61K8/46F