Indamines for dyeing keratinic fibers
United States Patent 1 Kalopissis et al.  
 [451 Apr. 8, 1975 1 INDAMINES FOR DYEING KERATINIC FIBERS Related U.S. Application Data [63] Continuation-impart of Ser. No. 180.455. Sept. 14.  
 1971, abandoned.  
 [30] Foreign Application Priority Data Sept. 18. 1970 France 70.34041 [52] U.S. Cl. 8/10; 8/101: 8/102;  
 424/D1G. l; 424/D1G. 2; 424/47; 424/71 [51] Int. Cl. HOlk l/12; D06p 3/04 [58] Field of Search 260/396 N, 270; 8/lO.1,  
 [56] References Cited UNITED STATES PATENTS 6/1914 Fischer 96/100 10/1965 Blanke et al 8/102 Primary Examiner-Stanley J. Friedman Assistant Examiner-Vera C. Clarke Attorney, Agent, or FirmCushman, Darby &amp; C ushman [57] ABSTRACT lmdamine having the formula wherein R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having l-4 carbon atoms lower alkoxy having l-4 carbon atoms. amino, acylamino wherein the acyl moiety has 1 to 4 carbon atoms and hydroxy, with the proviso that one. but not both of R and R is said amino. acylaminto or hydroxy; R and R each independently represent a member selected from the group consisting of lower alkyl having l-4 carbon atoms and lower alkyl having 1-4 carbon atoms and substituted with a member selected from the group consisting of hydroxy, aeylatmino wherein the acyl moiety has 1 to 4 carbon atoms, carbamyl. piperidino, benzoylamino and alkylsulfonam&#39;ido wherein the alkyl moiety has I to 4 carbon atoms; R;,, R R,-,. R R and R each independently represent a member selected from the group consisting of hydrogen. lower alkyl having l-4 carbon atoms and lower alkoxy having l-4 carbon atoms, and thesalts formed by these indamines with organic or inorganic acids, in particular their acetates, hydrochlorides, hydrobromides, persulfates.  
 &#39;perchlorates and the double zinc salts of these compounds. which can, of course. be in a tautomeric form of that represented by formula (1) are usefully employed for dyeing keratinous fibers, and, in particular. human hair.  
 11 Claims, No Drawings INDAMINES FOR DYEING KERATINIC FIBERS This application is a continuation-in-part of our application Ser. No. 180.455. filed Sept. 14. 1971. now abandoned.  
  The present invention relates to novel indamines having the formula:  
 wherein R and R each independently represent a member selected from the group consisting of hydrogen. lower alkyl having 1-4 carbon atoms. lower alkoxy having 1-4 carbon atoms. amino. acylamino wherein the acyl moiety has 1 to 4 carbon atoms and hydroxy with the proviso that one. but not both of R and R is said amino. acylamino or hydroxy: R and R each independently represent a member selected from the group consisting of lower alkyl having l-4 carbon atoms and lower alkyl having 1-4 carbon atoms and substituted with a member selected from the group consisting of hydroxy. amino. acylamino wherein the acyl moiety has 1 to 4 carbon atoms. carbamyl. piperidino. benzoylamino and alkylsulfonamido wherein the alkyl moiety has l to 4 carbon atoms: R,-,. R. R,-.. R... R; and R i R R5 Generally. the indamines of formula (I) are isolated in the form of their salts. these latter generally being more easy to obtain because of their solubility characteristics.  
  The indamines or indamine salts of formula (I) can be prepared by condensing a paraphenylene diamine having the formula:  
 wherein Z. and Z both represent hydrogen or both represent a member selected from the group consisting of lower alkyl having 1-4 carbon atoms and lower alkyl having 1-4 carbon atoms and substituted with a member selected from the group consisting of hydroxy. acylamino wherein the acyl moiety has I to 4 carbon atoms.  
 carbamyl. piperidino. benzzoylamino and alkylsulfonamido wherein the alkyl moiety has I to 4 carbon atoms. and Z 2.. Z and Z. each independently represent a member selected from the group consisting of hydrogen. lower alkyl having 1-4 carbon atoms and lower alkoxy having l-4 carbon atoms. on a compound having the formula:  
 wherein Y represents a member selected from the group consisting of amino. acylamino wherein the acyl moiety has 1 to 4 carbon atoms and hydroxy; Y and Y both represent hydrogen when Z and Z are other than hydrogen. or both represent a member selected from the group consisting of lower alkyl having 1-4 carbon atoms and lower alkyl having 1-4 carbon atoms and substituted with a member selected from the group consisting of hydroxy. acylamino wherein the acyl moiety has I to 4 carbon atoms. carbamyl. piperidino. ben zoylamino and alkylsulfonarnido wherein the alkyl moiety has I to 4 carbon atoms when Z, and 2 are both hydrogen; Y Y and Y each independently represent a member selected from the group consisting of hydrogen. lower alkyl having 1-4 carbon atoms and lower alkoxy having 1-4 carbon atoms. The condensation reaction is carried out in an aqueous alkaline medium. an aqueous acetonic alkaline medium or in an aqueous isopropanol alkaline solution. in the presence of an oxidizing agent. The initial reactants. represented by for mulae ll and Ill above can be used in the form of one of their salts. If necessary or desirable. the resulting indamine or indamine salt can be further transformed into the desired indamine salt.  
  The oxidizing agent used in the above condensation reaction is advantageously hydrogen peroxide or a water soluble inorganic peroxy salt such as an alkaline persulfate including ammonium persulfate. the use of which facilitates the isolation of the indamine of formula l in the form of an insoluble persulfate.  
  When the oxidizing agent used is hydrogen peroxide and it is desired to obtain an indamine salt that is relatively insoluble in water. the above condensation reaction can be followed by addition to the reaction mixture either of an acid corresponding to the desired salt.  
 or of a salt of that acid which is more soluble in water than the desired indamine salt. for example. ammonium persulfate.  
  It has further been noted that even when it is desired to prepare an indamine persulfate. itis often advantageous to proceed in two stages. the first stage comprising carrying out the condensation in the presence of hydrogen peroxide and the second stage comprising adding an alkaline persulfate. including ammonium persulfate, to the reaction mixture.  
  When it is desired to obtain indamine salts which are very soluble in water. it is necessary to produce these salts in a two-stage operation. In the first stage. there is prepared an indamine salt. such as a persulfate or a hydrochloride. which is relatively insoluble and. therefore, can be isolated. In the second stage. this salt is treated with an alkaline solution from which the indamine of formula I can be extracted with a suitable solvent such as chloroform or methylisobutyl ketone. This indamine can then be changed into the desired salt by the addition of the corresponding acid to the solvent phase. This way of operating is particularly applicable when it is desired to prepare an acetate of the indamine.  
  When it is desired to obtain an indamine of formula (l), which is not salified and which is insoluble in water, the condensation reaction is preferably performed in the presence of hydrogen peroxide and the resulting indamine is separated from the reaction medium by any suitable technique, for example. by filtering.  
  On the other hand. when it is desired to obtain an indamine of formula (I) which is so soluble in water that its direct isolation from the reaction medium is not feasible, the indamine, after being prepared by the above condensation reaction in the presence of hydrogen peroxide, is converted, in a first stage. into a water insoluble salt thereof, such as its persulfate or its hydrochloride, by operating in the way described above. The salt thus formed is isolated as by filtering, for instance. and then in a second stage is treated with a concentrated alkaline solution. operating in a minimum of water. Finally. if necessary or desirable, the indamine is extracted with a suitable solvent such as chloroform or methylisobutyl ketone.  
  To obtain double salts of zinc and the indamine of formula (I). it suffices to add an aqueous solution of a suitable zinc salt to an aqueous solution of a soluble indamine salt.  
  Representative paraphenylenediamines of formula (II) that can be used in accordance with the present invention are, for example, paraphenylenediamine, paratoluylenediamine. 2.5-diamino anisole, 2-methoxy S-methyl paraphenylenediamine, 2,6-dimethyl 3- methoxy paraphenylenediamine, 1,4-diamino durene, N.N-diethyl paraphenylenediamine, N,N-dimethyl paraphenylenediamine and N,N-(ethyl, B-mesylaminoethyl) 4-amino 3-methyl aniline.  
  Compounds representative of those having formula ([11) above include. for instance 2,4-diamino anisole, 3-amino ,4-methyl acetanilide, 3-amino acetanilide, N.N-dimethyl metaphenylenediamine, meta (N.N- dimethyl) amino acetanilide and N.N-diethyl metaaminophenol.  
  The condensation reaction is generally carried out at atmospheric pressure and at a temperature ranging from about l to C. Generally, the paraphenylene diamine and the compound represented by formula &#34;I are employed in essentially equimolar amounts. When the reaction medium is an aqueous alkaline solution, an alkalinizing agent such as ammonia or the like is present in amounts such that the pH is about 8 to l 1. When the reaction medium is an aqueous acetonic solution. acetone can comprise between about 20 to weight percent of the medium. When the reaction medium is an aqueous isopropanol solution, isopropanol can com prise between about 20 to 50 weight percent of the medium. The oxidizing agent is generally present in stoichiometric amounts when this oxidizing agent is a persalt, and in excess when it is hydrogen peroxide.  
  The indamines of formula (I) can also be prepared by condensing a benzoquinonediimine having the formula:  
 NH (IV) wherein Z Z 2;, and Z each represent a member selected from the group consisting of hydrogen, lower alkyl having l4 carbon atoms and alkoxy radicals having l4 carbon atoms with the proviso that at least two of Z 2,. Z,-, and 2.; do not represent hydrogen. on a compound of formula (III) above wherein Y, Y Y,  
 and Y have the meaning given above and Y and Y each represent a member selected from the group consisting of lower alkyl having l4 carbon atoms and lower alkyl having 1-4 carbon atoms and substituted by a member selected from the group consisting of hydroxy. acylamino wherein the acyl moiety has 1 to 4 carbon atoms, carbamyl, piperidino, benzoylamino and alkylsulfonamido wherein the alkyl moiety has 1 to 4 carbon atoms.  
  This condensation is carried out either in an aqueous medium which, if desired, can contain a salt of an acid corresponding to the desired indamine salt. which acid salt is more soluble in water than the desired indamine salt, or in an inert solvent such as methylisobutylketone, dioxane or benzene which can also contain an acid corresponding to the desired indamine salt.  
  When the condensation is performed in water. it is possible, by addition to the reaction mixture of stoichiometric amounts of a salt such as sodium chloride, ammonium persulfate, sodium perchlorate or zinc chloride. to isolate the indamine resulting from this condensation in the form of a salt that is relatively insoluble in water.  
  When it is desired to prepare indamine salts that are very soluble in water, this condensation is preferably performed in a solvent, as described above. There is then added to the solvent stoichiometric amounts of an acid corresponding to the desired indamine salt. Representative of such acids are, for instance, acetic acid and propionic acid.  
  Representative benzoquinonediimines of formula (IV) which can be used in this embodiment of the present invention include. for instance, 2-methyl 5- methoxy benzoquinonediimine, 2,5-dimethoxy benzoquinonediimine, 2,6-dimethyl 5-methoxy. benzoquinonediimine and durobenzoquinonediimine,  
 In the embodiment, the condensation reaction is also generally carried out at atmosphericpressure and at a temperature ranging between about 1 5 to 50C. Usu-&#39; ally, the benzoquinonediimine and the compound represented by formula (lll) as defined immediatelyabove are employed in essentially equimolar amounts.  
  In yet another embodiment of the present&#39;invention the indamines of formula (I) and their salts can also be prepared by condensing a compound of formula (III) above wherein Y. Y;,. Y. and Y,-, have the meaning given above and Y, and Y both represent hydrogen. on a nitroso derivative having the formula:  
 wherein Z, and Z each represent a member selected from the group consisting of lower alkyl having 1-4 carbon atoms and lower alkyl having l-4carbon atoms and substituted by a member selected from the group consisting of hydroxy. acylamino wherein the acyl moi ety has l to 4 carbon atoms. carbamyl. piperidino. benzoylamino and alkylsulfonamido wherein the alkyl moiety has I to 4 carbon atoms and Z 2.. Z and Z have the meaning given above. This condensation is carried out either in an aqueous medium. or in an ethanol medium containing zinc chloride. If necessary. the prod uct obtained can be converted into the desired indamine or indamine salt in the manner described hereinbefore.  
  Preferably the nitroso derivative of formula (V) is used in the form of its hydrobromide or hydrochloride when the condensation reaction is carried out in an aqueous medium. The operating temperature is then between and 50C and. after cooling. the indamine of formula (I) is isolated in hydrochloride or hydrobromide form which can then be converted into the indamine itself or another of its salts.  
  When the condensation reaction is effected using the above nitroso derivative of formula (V) in the aforementioned ethanol medium, the operation .is carried out at reflux and in the presence of zinc chloride. The resulting indamine of formula (I) is then isolated in the form of its double zinc chloride. which can then be converted into the indamine itself or another of its salts, also in the manner as described heretofore.  
  Representative nitroso derivatives of formula (V) that can be used in this embodiment of the present invention include, for instance, paranitroso N,N-diethylaniline, paranitroso-N.N-(ethyl, B&#39;piperidinoethyl) aniline, paranitroso N.N-(ethyl. ,B-acetylaminoethyl) aniline and paranitroso N,N-di-fi-hydroxyethyl) aniline.  
  Again, the nitroso derivative defined above and the compound of formula (III) are employed in essentially equimolar amounts. When the reaction medium used is an ethanol medium containing zinc chloride, the latter is used in amounts sufficient for precipitating the product. t  
  The indamines according to the invention, and their salts. constitute dyes which have a great dyeing power in a broad pH range, which can vary from pH 3 to pH 10. Because of their very great affinity for keratinous fibers, very slight concentrations of these dyesare sufficient to obtain intense shades, which explains why those salts thereof which are relatively insoluble in water, such as the persulfates and certain chlorides, are  
 perfectly usable.  
  Consequently. the present invention also provides novel dye composition for keratinous fibers. in particular. for human hair, characterized by the fact that it contains in solution at least one compound represented by formula (I) or a salt of this compound.  
  The dye compositions according to the invention can contain only the compounds of formula (l). in which case they make it possible to obtain on white hair colorings which go from violet to green. after an extremely short application period of the order of three minutes at ambient temperature.  
  Because of the great dyeing power of the novel compounds of formula (1) their concentration in the compositions according to the invention can, as said above. be extremely slight. of the order of 0.002 percent by weight. However. this concentration can vary from 0.002 to 1 percent by weight.  
  The compositions according to the invention can also contain other direct dyes. for example. anthraquinone dyes. nitro dyes of the benzene series. indoanilines. indophenols or indamines other than those of formula (I).  
  The compositions according to the invention make it possible to obtain shades rich in glints which often give the hair a pearly appearance.  
  The dye compositions according to the invention are generally in the form of aqueous or aqueous alcohol solutions which can easily be prepared by dissolving in water one or more compounds of formula (I) in mixture or not with other direct dyes. However. they can also contain thickeners and be in the form of creams or gels. When an alcohol solution is employed generally the alcohol will be a lower alkanol such as ethanol or isopropanol, the alkanol being present in the aqueous solution in amounts of about 20 to percent by weight thereof.  
  The compositions according to the invention can further contain various ingredients usually used in cosmetics, for example, wetting agents. dispersing agents. swelling agents. penetrating agents, softeners or perfumes.  
  Representative of such materials are nonylphenol oxyethylenated with 4 moles of ethylene oxide. lauryl alcohol oxyethylenated with 10.5 moles of ethylene oxide, a mixture of 19 percent of dodecyl alcohol oxyethylenated with 2 moles of ethylene oxide and 81 percent of the sodium sulfate of this same oxyethylenated alcohol. ethanolamides of the fatty acids of copra which are surface active agents usefully employed as wetting agents, carboxymethyl cellulose as a thickening agent. monomethyl ether of ethylene glycol and butyl glycol as solvents and ethylene diamine tetraacetic acid as a sequestering agent.  
  The compositions of this invention can also be packaged under pressure in aerosol bombs or containers. together with a conventional aerosol propellant such as dichlorodifluoromethane. trichloromonofluoromethane and their mixtures. Obviously other conventional aerosol propellants can be used.  
  The pH of the dye compositions according to the invention can vary from 3 to 10. Preferably. however. the pH ranges between about 69..  
  Dyeing of keratinous fibers. in particular. human hair. with the dye compositions according to the invention, can be performed in the usual way by application of the composition to the fibers to be dyed. the composition being left in contact with the fibers for a time varying from about 3 to 30 minutes. Following this application. the fibers are rinsed and. if desired. washed. Thereafter. the thus treated fibers are dried.  
  In another embodiment of the present invention. the novel indamines can be employed in the production of capillary hair-setting lotions. These lotions comprise an aqueous alcohol solution, at least a cosmetic resin and at least one compound of formula (I) or a salt thereof. The amount of indamine present in the hair-setting lotion according to this invention can be extremely low. Such an amount generally ranges between about 0.002 to 0.5 percent by weight of the total hair-setting lotion composition.  
  Representative cosmetic resins that can be employed in the hair-setting lotion composition of the present invention include. for instance. polyvinylpyrrolidone having a molecular weight of l0.000-70.000. copolymer of crotonic acid and vinyl acetate :90) having a molecular weight of 45000-50000. copolymer of vinylpyrrolidone and vinyl acetate wherein the ratio of VP to VA ranges between 30-70170-30 and having a molecular weight of 40.000 to 160.000 copolymer of maleic a nhydride and butylvinyl ether and the like. These resins are utilized in a proportion of about 1 to 3 percent by weight of the hair-setting lotion composition.  
  The alcohols suitable for the preparation of the hairsetting lotions of the invention are low molecular weight alkanols. preferably ethanol or isopropanol. which are present in amounts of about to 50 percent by weight of the total hair-setting lotion composition. The pH of the hair-setting lotion of the invention can vary between 3-10 and preferably between about 6-8.  
  Hair-setting lotions of the present invention that contain only the dyes of formula (I) constitute shading compositions which make it possible to impart to the hair extremely luminous glints and often give it a pearly or iridescent appearance.  
  However. the hair-setting lotions of this invention can also contain other direct dyes. for example, anthraquinone dyes. nitro dyes of the benzene series. indoanilines. indophenols or again other indamines.  
  The hair-setting lotions according to the invention are usually used by application to wet hair previously washed and rinsed. followed by rolling up and drying of the hair.  
  The following examples are intended to illustrate the various aspects of the present invention. Unless otherwise specified, all parts and percentages are by weight and all temperatures are expressed in degrees centigrade.  
 EXAMPLE I The hydrochloride of N-[ (4&#39;-dimethylamino)phenyl] 3-amino 6-methoxy benzoquinonediimine is prepared as follows:  
 NH RC1 OCH 0.l7l mole (32 g) of p-nitrosodimethylaniline hydrochloride is dissolved in 320 cc of water at 50. There is then added to this solution. with stirring, 0.l7l mole (23.7 g) of 2.4-diamino anisole in 320 cc of water. The reaction medium is allowed to stand for two hours at ambient temperature. Then 41.7 g of chromatographically pure indamine hydrochloride are filtered therefrom. which indamine hydrochloride melts with decomposition at 220.  
 EXAMPLE 2 N-[(4&#39;-dimethylamino)phenyl] 3-amino b-methoxy benzoquinonediimine is prepared asfollows:  
  0.003l mole (l g) of the indamine hydrochloride prepared in Example l is introduced. with stirring. into 20 cc of water to which have been added 5 cc of ammonia at 22 B. 0.74 g of the above desired product is filtered therefrom, washed with water and dried under vacuum. This product melts at 205.  
 7 Molecular mass calculated for C H N O 270.  
  Molecular mass found by potentiometer determination by perchloric acid in acetic acid: 276.  
  Calculated for 25 Analysis -.H N .0 Found C&#39;t 66.66 66.60 66.22 HV: 6.66 6.83 6.76 NV, 20.74 20.64 20.72  
 EXAMPLE 3 The double chloride of zinc and N-[ (4&#39;-[ethyl. acetylaminoethyl]amino)phenyl1 3-amino 6-methoxy benzoquinonediimine having the below formula is prepared as follows:  
  NH rnr-ca -ca 3 coca To a solution of 0.01 mole (2.35 g) of paranitroso N.N- (ethyl. B-acetylaminoethyl) aniline in IQ cc of absolute ethanol there are added. on the one hand. 0.01 mole L38 g) of 2.4-diamino anisole in solution in IQ cc of absolute ethanol and. on the other hand. 1.36 g of zinc chloride. The reaction medium is heated for a half hour at reflux. Then the above double salt of zinc and indamine which has precipitated in crystallized form (4.2 g) is filtered therefrom. This salt. after washing with ethanol, is chromatographically pure.  
 EXAMPLE 4 The double chloride of zinc and N-l(4[ethyl&#39; B-piperidinoethyl]amino)phenyll 3-amino -methoxy benzoquinonediimine having the below formula is prepared as follows:  
 CN-CHE-CHE /N N EXAMPLE 5 The persulfate of N-[(4-dimethylamino)phenyll 3 acetylamino 6-methyl benzoquinonediimine is prepared as follows:  
  My 1 lCH --CH paraphenylenediamine dihydrochloride in cc of water to which have been added 20 cc of ammonia at 22Be&#39;there are added. on the one hand. 0.03 mole of 3-amino 4-methy1 acetanilide (4.92 g) in solution in 40 cc of acetone and. on the other hand. 50 cc of 50 volume hydrogen peroxide. The reaction mixture is allowed to stand for 10 minutes at ambient temperature. There are added to this reaction mixture 13.7 g of ammonium persulfate in solution in 25 cc of water. The above indamine persulfate precipitates and is filtered from the reaction medium. washed with a little water and then with acetone. 4.5 g of indamine persulfate in the form of green crystals with golden glints are thus recovered in chromatographically pure form.  
 EXAMPLE 6 Calculated for Anal \&#39;sis C H .,N,O Found C/( 68.91 68.24 68.37 H71 6.75 6.73 6.82 N71 18.91 18.77 18.81  
 OCH  
 To a solution of 0.03 mole (6.27 g) of N.N-dimethy1 EXAMPLE 7 The perchlorate of N-[ 2 &#39;-amino 4- dimethylamino)phenyl] benzoquinonetliimine is prepared as follows:  
 NHCOCH \N N NH CH 0.01 mole (l g) of paraphenylenediamine and 0.005 mole l g) of N.N-dimeth vl metaphenylenediamine dihydrochloride are dissolved in 20 cc of water. To this solution are added 5 cc of ammonia at 22 B and 20 cc of 20 volume hydrogen peroxide. The resulting reaction mixture. having been allowed to stand for a half hour at ambient temperature is then saturated with sodium perchlorate. After 5 hours at 0, 0.65 grams of crude indamine perchlorate is filtered therefrom and contains. as its chromatogram shows. N.N-dimethy1 metapheneylenediamine and traces of paraphenylenediamine. After washing in ethyl acetate. the product (0.55 g) is chromatographically pure.  
 EXAMPLE 8 The acetate of N1 (2 -acetylamino 4 dimethy1amino)phenyll 3-methoxy 6-methyl benzoquinonediimine is prepared as follows: CH NHCOCH 001-1 N N NH cn co r1 ca 0.05 mole (7.5 g) of Z-methyl S-methoxy benzoquinonediimine is dissolved in cc of methylisobutylketone. There is then immediately added to this solution 0.05 mole (8.9 g) of meta-(N.N- dimethylamino) acetanilide dissolved in 100 cc of methylisobutylketone to which have been added 5 cc of acetic acid. The above indamine acetate precipitates and is immediately filtered from the reaction medium.  
  washed with a little methylisobutylketone and dried under vacuum. The desired indamine acetate which .is  
  Calculated for Analysis C H O N CH CO H Found C71 (12.17 61.80 61.58 H? 6.73 6.57 6.60 N? 14.50 14.214 14.26  
 EXAMPLE 9 The double chloride of zinc and N[(4&#39;-diethylamino 2&#39;-hydroxy)phenyl] 3-methoxy 6-methyl benzoquinonediimine having the below formula is pre-&#39; pared as follows:  
 OH OCH On the one hand, 0.005 mole (1 g) of the hydrochloride of meta-(N.N-diethylamino) phenol is dissolved in cc of water and cc of isopropanol to which have been added 3 cc of ammonia at 22 B. On the other hand. 0.01 mole (2.25 g) of dihydrochloride of 2 methyl S-methoxy paraphenylenediamine is dissolved in 10 cc of water and 10 cc of acetone to which have been added 3 cc of ammonia at 22 Be. To this latter solution is immediately added the above solution of meta-(N.N-diethylamino)phenol and cc of 20 volume hydrogen peroxide. The resulting reaction mixture is allowed to stand for 10 minutes at ambient temperature and a small amount of the 2-methyl S-methoxy paraphenylenediamine is eliminated by filtering. The remaining reaction mixture is then neutralized to a pH of 7 by the addition thereto of acetic acid. and 8 g of zinc chloride in solution in 50 cc of water are also added. After cooling in ice, 2.4 g of the above chromatographically pure double zinc chloride are filtered and recovered.  
 EXAMPLE 10 The double chloride of zinc and N-[(4&#39;-diethylamino 2&#39;-hydroxy)phenyl] 2,6-dimethyl-3-methoxy benzoquinonediimine having the below formula is prepared as follows:  
 0H OCH 0.005 mole (0.82 g) of 2,6-dimethyl 3-methoxy benzoquinonediimine is dissolved in 6 cc of water. There is immediately added to this solution 0.005 mole (1 g) of meta-(N.N-diethylamino)phenol hydrochloride previously dissolved in 5 cc of water to which have been added 6 cc of isopropyl alcohol and 0.5 cc of ammonia at 22 B. The resulting mixture immediately takes on an intense blue violet coloring. To this mixture there is then added a solution of 2 g of zinc chloride in 3 cc of water. 1.3 g of the above double chloride of zinc and indamine precipitate and are filtered therefrom and washed with a little water. then with acetone. and finally dried. The product is chromatographically pure.  
 EXAMPLE 11 The perchlorate of N-[(4&#39;-diethylamino 2&#39;-amino phenyl] 2,6-dimethyl 3-methoxy benzoquinonediimine is prepared as follows:  
 OCH  
 0.01 mole (1.64 g) of 2.6-dimethyl 3-methoxy ben-&#39; zoquinonediimine is dissolved in 6 cc of water. There is immediately added to this solution 0.01 mole (2.4 g) of N,N-diethy1 metaphenylenediamine dihydrochloride previously dissolved in 6 cc of water to which have been added 2 cc of ammonia at 22 Be. The resulting mixture immediately takes on an intense blue coloring. To this mixture is added 0.0131 mole (1.6 g) of sodium perchlorate dissolved in 3 cc of water. 0.8 g of the above indamine perchlorate precipitates and is filtered from the reaction mixture. Thereafter the said indamine perchlorate is washed with a little water then with a little dioxane. The product is chromatographically pure.  
 EXAMPLE 12 The hydrochloride of N-[(4&#39;-diethylamino) phenyl] 3-amino-6-methoxy benzoquinonediimine is prepared as follows:  
 0.1 mole (21.4 g) of p-nitrosodiethylaniline hydrochloride is dissolved in 250 cc of water at 50. There is then added to this solution. with stirring, 0.1 mole (21.1 g) of 2,4-diamino anisole dihydrochloride in solution in 210 cc of water to which have been added sufficient ammonia at 22 Re: to achieve a pH of 8.5. The resulting reaction medium is heated for several minutes at then left to return slowly to ambient temperature. The precipitate obtained (24.8 g), which is the above indamine hydrochloride. if filtered. washed with a little water and then with acetone. This product is chromatographically pure and melts with decomposition at EXAMPLE l3 Calculated for Analysis C H N Found (9% 68.43 68.47 68.39 HQ 7.43 7.47 7.39 N9? 18.78 18189 18.64  
 EXAM PLE 14 The persulfate of N.,N-[(4&#39;-[ethyl. B-mesylaminoethyl] amino 2&#39;-methyl)phenyl] 3-acetylamino-6- 7 methyl benzoquinonediimine is prepared as follows:  
 H 0 N N H C-O S-HN-(CH 0.0025 mole (0.68 g) of N.N-(ethyl, B-mesylaminoethyl) 4-amino 3-methyl aniline and 0.0025 mole (0.42 g) of Z-methyl 5-acetylamino aniline are dissolved in cc of water to which have been added 10 cc of isopropanol and 1 cc of ammonia at 22 Be. To this resulting solution, cooled to 0, is added little by little, with stirring, 0.005 mole (1.15 g) of ammonium persulfate in solution in 12 cc of water. The above desired indamine persulfate precipitates and is filtered therefrom and is washed with isopropanol. The product is chromatographically pure. 1  
 EXAMPLE 15 The hydrochloride of N-[(4-dibutylamino )phenyl1- ,2-methyl-5-amino benzoquinonediimine having the following formula is prepared as follows:  
 dibutylaniline and 0.01 mole (1.22 g) 2,4-diamino toluene are introduced into cc of water. The resulting mixture is left to stand for one hour at ambient temperature and then overnight at10C. The above indoaniline which crystallizes in the reaction mixture in the form of the hydrochloride thereof is then&#39;filtered. washed with water and dried under a vacuum. lt melts with decomposition at 146C.  
  Calculated for Analysis C H N CI Found EXAMPLE 16 N-[ (4&#39;-di-B-hydroxyethylaniino )phenyl l-2-methoxy- S-amino benzoquinonediimine of the formula OCH OH-CH -CH OH-CH2-CH2 is prepared as follows:  
  0.02 mole (4.92 g) of 4-nitroso-N,N-di-B- hydroxyethylaniline hydrochloride and 0.02 mole (4.22 g) of 2,4-diamino anisole dihydrochloride are dissolved in cc of a 0.7 N NaOH solution. The resulting solution is maintained for 1.5 hours at ambient NHCOCH temperature with agitation at which time there are added little by little and with cooling. 25 cc of ammonia (22 Be). The above indoaniline precipitates and is filtered, washed with water. recrystallized in a mixture of dimethylformamide and water and dried under vacuum. 1t melts at 171C.  
 Calculated for Analysis C i H MQ, Found CV1 61.80 61188 62.10 H71 671 6.79 6.77 N77 16.96 17.14 17.04  
  EXAMPLE 17 Monohydrated N-[ (4-(ethylcarbamylmethyl- )amino) phenyl1-2-methyl-5-amino benzoquinonedii- CH N- N: NH H01 11 Q 0.01 mole (2.7 g) of hydrochloride of 4-nitroso-N,N&#39; W  
 mine hydrochloride of the formula:  
  NNI 3NH HCl H20 1 CH2 1 NH2 (301111 is prepared as follows:  
  lnto .cc of a 0.25 N HCl solution there are introduced 0.005 mole 1.03 g) of 4-nitroso-N,N-ethylcarhamylmethyl aniline and 0.005 mole (0.61 g) of 2.4- diamino toluene. The resulting mixture is left to stand 5 with agitation for 1 hour at ambient temperature. The above monohydrated indamine hydrochloride crystallives and is the filtered. washed first with ice water and then with acetone and finally dried under a vacuum. lt  
 melts with decomposition at 217C. W  
  Calculated for Analysis (&#39;,;H t N,-,()- -(l Found (&#34;&#39;4&#39; 55.90 55.00 55.514 H; 0,57 0.33 (1.30 N) 19.15 19.01 19.24 (&#34;l&#39;i 1.72 9.624 Hi4 EX A M PLE l 8 is prepared as follows:  
  Into 15 cc of isopropa&#39;nol to which has been added 5 cc of water there are introduced 0.005 mole (1.03 g) of 4-nitroso-N,N-ethyl-carbamylmethyl aniline and 0.005 mole (1.05 g) of 2,4-diamino anisole dihydrochloride. The resulting mixture is left to stand with agitation for minutes at ambient temperature. The above monohydrated indamine hydrochloride crystallizes and is then filtered, washed first with isopropanol and then with acetone, and recrystallized in boiling water. It melts with decomposition at 214C.  
 oca  
 Calculated for Analysis c,,11. ..N -,0,.c1 Found C; 53.47 53.69 H56 H 6.27 6.33 6.35 N01 18.34 17.99 18.06 Cm 9.31 9.31 9.41  
  EXAMPLE 19 N-[ (4&#39;-( ethyl-B-piperidinoethyl )amino )phenyl l-Z- methyl-5-amino benzoquinonediimine hydrochloride of the formula N NH HCl 1 CH 2 NH 0.005 mole 1.67 g) of 4-nitroso-N.N-(ethyl-B- piperidinoethyl) aniline dihydrochloride and 0.005 mole (0.61 g) of 2.4-diamino toluene are introduced into 20 cc of water. The resulting mixture is maintained with agitation at ambient temperature for l hour at which point there are added cc of water and then sufficient ammonia (22B) to adjust the pH thereof to 7.5. The above indoaniline hydrochloride precipitates and is then filtered. washed with a little ice water and dried under a vacuum. lt melts with decomposition at 157C.  
 Calculated for Analysis -H;. -N -,Cl Found (&#34;2 65.76 65.11 65.24 H; 8.03 8.26 7.98 Nl l 17.44 17.36 17.23 (lii 8.84 8.46 8.49  
 EXAMPLE 20 Monohydrated N-[ (4 ethyl-B- piperidinoethyl )amino) phenyll-Z-methoxy-S-amino benzoquinonediimine hydrochloride of the formula:  
 is prepared as follows:  
  0.0] mole (3.34 g) of 4-nitroso-N.N-(ethyl-B- piperidinoethyl) aniline dihydrochloride and 0.01 mole (2.11 g) of 2.4-diamino anisole dihydrochloride are dissolved in 100 cc of water. The resulting mixture is maintained with agitation for one hour at ambient temperature at which point it is alkalinized, while cooling it to 0C with agitation by adding thereto sufficient ammonia (22B) to adjust its pH to 7.5. The above monohydrated indamine hydrochloride precipitates and is then filtered. washed with a little ice water and then recrystallized in boiling water 10 cc of water per gram of product). After drying under a vacuum the crystallized product melts with decomposition at l(.  
 (:tlculated for liXA M PLE 2| N-l 4-ethyl-[i-henzoylaminoethyl )amino )phenyl 2metl1oxy-5anlino henzoquinonediimine hydrochloride of the formula:  
 OCH  
 N NH HCl is prepared as follows:  
  0.02 mole (4.22 g) of 2.4-diamino anisole dihydrochloride is dissolved in 40 cc of water. The resulting solution is then alkalinized by the addition thereto of sufficient ammonia (22B) to adjust the pH thereof to 8.5. There is then introduced, with agitation, 0.02 mole (7 g) of 4-nitroso-N.N-(ethyl-B-benzoylamino ethyl) aniline hydrochloride suspended in [0 cc of isopropano]. The resulting mixture is maintained with agitation at ambient temperature for 2 hours at which point the above ind-amine hydrochloride which has crystallized is filtered. washed with ice water and dried under a vacuum. It melts with decomposition at l62C Calculated for EXAMPLE 2:  
  l\&#39;-[ 4-( ethyl-mcsylaminoethyl )aminoJ -methyl) phenyl|-Z-methyl-S-amino hcnzoquinonediimine perchlorate of the formula:  
 EXAMPLE 23 The following dye composition is prepared:  
 Dye of Example l (H g Ethyl alcohol. )htitcr 20 g Water. t .s.p. 100 g Ammonia at 22B. asp. pH l0 This dye composition when applied to percent naturally white hair for 10 minutes imparts thereto. after rinsing and shampooing. a very luminous intense blue Shading.  
 EXAMPLE 24 The following hair-setting lotion composition is prepared:  
 Tricthanolamine. q.s.p. pH 7 This hair-setting lotion when applied to bleached hair After rinsing and shampooing. a light pearly green imparts thereto a periwinkle blue shade with pearly shade is obtained.  
  lints. g EXAMPLE 3() as EXAMPLE lhe tollowin i h&#39;tlll&#39;-$t3lllll lotion com osition is rett P The following hair-setting lotion composition is prepared: pared:  
  Dye of Example 7 0.025 g y \&#39;in \&#39;l acetate-crotonic acid copolyiner 3%: i l:: l H hm r g o (90; vinyl acetate. Ill) crotonic &#39;tcetc-tt &#39;tctctt&#39;c m, 1 H30? vinyl acetate ll)&#34;; crdioiiic lunch! JMMSHC 2 i:  
 . Ethyl alcohoL 96 titer. ts p. 0 acid molecular weight tattoo 2 g wwicr q g P Wu F l 3U &#39;lriethanolaniine, asp. Pll Triethanolaniine. qsp. pH 7 Water. q.s p. llltl g This hair-setting lotion when applied to bleached hair This hair-setting lotion when applied to bleached hair lmplms thercm c blue Shadeimparts thereto a strongly sil ered light blue shade. EXAMPLE 3l EXAMPLE 36 The following dye composition solution is prepared: The following hair-setting lotion is prepared: 30  
 , Dye of Example 4 (H15 g DY? i i X g \inyl acettite&#39;crolonic acid if r a l l 7 copolynier (90? \in\l acetate. i ll) L&#34;) l W ltl&#39;) crotonic acid niolecular &#39;IiHllmflh-H hcm&#39;mlmmmc cum 4; U0&#34;) u diimiiie acetate 0.] g i &#39;d o mgr &amp; 0 l\&#39;|(2.-l&#39;-diaminov 5 lllt3lll\t\ \l w q p 100 g plicnyl] ben/ooiiiuoneiniine 0.05 g Triethanolaininc. asp pH 7 Winn&#34; 100 g The dye composition when applied to bleached hair for 10 minutes imparts thereto. after rinsing and shampooing. a very intense violet shade.  
 EXAMPLE 32 This hair-setting lotion when applied to bleached hair imparts thereto a very light pearly blue shade.  
 EXAMPLE 27 The following dye composition is prepared:  
  The following dye composition is prepared:  
  Dye of Example 5 (Ll g D f E I 7 O l ;t\ HQ 0 Xill&#39;llp C g Aniriiluiia tli 2286. t .s.p. pH 9.5 E alcllmL 960 20 g Water. qspt lllll g l5; lactic acid solution. qsp. pH 3 This dye composition when applied to 95 percent naturally white hair for 20 minutes imparts thereto- T i dye composition whcn applied to 95 percent after rinsing and shampooing. an iridescent blue green naturally hi h i f 20 minutes imparts thereto Shlldeafter rinsing and shampooing. a rather intense blue gray Sl&#39;lld EXAMPLE 2s e The following hair-setting lotion composition is pre- EXAMPLE 33 pared: Y The following hairsetting lotion composition is prepared:  
 Dye of Example 6 (LI g Vinyl acetatc-crotonic acid copolymer H x 006-; vinyl acetate. 100i crotonic @56 iifwlfli l acid (W05 g acid molecular weight 45.000) 2 g u-)p()h,mc:(9(m vim Mew: aflfis r g g Hm g I054 crotonic acid inolecular f &#34;1 weight 45 Ul)()) 2 g Tnuhmulmnne pH 7 5e Ethyl alcohol. 96titer. t].\.p 50  
  Water. q,s,p. 100 g This hair-setting lotion when applied to bleached hair PH 7 imparts thereto an intense emerald green shade.  
  This hair-setting lotion when applied to bleached hair EXAMPLE 29 imparts thereto a bluish silver shade.  
  60 The following dye composition 18 prepared: EXAMPLE 34 The following dye composition is prepared:  
 Dye of Example 6 0.] g Ethyl alcohol. 96 titer 50 g Wale? l -P- 100 E 5 Dye of Example 2 (L025 g Nitroorthophenylenediamine (Ll g Ethyl alcohol. 96titer 20 g This dye composition, the pH of which is 8.5, is apwatch mu g plied to percent naturally white hair for 20 minutes. Ammonia at 22B. q.s.p. pH 9 &#34;21 I y 22 I .3 i I. i I i 7 -Continued This dye composition when applied to 95 percent Water. q.s.p. I 100 g naturally white hair for 10 minutes imparts thereto. Ammflnia t -t [P after rinsing and shampooing. a deep intense green shade. i This dye composition when applied to 95% naturally white hair for 3 minutes imparts thereto. after rinsing and shampooing. an intense blue green shade.  
 EXAMPLE 4() It) The following composition is prepared:  
 EXAMPLE 35 The following dye composition is prepared:  
 Dye of Example 2 0.002 g Ethyl alcohol. 96titer Qt) g Water. q.s.p. ltlt) g 2 s t Dye ofExample y y v 0.01 g I Ethyl alcohol. 96&#34; titer 50 g This dye compos1tlon. the pH of which is equal to 9. Watcmqtsp, 100 g is applied to 95 percent naturally white hair for 10 mini utes. After rinsing and shampooing. a very light pearly This dye composition. which has a pH of 8. is applied turquoise shade is obtained. to bleached hair for 10 minutes. After rinsing and sham ooin &#39;1 clear earl reen shade is obtained.  
  EXAMPLE 36 p e P lg The following hair-setting lotion composition is pre- EXAMPLE 4] pared: i The following dye composition is prepared:  
 Dye of Example 3 i 7 l g Dye of Exam le II 0.05 g N-[(2.4&#39;-diamino 5-methoxy) Ethyl alcohol. 9otiter 25 g phenyl] henyoquinoneimine (H15 g Water. q.s.p. Itltl g \inyl acetate-crotonic acid copolymer (90% vinyl acetate. HM crotonic acid molecular weight 45.000) 2 g y &#39;ThlS dye composition. the pH of which is equal to s. 0 O I o l alz gy l g &#39;00 u is applied to 95 percent naturally white hair for 3 mm- PH 7 z utes. After rinsing and shampooing. a strongly silvered pale blue green shade is obtained. This h&#39;tir-settin lotion when t lied to bleached hair g EXAMPLE 42 imparts thereto a silver gray blue shade.  
  The following hair-setting lotion composition IS pre- EXAMPLE 37 The following dye composition IS prepared:  
  Dye of Example H 0.05 g H \inyl acctatecrotonie acid D-W i i 1 0&#39;95 g copolymer (same as in Example 24) 2 g N-[(4 -hydroxy 3 .5 -dimethyl) Em 1| h I 96 m, in phenyl] 2. dimethyl henzo- 40 5 rater. q.s.p. ltlt) g qulnonumrne (Ll g T I H 7 Ethyl alcohnL 60 g I rte ano ammc. asp. p. Water. asp. I 100 g 32 P PH a This hair-setting lotion when applied to bleached hair I .1 imparts thereto a pearly light green shade. ThlS dye composition when applied to 95 percent naturally white hair for 20 minutes imparts thereto, EXAMPLE 43 after I&#39;ll&#39;lSll&#39;lg and shampooing. a very brilliant silver gray The following dye composition is prepared: shade.  
 . EXAMPLE 38 7 e0 Dye of Example 12 0.1 g Water. Q.S.P. .rw?= 100 g The following dye composition s prepared... Ammonia; 22 Bi (ML pH m Dye 0f Example 6 i 1 (m5 g This dye composition when. applied for 15 minutes to N-[t4-hyd rtaxglp yll 0 I t 95 percent naturally white hair imparts thereto. after lr-met y enzoqumonelmme g 1 I Ethyl ulwhol mar 25 g rinsing and shampooing. a very intense lung s blue Water. q.s.p. V; y 100 g shade.  
  This dye coinposition, the p H of which is equal to 9. E is appliedfto bleached hair forflO minutes. After rinsing The following hair-setting lotion composition is and shani&#39;pooihg, a very pale green shade with golden 6O fi dgi glints is obtained.  
  EXAMPLE t y y Dye of Example 13 0.025 g Vinyl acetate-crotonic acid Th followmg y Composltlon 15 P p cop&#39;olyrner (same as in Example 24 2 g 1 a V ,so. Ethyl alcohol. 96 titer 50 g 1 1 t my 5 by Water. q.s.p. IOU g Dve of Example 9 (m5 g Triethanolamine. q.s.p. pH 7 Ethyl alcohol, 96 titer 20 g This hair-sctting lotion when applied to bleached hair imparts thereto pearly light blue shade.  
 EXAMPLE 45 The following hair dye composition is prepared:  
 Dye of lisamplc l5 0.25 g Dicthanolamides of fatty acids of copra 5 g Ammonia (22&#34; udl o.s. pH l Water. asp. loll g This dye composition when applied for 25 minutes at ambient temperature to percent naturally white hair imparts thereto. after rinsing and sham moing. a pearly light emerald green coloration liXAMPLli 4( The following hair dye composition is prepared:  
 l \c of lzsample i! 0.] g (&#39;arhoxymcthyl cellulose 4 g Monomethyl ether ol ethylene glycol lmethyl ccllosohei lh g Ammonia ilfHt&#34;) asp. pll (r5 ater. asp lllll g lhis dye composition when applied for 25 minutes at ambient temperature to )5 percent naturally white hair. after rinsing and shampooing. imparts thereto a \cry sil ct&#39;} light blue coloration.  
 EXAMPLE 47 The following dye composition is prepared:  
  This dye composition when applied for 20 minutes at ambient temperature to 95 percent naturally white hair imparts thereto. after rinsing and shampooing a gcntian blue coloration.  
 EXAMPLE 4h The following dye composition is prepared:  
 Dye of Example 20 (H5 g llutylglycol 5 g l.aur \l alcohol oxyctllylenated with l0.5 moles of ethylene oxide 5 g Ammonia (22 lie L 1. .s.pv pH 7 Water. t .s.p. I00 g This dye composition when applied for 20 minutes at ambient temperature to 95 percent naturally white hair imparts thereto. after rinsing and shampooing. a lawnder blue coloration.  
 EXAMPLE 49 The following hair-setting lotion composition is prepared:  
 Dye of Example IX 0.09 g Polyrinylpyrrolidone (MW 40.000) 2 g lsopropyl alcohol 35 g Ammonia (22 Be). q.s.p. pH l0 Water. q.s.p. I00 g This hair setting lotion when applied to bleached hair imparts thereto a very rich royal blue coloration.  
 EXAMPLE 50 5 The following dye composition is prepared:  
 l) \c of l&#39;.\amp|c lb (L2 g Dicthamilamides of fatty acids of copra 10 g Lactic acid (5; solutionl t .s.p. pH 7 ill ater. qs p llll) g l his dye composition when applied for minutes at ambient temperature to )5 percent naturally white hair 1 imparts thereto. after rinsing and shampooing. a hori- /on blue coloration.  
 AMPLE 5 l The following dye composition is prepared:  
 Dye of lisample 21 1.3 g Butylglycol 5 g l.aur \l alcohol osycthylcnated with 10.5 moles of ethylene oxide 5 g Water. asp. I00 g .-\mmoma (22 He: L[ .p pH 0.5  
  lhis dye compositionwhen applied for 15 minutes at ambient temperature to )5 percent naturally white hair imparts thereto a pure blue coloration.  
 EXAMPLE-52 The following dye composition is prepared:  
 l) \c of lzxample 22 0.25 g Mixture of l dodecylalcohol osyethylenatetl with 2 moles of ethylene oxide and S l; of the sodium sulfate salt of thi same o.\ \&#39;cth \lcu&#39;.ited alcohol In T \lcnediamine tetraacetic acid L5 anol. 05&#34; liter 25 g Ammonia (22 BLI&#39;I t .s.p pH 8 Water. qsp. l0l  
 wherein R and R each independently represent a member selected from the group consisting of hydrogen. lower alkyl having 1-4 carbon atoms. lower alkoxy having 1-4 carbon atoms. amino. acetylamino and hy- Rn R5 droxy with the proviso that one. but not both of R and R. is said amino, acetylamino or hydroxy; R and R each independently represent a member selected from the group consisting of lower alkyl having l-4 carbon atoms and lower alkyl having l-4 carbon atoms and substituted with a member selected from the group consisting of hydroxy, acetylamino. carbamyl. piperidino, benzoylamino and alkylsulfonamido wherein the alkyl has 1 to 4 carbon atoms.  
 R;,, R, R R R; and R, each independently repre sent a member selected from the group consisting of hydrogen, lower alkyl having 1 to 4 carbon atoms and lower alkoxy having I to 4 carbon atoms.  
 b. an acid salt of said indamine in (a) and c. a double chloride of zinc and said indamine in (a). said compound being present in amounts of about 0.002 to 1 percent by weight of said composition.  
 2. The&#39;composition of claim 1 wherein said compound is selected from the group consisting of the hydrochloride of N-[(4&#39;-dimethylamino)phenyl] 3-amino o-methoxy benzoquinonediimine.  
 N[(4&#39;-dimethylamino)phenyl] 3-amino 6methoxy benzoquinonediimine,  
 the double chloride of zinc and N-l(4&#39;-[ethyl. acetylaminoethyllamino)phenyl] Bamino o-methoxy benzoquinonediimine.  
 the double chloride of zinc and N-[(4&#34;[ethyl.  
 B-piperidinoethyl]amino)phenyl] 3amino 6- methoxy benzoquinonediimine.  
 the persulfate of N-l(4&#39;-dimethylamino)phenyl] 3- acetylamino o-methyl benzoquinonediimine,  
 N-[(4&#39;-dimethylamino)phenyl] 3-acetylamino methyl benzoquinonediimine.  
 the perchlorate of N-[(2&#39;-amino .4-dimethylamino) phenyl] benzoquinonediimine.  
 the acetate ofN-l (2&#39;-acetylamino 4&#39;-dimethylamino) phenyl] 3-methoxy o-methyl benzoquinonediimine.  
 the double chloride of zinc and N-[(4-diethylamino 2&#39;-hydroxy)phenyl] 3-methoxy 6-methyl benzoquinonediimine,  
 the double chloride of zinc and N-[4&#39;-diethylamino 2&#39;-hydroxy)phenyl] 2,6-dimethyl 3-methoxy benzoquinonediimine.  
 the perchlorate of N-[(4&#39;-diethylamino 2&#39;-amino) phenyl] 2,6-dimethyl 3-methoxy benzoquinonediimine.  
 the persulfate of N.N-[(4&#39;-[ethyl, B-mesylaminoethyl] amino 2&#39;-methyl)phenyl] 3-acetylamino 6- methyl benzoquinonediimine.  
  3. The composition of claim 1 having a pH between 3-10.  
  4. The composition of claim 1 having a pH between 6-9.  
  5. The composition of claim 1 wherein the aqueous solution further contains a lower alkanol and a film forming resin in amounts of about 1 to 3 percent based on the weight of said composition.  
 6. The composition of claim 5 wherein said lower alkanol is selected from the group consisting of ethanol and isopropanol.  
  7. The composition of claim 5 wherein said lower alkanol is present in amounts ranging from about 20-50 percent by weight of said composition.  
  8. The composition of claim 5 wherein said compound is present in amounts of about 0.002 to 0.5 percent by weight of said composition.  
  9. The composition of claim 5 wherein said film forming resin is selected from the group consisting of polyvinylpyrrolidone. a copolymer of crotonic acid and vinyl acetate, a copolymer of vinylpyrrolidone and vinyl acetate and a copolymer of maleic anhydride and butyl vinyl ether.  
  10. A process for dyeing human hair which comprises applying to said hair in an amount effective to dye the same an aqueous solution containing 0.002 to l percent by weight ofa compound selected from the group consisting of a. an indamine. including the tautomeric forms thereof, having the formula 1 N N NH 2 R R5 R8 3 wherein R and R each independently represent a member selected from the group consisting of hydrogen. lower alkyl having l-4 carbon atoms. lower alkoxy having l-4 carbon atoms. amino, acetylamino and hydroxy with the proviso that one. but not both of R and R&#39; is said amino. acetylamino or hydroxy; R and R each independently represent a member selected from the group consisting of lower alkyl having 1-4 carbon atoms and lower alkyl having l-4 carbon atoms and substituted with a member selected from the group consisting of hydroxy. acetylamino. carbamyl, piperidino. benzoylamino and alkylsulfonamido wherein the alkyl has 1 to 4 carbon atoms.  
 R R R R R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having I to 4 carbon atoms and lower alkoxy having 1 to 4 carbon atoms,  
 b. an acid salt of said indamine in (a) and c. a double chloride of zinc and said indamine in (a), said composition remaining in contact with said hair for a period ranging from about 3 to 30 minutes, rinsing and drying said hair.  
  11. The composition of claim 1 wherein said compound is the persulfate of B-mesylaminoethyl] mino 2&#39;-methyl)phenyl]-3- acetylamino--methyl benzoquinonediimine.