US3168442A - Compositions and methods of dyeing human hair with nitro-p-phenylenediamines - Google Patents

Description

United States PatentO A CQMPUSITIGNS ANjD METHQDS 9F DYEENG HUMAN HAlR WITH NI'lRihp-PHENYLENEDI- AMINES f Walter H. Brunner, Easton, Pa, and Alexander Halasz, Stamford, Conn, assignors to (Flairol Incorporated, New York, N.Y., a eorperationlo'f Delaware No Drawing. Filed June 12, 1964, Ser. No. 374,562

r 31 Claims. (ill. 161-33) This application is continuationin-part of our-application of Serial No. 67,166, filed November 4, 1960, now abandoned.

This invention relates to novel compounds, dyeing compositions containing the novel compounds, and methods for dyeing keratinaceous material by the use of the nove compounds.

The novel compounds of this invention can be repre- 'sented by the following generic formula:

FormulaI v V wherein R is a hydrocarbon radical free from olefinic and acetylenic .unsaturation having from 1 to about 8 carbon atoms, or a hydroxyalkyl radicalhaving from 1 to 4 carbon atoms; and wherein R is a saturated aliphatic hydrocarbon radical, i.e., alkyl, having from 1 to4 carbon atoms, a hydrozgyalkyl radical having from i to 4 carbon atoms, and R" is hydrogen or hydro x yalkyl having from 1 to 4 carbon atoms, provided that R" is hydroxyalkyl mentioned those wherein: R is a monoliydroxyalkyl having from 1 to 4 carbon atoms and R is an alkyl having from 1 to 4 carbon atoms; R is phenyl and R is an alkyl having from '1 to 4 carbon atoms; R is'a cycloalkyl'having4 to 6 carbon atoms, and particularly 6 carbon atoms and R'sis an alkyl having from 1 to 4 carbon vatoms; R is an alkyl having from 1 I04 carbonatoms and R is a monohydroxyalkyl having from lto'4 carbon atoms;

R islan alkyl having from 1 to 4carbon atoms and R is an alkyl having from 1 to 4 carbon atornsyR is phenyl and R is a monohydroxyalkyl having fromx'l to 4 carbon atoms; R is a cycloalkyl having from 4 to 6'carbon atoms, i and particularly 6 carbon atoms and R is a monohydroxyalkyl having from 1 to 4 carbon atoms.

In addition to the above illustrated compounds the fol- I lowing-compounds can also be mentioned:

only When R' is also hydroxyalkyl and further provided j that at least one of R and 'R' is a hydrocarbon radical.

The preferred compounds of this invention are those whereinR is ahydrocarbon radical;

. Illustrative of the'hydrocarbon radicals 'represeiiteli by R in the above generic formula therecan be mentioned:

. alkyl radicals containing from 1 to about 8 carbon atoms I and, preferably 1 to 4 carbon atoms,"e.g., methyl, ethyl,

propyl, isopropyl, butyl, t-butyl, n-hexyl andthelike; cycloalkyl radicals such as those having from 4 to 6 carbon atoms, e.g;, cyclobutyl, cyclopentyl, and cyclohcxyl; the phenyl,"-alkylphenyl or phenalkyl radicals, e.g.,

benzyl, 4-met-hylpl1enyl, 4-ethylphenyl and the like; and lower alkyl substituted cycloalkyl radicals, such as 4- 1-rnethylamino-2-nitro-4-propylaminobenzene; 7'

1-methylamino-2-nitro-4-hydroxymethylaminobenzene;s

l-methylamino-Z-nitrol- 3 -hydroxypropy1) aminobem zene;

lr-methylaminoQ-nitrol- (2,3 -dihydroxypropyl) aminobenzene;

l-me thylamino-2-nitro-4 4'-hydroxybutyl) aminobe'nzene;

'1-phenylamino-2-nitro-4-methylaminobenzene; l-phenylamino-Z-nitro-4-ethylan inobenzene; l-phenylamino-Zmitrb -4- (t-butyl) aminob enzene';

Vl-phenylamino 2-nitro-4-hydroxymethylaminobenzene;

ll-phenylainino-2-nitro-4-(Z', 3!.dihydroxypropyl)amino- I I l-cyclohexylamino-2-nitro-4-hydroiiymethylaminoben-"' zene;

. l-cyclohexylaniino-2-hitro-4Q 2'-hydroxyetliyl )Laminobenzene;

i 1-cyc1ohexylamino-2 nitro-4-l 3f -hydroirypropyl) aminbmethylcyclohenyl,'4-ethylcyclohexyl and the like. When i R is a hydroxyalkyl radical, the alkyl can be methyl, ethyl,

propyl, isopropyl, butyl, etc; V V

T hevarious radicals as represented by R'of the generic formula can be alkyl having up-to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, but-yl, t-butyl, andthe tlikeyhydroxyalkyl radicalshaving from I to 4 carbon,

atoms, such as hydroxymethyl, Z-hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl and 4-hydroxybutyl. The,

term hydroxyalkyl is intended to embrace bothmonohydroxy or polyhydroxy substituents, e.g.,- dihydroxy, although it is preferred that when-either R orlR' of generic Formula I is a hydroxyalkyl, it be a monohydro iyalkyl:

R in Formula I above may be hydrogen or hydroxyall-:yl and has the'value hydroxya'lkyl only when R is also hydroxyalkyl. Moreover, preferably, both R" and R" i are the same hydroxyall ryl group, e.g., hydroxyethyl. t

' It can be seen from generic Formula I that both R and benzene; -7 l-hydroxymethylaniino-2-nitro-4-methylaminobenzene;

, 1-(3,' hydroxypropyl amino-2mitro-4-methylaminobenzene;

i 1-( 2,3 -dihydroxypropyl) amino 2-nitro 4 methylamino benzene; v p 1-hydroxymethylamino-Z-nitroat-ethylaminobenzene 1- 2'-hydroxyeth yl) amino 2-nitro-4-ethylaminobenzehe';

anathema." i v The compounds of this inventionican be produced by reacting a 1-secondaryamino-Z-nitroA-aminobenzene with a reactantor reactants soas to replace at least one of the,

"hydr'ogen' atomsof the i l-amino group'with the desired radical. The i lrsecondaryamino-2 rritro-4-aminobenzene I reactant-can be representedby theffollowing genericij formula:

R can be hydrocarbon radicalsor only one of .R and R 7 need be a hydrocarbon radical. illustrative of some of the combinations of R and R of novel classes of 00m? pounds represented by generic Formula I there can be I Formula II wherein represents the sameradic'als as in generic Formula 1, namely, a hydrocarbon radical free from olefinic' and 'acetylenic 'unsaturation havingfrorn'l to about 8 carbon atoms, or a hydroxyalkyl radicalhaving from i p to 4carbonatoms;'lllustrative'ofcompounds re'pres'efnb Patented Feb. 2, 1965 t 7 ed by generic Formula 11 there can be mentioned: l-methylamino-2-nitro-4-arninobenzene; l-(2-hydroxyethyl)ami no-2-nitro-4-aminobenzene; '1-phenylaminoa2-nitro-4-aminobenzene; 1-cyclohexylamino-2-nitro-4-arninobenzene; and the like.

The l-secondaryamino-2-nitro 4 alkylaminobenzene compounds of this invention can be produced byreacting'a 1-secondaryamino-2-nitro-4-aminobenzene with an alkylating agent. 'Illustratively, a l-sec'ondaryamino-Z- T nitro-4-aminobenzene, e.g., 1 -methy1amino-2-nitro-4-;

aminobenzene (about 60 parts by weight) is'dissolved,

preferably with heating. to about 65 C., in alower alkyl monohydricalcohol (about 1,000 parts), such as methanol. An aqueous solution of a base, such as sodium carbonatetabout 30.parts of sodium carbonate, in 180 a parts of water), 'is then added to the alcoholic solution and the mixtureis-then'permitted to cool to about with a molar excess of sulfuric acid and permitted to remain at a temperature of about 3C. to about 4 C. until thetosyl product is completely dissolved. The sul-.

fate salt is then neutralized with ammonia to obtain the base :form of the--l alkylamino}2-nitro 4-hydroxyalkylaminobenzene Which-can be recovered from the reaction C., after which time a dialkyl sulfate, e.g., dimethyl sulfate (about '25 parts) is slowly added to'the reaction 1 mixture. .The reaction-mixture is then boiled for about two hours, with the optional addition of more of the dialkyl sulfate (e.g., about 17 parts). Generally, from about 1.5 r'noles to about 2 moles of the dialkyl sulfate per mole of the nitro compound is employed, and preferably 2 moles of the dialkyl sulfate The l-secondaryamino-Z-nitro-4-alkylaminobenzene which is thus produced is recovered from the reaction mixture by conventional techniques, such as'fr'actional distillation, ex-

]traction, extractive distillation, precipitation or combina tions of two'or more ofthe'se-techniques. 1

In order toprepare the novelcompounds of thisinvention wherein the 4 -amino group is substituted with at least one hydroxyalkylggroup, a I-secondaryaminO-Z nitro-4-aminobenzene can be reacted with a halogen substitution product of a'monohydric or polyhydric aliphatic alcohol by refluxing or simply heating above r'oom. temperature and in thepresence of an aqueous solution of an acid-binding agent, such as an alkali metal hydroxide, calcium oxide, etc, The reaction time can vary from about 4 to 6 hoursQand preferably about 4 hours. ;Generally, molecular proportions of the nitro cornpound and the alcohol reactant are employed. The quantity'of the I 'acid binding agent employed is in excess of the theoretical quantity required to neutralize the acid formed, and this excess can var'y from; about 10% to 100%";niore than theory. Illustrative of the halogen substituted alcohol reactant there canbe mentioned: -1-hydroxy-2rchlorethane and 1\,2-dihydroxy-3-chlorpropane. 'The' hydroxyalkyl derivative-of the nitro compound can berecovered by conventional means, such as by boiling toconcentrate the reaction mixture and then salting out by addition; of sodium chloride. V I

When/the l-secondaryamino,radical of the compounds of genericiiFormula II is1an alkylamino radical audit is desired tosubstitute the l-arnino group with a hy' droxyalkyllradical to'produc'e one of the compounds of Q generic' Fo'rmula I, it is preferable first, to rea'ctthe 4- j j ductingthis reactiona l-alkylamin-o compoundflo'f Formula 'II is first dissolved in an organic base, such as j pyridine or a homologue thereof. The ptoluenes'ulfonyl' chloride, about 1.2 to about 1.4'moles for. each mole, of the l-alkylamino compound of Formula II, is' then.

added slowly'at about-roomjtemperature to the organic base solution of the l-alkyla'minocompound of Formula II. The'reaction mixtureis then refluxedlfor about 0.5 to 1.5 hours and preferably about l hour to effect reand cooled to about 20 C. to about 25 C. in order to precipitate the tosyl derivative of the lalkylamino come amino group of 'a Formula Ill-compoundfwith p-toluene-J sulfon'yl'chloride-ari'd 'forrn' the tosyl derivative. "-In'con- 7 action. The reaction mixture lS'lhI] poured in water pound. The precipitate is then filtered." The l-alkylaniino-2-nitr0-4,-tosyl farninobenzene is' then dissolved in r water and sodium hydroxide. The solution is cooledto about 1,0? C. and ethylenechlorohydrin about'. 1.25 to.

,propriate 1-secondaryamino 2-nitro-4-aminobenzene dissolved in a lower alkyl monohydric alcohol, such as mixture by conventional techniques, such as first cooling the mixture and then salting out by, the; addition of sodium chloride.

In orderto prepare the novel compounds of this invention, wherein the 4-amino'group-is substituted with two hydroxyalkyl radicals, e.g., two hydroxyethyl radicals, the following process can be employed. The apethanol, anda small quantity of water is added to the solution, e.g.,'from about 1 to about 12% by Weight of the quantity of alcoholjernployed. The solution is refluxed and an alkylene oxide, e.g., ethylene oxide is bubbled into therefluxing mixture until the mixture has absorbed the desired molar quantity of the alkylene oxide, e.g., .2 moles of ethylene oxide per mole of the nitro compound when it is desired to produce the bis-hydroxyp The 1-secondaryamino-2-nitro-4-[bis-. (hydroxyalkyl)amino] benzene is thenrecovered by, conalkyl derivative.

ventional techniques, such as fractional distillation, ex

traction, extractive distillation, precipitation orcombi-na- V tions of two or. more of these methods; By still another method the 1-secondaryamino-2-nitrd4-[bis(hydroxyalkyl)amino]ben zene compoundscan be prepared by bydroxyalkylating an appropriate l-secondaryamino-Z-nitro- .'4-aminobenzene in the presence of an aqueous sodium hydroxide solution. 7 p

i The 1-secondaryamino-2-nitro-4-aminobenzene react-. ants can beproduoed bya number of methods including the reduction of a l-secondaryamino-2,4-dinitrobenzene to. the corresponding lj-secondaryamino-2-nitro-4-aminobenzene. {The l-seco-ndaryamino-2,4-dinitrobenzene re? actan t can be represented by the following generic for- Formula III Wherein R represents the vsame radicals asin generic Formula l, namely, a hydrocarbon radical freefrom olefinic and acetylenic unsaturation having from '1, to

'about8 carbon 1 atoms, or a "hydro'xyalkyl radical having 1 from 1 to 4 carbon atoms. One process forthe reduction of the 1-secondaryamino,-2;4-dinitiobenzene to the corre 1 sponding 1l-secondaryamino-Z-nitroa4aminobenzene is by introdueing about 3 moles of hydrogen into a hydrogena tion apparatusmaintained at about 25 to 70 C. and' 2t to '3 atmospheres of pressure and containing a mixture of (a) an"isopropanolic orjethanolic solution of about 1 -mole of a l l-secondaryaminor2g4 dinitrobenzene; (b) a eatalytically'effective quantity of ,platinfim or palladium and'(c) about 2 mo1es ofa'n aqueous solution of a strong inorganic acid, such'as hydrochloric or'sulfur'ic acid, e.g.,

' a' 50% solution of H' SOQin water, to give a strongly acid reaction mixture; This hydrogenation can be carriedout in less than-one hour to produce the-acid addition salt of the 1-secondaryamino-Z-nitro-4-aminobenzene. The acid addition salt is then reacted with an alkaline material to produce the free base form of the amino compound by the conventional methods well known in the art. This reduction process is illustrated in Examples 7 to 9 of this specification.

The novel compounds of this invention have utility for dyeing keratinaceous materials and particularly living human hair. When used as dyes, they possess many advantageous properties. Illustratively, they havea pronounced atfinity for the hair; they exhibit a good dyeing union with both normal and permanently waved hair, particularly gray hair; they give a wide spectrum of colors, such as that of bluish-red over a violet to a blue and when used in combination with known dyes, they can easily produce various blonde to brown shades; they lose little color upon shampooing; have good lightfastness and rubfastness; they produce bright and lusterous shades; they have good storage stability; and do not stain the scalp. A further advantage is that they do not require the use of the conventional peroxide additives, e.g., hydrogen peroxide, for color formation or fixation to the hair. Although the prior art describes certain nitro derivatives of p-phenylene diamines as hair dyes, the prior art p-phenylene diamines do not have two secondaryamino groups wherein at least one of the secondaryamino groups carries a hydrocarbon radical. The compounds of the instant invention have many advantageous properties over the prior art compounds, and particularly in the range of colors produced; good dyetake at pH values of 7 to about 9; uniformly of dyetake between permanent waved parts of the hair and non-permanent waved parts of the hair; the ability to be removed more easily from the hair by special treatments; and improved lightfastness, rubfastness and washfastness.

The dyeing compositions of this invention comprise neutral or alkaline aqueous solutions of the novel compounds. In addition to the water, alkalizing agent and dye, the compositions can also contain the conventional ingredients found in dyeing compositions, such as organic solvents for the dye, thickeners, detergents, gums and the like. Alkalizing agents are ordinarily added to the compositions, since the pH of the dyes varies from that of weakly acidic to about neutral.

The dyeing compositions of this invention can be applied to keratinaceous materials by the conventional techniques used in the art. Illustratively, when applied to living hair on the human head, the compositions 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 the wide range used in the hair dyeing art such as periods of about 5 minutes to about 2 hours, and preferably from about minutes to about 60 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 C. to above about 60 C. and preferably from about 20 C. to about 45 C.

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 dis persing the dye in water of 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. Illustrative of the organic solvents which can be used, there can be mentioned: the lower alkyl monohydric alcohols, such as ethanol or isopropanol; lower aliphatic dihydric alcohols, e.g., propylene glycol; various polyhydric alcohols; ketones; and esters. The dispersion of the various ingredients can also be facilitated by addition of a detergent or dispersing agent, such as lauryl or myristyl sulfate or sulfonate. The water miscible organic solvents employed to facilitate solution of the dye can vary from about 1% to about 30% by weight of the composition, and preferably from about 2% to about 10%. The detergent or dispersing agent can vary from about 1% to about 30% by weight of the composition.

Any water-soluble alkalizing agent that 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 or hide of the pelt, at its ultimate concentration in the composition to be applied to the keratinaceous material, can be used. A preliminary test of some selected alkalizing agent can be made to note its compatibility with the dye or to introduce 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 the ammonia, any other compatible ammonia derivative alkalizing agent, such as a lower alkanolamine, such as mono-, dior triethanolamine, or alkyl amines or alkylenediamines, such as monoethylamine, diethylamine, propylarnine, dipropylarnine or propylene diamine or a heterocyclic amine, such as morpholine. Any of these ammonia derivative alkalizing agents as well as ammonium hydroxide may be broadly referred to as an ammonium alkalizan Also, as alkalizing agent, any alkaline earth hydroxide, for example, calcium hydroxide or magnesium hydroxide, can be used up to the limit of its water stability and at any concentration that fails to produce a precipitate with any of the components of the composition. 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, or injure the hide of the fur pelt.

The quantity of the various ingredients in the dyeing compositions of this invention can vary over a wide range. The novel dyes of this invention can be employed in the conventional concentrations used in the dyeing of the various keratinaceous materials. Illustratively, tinctorial- 1y effective quantities can vary from less than about 0.01% to greater than about 10% by weight of the aqueous solution. In the dyeing of living human hair the concentration of the dye will preferably vary from about 0.05% to about 5% by Weight of the aqueous solution, and particularly from about 0.1% to about 3%. Any selected compatible alkalizing agent should be used to give .a pH of about 7 or 7.5 to about 12, and preferably a pH of about 7.5 or 8 to about 11. The quantity of the alkalizing agent employed can vary over a wide range depending on the dye and particular alkalizing agent employed. Thus the alkalizing agent can vary from less than about 0.1% to about 5% and preferably from about 0.5% to about 2% by weight of the aqueous solution. 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, such as solvents.

The dyes of this invention are water dispersible in the usual generic sense as embracing true solutions of the dyes in water or any aqueous medium within the bounds of the invention, as well as stable homogeneous colloidal solutions of them in such aqueou medium. Thus, the aqueous medium includes the aqueous alkaline medium. It includes also any aqueous medium containing, for example, a sufl'icient amount of a compound, e.g., ethanol employed as a common solvent to enhance the solution of the dye or some other organic material. The compositions can be formulated as solutions, gels, emulsions,

dispersions, and the like.

The 'following examples are illustrative of the inven specification refers to parts by weight, unless otherwise specified. EXAMPLE 1 Preparation .of I-(Z'Jzydroxyethyl) amino-2-nitro-4- methylaminobenzene Sixty parts o-f 1-(2-hydnoxyethyl)arnino-2-nitro-4- aminobenzene were dissolved at 60 C. to 70 C. in 1,000 parts of methanol. An aqueous solution of 30 parts of sodium carbonate in 180 parts of water was then added to the methanolic solution. After cooling the mixture to C., 25 parts of dimethyl sulfate was added dropwise. The mixture wasthen boiled. After boiling for 1 hour, 17 parts of dimethyl sulfate was added dropwise and boiling was continued for another hour to produce the 1-(2-hydroxyethyl)amino-2-nitro-4-methylarninohenzene. This product was recovered from the reaction mixture by distilling otf'the methanol, digesting the residue with 100 parts of water, and finally filtering the reaction mixture to recover the product as a precipitate. The product, 1 (2' hydroxyethyDamino 2 nitro 4 methylaminobenzene was recrystallized in ethyl acetate and found to have a purple color and 'a melting point of 965 C.

EXAMPLE 2 Preparation of 1-methylamino-2-nitr0-4-methylamin0- benzene 1-methylarnino-2-nitro-4-aminobenzene (3.3.4 parts) were dissolved at 60 C. to 70 C. in 660 parts of methanol. An aqueous solution of 20 parts of sodium carbonate in 120 parts of water was added-to the methanolic solution and the mixture was permitted to cool to 2 C. This mixture was poured in 300 parts of ice, giving a yellow solution of the dye sulfate; and by neutralizing with ammonia, a bluish violet dye, larnethylamino- '2-nitro-4-(2-hydroxyethy1)aminobenzene, was obtained C. and 26.5 parts of dimethyl sulfate was then added 1 dropwise to the mixture. The mixture was then boiled for 5 hours. The methanol was distilled off and the concentrated solution of the 1 methylamino-2-nitro-4-methylaminobenzene product was digested with 100 parts of water. After the mixture was cooled, it was filtered and the product was recovered from the reaction mixture as the precipitate. The 1-methyla.mino-2-nitro-4-methyl- 'aminobenzene crystals had a violet color and a melting point of 81-82 C. f V

EXAMPLE 3 Production of 1-methylaminoQ-nitrol-(2-hydr0xyethyl) -aminobenzene 1-methylamino-2-nitro-4-aminobenzene (66.8 parts) was dissolved in 450 parts of pyridine. At approximately 20 C., 100 parts of p-toluene sulfony-l chloride was added slowly. The bath was then boiled for one hour. The red color of the. solution at the beginning was changed to yellow. The solution was poured into 2,000 parts of water and ice was added for cooling. The tosyl derivative which was thus produced was in the form of red crystals which were filtered and dissolved in 1,500 parts of water and parts sodium hydroxide. This gave a purple solution. The solution after filtration was acidified with 65 parts of concentrated hydrochloric acid (38% by weight HCl content) to a clear blue congo paper reaction. It was then filtered, washed acid free, and dried in vacuo. This tosyl derivative, l-methylamino-Z- nitr-o-4-tosylaminob-enzene had a melting point of 160 C. The 1 methylamino 2-nitro-4-tosylarninobenzene (125.4 parts) was dissolved in 1,500 parts of'water and 15.6 parts of sodium hydroxide. The solution was cooled I to 10 C. and 37.5 parts ethylene chlo-r-ohydrin were added dropwise over a period of about 1.5 hours. After an additional half hour stirring at 10 C the batch was heated at 95 C. to 98 C. for 2 hours. The pH was 6.8.; After cooling the orange crystals of the l-methyl parts of this tosyl product was dissolved in 3 par-ts of sulfuric acid (50% by weight) at a temperature of about which had a melting point of 100 to 101 C.

EXAMPLE 4 Preparation of 1-methylamino-2-nitr0-4-[bis(2'- hydroxyethyl amino] benzene 1-methylamino-2-nitro-4-aminobenzene, 33.4 .parts (0.2 mole) were dissolved in a mixture of 350 parts ethanol and 50 parts of water. This solution was refluxed and a current of ethylene oxide, 17.8 parts (0.4 mole) was bubbled in the reaction mixture; The reaction mixture was then steam distilled to eliminate the ethanol. Upon permitting the reaction mixture to cool the l-methylamino 2 nitro-h[bis(2'-hydroxyethyl)amino]benzene crystallized out as blue crystals which were recovered by filtration. The melting point of this material was 101 to 102 C.

EXAMPLE 5 Preparation of 1-phenylamino-2-nitr0-4-(2'-hydroxy- V eIhyD-aminobenzene To 1 gram of 1-phenylamino-2-nitro 4-arninobenzene there were added 100 ml. of l-hydroxy-Z-chlorethane. This mixture was then refluxed and 100 grams of 25%. by'weight sodium hydroxide solution was added slowly over a period of about'one hour. The mixture was steam distilledand then cooled and the l-phenylamino-Z-nitro- 4-(2-hydroxyethyl)aminobenzene was extracted from the reaction mixture with ethyl acetate. The ethyl acetate was evaporated to leave the 1-phenylamino-2-nitro-4-(2- hyd'roxyethyl)aminobenzene as purplewiolet crystals.

' EXAMPLE 6 Preparation of 1-cyclohexylamino-2-nitro-4-(2'- hydroxyethyl)aminobenzene To 1 gram of 1 cyclohexylamino-2-nitro-4-aminobenzene (2-nitro-4-amino-N-cyclohexyl aniline), there was added 100 ml. of l-hydroxy-Z-Chlorethane. The mixture was refluxed and there was added 100 grams of an aqueous solution of sodium hydroxide (2 5% by weight NaOH content) over a period of 1 hour during refluxing. The mixture was permitted to reflux for an additional 0.5 hour and then steam distilled, cooled, and the l-cyclohexylamino-Z-nitro-4-(2'-hydroxyethyl)aminobenzene was extracted from the reaction mixture with ethyl acetate. The ethyl acetate extract was heated to evaporate the ethyl acetate to leave the product as bluish-purple crystals.

' EXAMPLE 7 Reduction of 1-methylamino-2,4-dinitrobenzene t0 1- methylamino-Z-nitro-4-aminobenzene In a hydrogenation apparatus there were charged 0.5 gram of 5% platinumon charcoal, a mixture of 9.85 grams (0.05 mole) of pulverized 'N-rnethyI-ZA-dinitroaniline, also referred to in this specification as l-methylamino-2,4-dinitrobenzene, in 200 ml. of ethanol (96% ethanol content) and 20 m1. of concentrated (38%) hydrochloric acid. The reaction mixture was heated to 60 C. and held at this temperature while there was introduced into the reaction chamber, with constant shaking 0.303 gram (0.15 mole) of hydrogen at a pressure of 50 to 40 p.s.i. (over a period of about 30 minutes). After cooling the reaction mixture to room temperature, a mix ture of the catalyst and the hydrochloride of the nitroaniline separated as yellow crystals. These crystals were filtered 01f, dissolved in 50 ml. of hot water and the undissolved catalyst filtered oif. The filtrate was cooled and the resulting acid addition salt of l-methylamino-2-nitro-4- aminobenzene which precipitated out of solution was recovered by filtration. The salt was alkalized with aqueous ammonia to obtain the free base form of the aminoaniline product, i.e., 1-rnethylamino-2-nitro4-aminobenzene as dark red crystals.

' Dyeing of hair with 1-methylamin0-2-nitr0-4+(ZT-hydroxy- Into a hydrogenation apparatus there were charged 0.2 gram of platinum on charcoal 2 ml. of water, 20

' ml. of isopropanol, 13.2 grams & mole) N-phenyl 2,4-

dinitroaniline, also referred to in this specification as lphenylamino-Z,4-dinitrobenzene, and an additional 80 ml. of isopropanol and 20 grams of a 50% aqueous solution of H 30 Theternperature of the reaction mixture was brought up to about 65 C. andthen there was introduced into the reactor at a pressure of 50 to 40 psi. about .303 gram (0.15 mole) of hydrogen over a period of 17 minutes. The temperature of the reaction mixture at the end of the 17 minute period was 52 -C. The reaction mixture was permitted to cool, the autoclave was opened and the sulfate salt or" 1-phenylamino-Z-nitro-4-aminobenzene which was produced by the hydrogenation was filtered oil as a precipitate. The sulfate salt was subsequently alkalized and separated to obtain the l-phenylamino-2-nitro-4- aminobenzene as red crystals.

EXAMPLE 9 Reduction of 1-(2-hydroxyethyl)amino-2,4-dinitr0benzene to 1-(2-hydroxyethyl)amino-2-nitro-4-amin0benzene In a hydrogenation apparatus there were placed: 0.5

gram of 10% palladium on charcoal, ml. of concentrated hydrochloric acid (38%) and a solution of 22.7

grams (0.10 mole) of N-(2-hydroxyethyl)2,4-dinitroaniline, also referred to in this specification as 1-(2'-hydroxyethyl)amino-2,4-dinitrobenzene, in 150 ml. of ethanol.

This reaction mixture was hydrogenated at a pressure of 50 to p.s.i. and a temperature of 60 C. After absorption by the reaction mixture of 0.3 mole of hydrogen, the apparatus was permitted to cool. The yellow hydrochloric acid salt of 1-(2-hydroxyethyl)amino-Z-nitro-4-aminobenzene was separated from the catalyst by dissolving in hot water. The free base 1-(2hydroxyethyDamino-Z-nitro-4- of monoethanolamine, l gram of triethanolamine, 1 gram.

of polyacrylic acid and 1 gram of glycerol at 50 This composition was heated to about C. to 37 C. and

T0 EXAMPLE 12 By employing the procedure and composition, including the various quantities of ingredients except for the substitution of the following dyes .in place of the lmethylamino 2-nitro-4-(2'hydroxyethyl)aminobenzene of Example 11 there are produced the following colors on gray hair: l-(2'-hydroxyethyl)amino-2-nitro-4-methylaminobenzene produces a blue color; l-methylamino- Z-nitro-4-methylaminobenzene produces a reddish purple color; 1 methylamino-2-nitro-4-[bis(2'-hydroxyethyl) amino1benzene produces a blue color; l-phenylamino-Z- nitro-4-(2-hydroxyethyl) aminobenzene produces a violet color; and 1-cyclohexylarnino-2-nitro-4-(2-hydroxyethyl) aminobenzene produces a violet color.

' EXAMPLE 13 Preparation of I -methy lamina-2 -1zitro-4 [bis( 2'- hydroxyezhyl) amino] benzene One mole of l-methylamino-2-nitro-4-aminobenzene was admixed with 10 moles of l-hydroxy-Z-chlorethane in 200 grams of Water. This mixture was then heated to about 95 to 98 C. and maintained at that temperature while 4 moles of a 25% aqueous solution of sodium hydroxide was added dropwise to the mixture. The mixture was then cooled and 100 grams of sodium chloride was added to the mixture to salt out the l-methylarnino- 2-nitro-4-[bis(2'-hydroxyethyl)amino1benzene as blue crytals. The mixture was then filtered to recover this glycol derivative.

Illustrative o't specific novel compounds of this invention there can be mentioned:

aminobenzene was obtained by neutralizing the salt with 1 then applied to gray hair. After about 20 minutes, the

hair was thoroughly rinsed .and washed with soap and water. The hair was colored blue by the composition and the resulting shade was rubfast and not removable by.

washing with soap and water.

EXAMPLE 11 ethyl) amihobezizene About Zgrams of l-methylamino-2-nitro-4-(2 hydroxy- -ethyl)aminobenz'ene was dissolved in about 17 grams ot isoprop anol, and then about 200 grams 'of'water was added,

with stirring to effect solution. To this solution there I v were added 2 gramsof monoethanolarnine, 1 gram of tri- 'ethanolamine and 1 gram of glycerine,and about 3 grams of .Carbopol 934 (a polycarboxylated vinyl resin produced by the B F. GoodrichflCoJ. The mixture was thoroughly agitated; This composition was then poured onto the hair 7 ENG HiOH O H (1 1-methy1amlno.-2-nitro-4- (2-hydr0xyethy1) amiuobenzene HN-om H-N'CH "(2) .l-methylamino-2-nltr0-4-methylaminobenzene HNOHa onj omon l/ N orrzomorr (3) l-m'e'thylamlnoQ-nitro-d [bis (2' hydroxyethyl) amino] I benzene V aresnaa Although the invention has been described with reference to specific forms thereof, it will .be understood that 1 prising an aqueous solution of atinctorially elfcctive' quantity of a p-phenylene diamine represented by the following formula:

E-N-RQ V RII N RI wherein R is a member selected from the group cnsisting of non-olefinic and non-acetylenic hydrocarbon and havingv from 1 to vabout 8 carbon atoms, and hydroxyalkyl having from 1 to 4 carbon atoms; and R' is a member selected from the group consisting of saturated aliphatic hydrocarbon having from l to 4 carbon atoms and hydroxyalkyl having from 1 to 4 carbon atoms and 'R is selected from the group consisting of hydrogen and hydroxyalkyl having from 1 to 4 carbon atoms, provided that R is hydroxyalkyl only when R is also hydroxyalkyl and further provided that at least one of R and R is hydrocarbon; and a suflicient quantity of an alkalizing agent to give the aqueous solution a pH of about 7.5 to about 12.

2. vThe composition of claim 1 wherein both R and 'R of the formula are alkyl having from ,1 m4 carbon R represents monohydroxyalkyl having from 1 to 4' carbon atoms and R is hydrogen.

4. The composition of claim l whereinlR of the formula represents alkyl having from 1 to 4 carbon atoms and R and R are the same hydroxyalkyl 5. The composition of claim 1 wherein R -off-the formula represents alkyl having from 1 to 4 carbon atoms and R and R" represent the same hydroxyethyl.

6. The composition of claim 1 wherein R is monohydroxyalkylhaving from 1 to 6 carbon atoms; R is an alkyl having from 1 to 4 carbon atoms and R is hydrogen; p

7.,The composition of claim 1 wherein R is phenyl and R is monohydroxyalkyl havingifrom '1 to 4 carbon 'atoms'and R is'hydrogen; 1

'8. The composition of claim 1 wherein R is cyclovided that R is hydroxyalkyl onlywhen R is also hydroxyalkyl and further provided that at least one of R and R is hydrocarbon; and a suflicient quantity of an alkalizing agent to impart a pH of about 8 to about 11 vto the said aqueous solution.

11. A hair dyeing composition for living human hair comprising an aqueous solution containing from about 0.1% to about 3% by weight of a p-phenylene diamine represented by the following formula:

JI-lTl-R 'from the group consisting of saturated aliphatic hydrocarbon having from 1 to 4 carbon atoms and hydroxyalkyl having from 1 to 4 carbon atoms and R is selected from the group consisting of hydrogen and hydroxyalkyl having from 1 to 4 carbon atoms, provided that R is hydroxyalkyl only when R is also hydroxyalkyl and fur- 'ther provided that at least one of R and R is hydrocarbon;

and from about 0.1% to 5% of an ammonium alkalizant solution. I

'12. The composition of claim 11 wherein the p-phenyl- ,ene diamine is 1-methylamino-2-nitro-4-(2-hydroxyethyl) aminobenzene v 13. The composition of claim 11 wherein the p-phenylene diamine is 1-(2-hydroX yethyl)-2-nitro-4-methylaminobenzene.

r 1 14. The composition of claim 1 1 wherein the p phenyl- ,ene diamine is 1-methylamino-2-nitro 4-methylaminobenzene. 7 15 The composition ofclaim 11 wherein the p-phenylene diamine is 'l-phenylamino-2-nitro-4-(2-hydroxyethyl) aminoben'z ene.

v16. The composition of claim ;11 wherein the p-phenylene diamine is 1-methylamino-2-nitro-4-[bis(2-hydroxyethyl)amino]benzene.f f I s 1 17. The composition of claim 11 wherein the p-phenylene diamine is 1-cyc1ohexylamino-2-nitro-4-(2-hydroxyhexyl and R is monohydroxyalkyl having'from'I to 4 7 carbon atoms and R is hydrogen.

aqueous solution varies from about 8 to about 11.

10. A hair dyeing composition for living human hair 3 B a r-R I sis-ting of nori-olefinic and'non acetylenic hydrocarbon having from 1 to about 8 carbon atoms, and hydroxy-;

alkyl having fromclr to 4 carbon atoms; R is a member selected fro'm the group consisting of saturated aliphatic hydrocarbon having from 1' to 4 carbon'atoms and hy-f' droxyalkyl having from 1 to 4 carbon atoms and R" is selected from the'group consisting' oflahydrogen andhydroxyalkyl having from 111014 carbon atoms, proethyl) aminobenzene.

. 18. A proc'essfor dyeing living human hair which comprises applying thereto a tinctorially effective quantity of an aqueous solution; containing a p-phenylene diamine 7 V 1 derivative represented by the following formula: 9. The composition of claiml wherein the pH of the w a Y wherein R is a member selected from ,thegroupco nsist- 3 ing of non-olefinic and non acetylenic hydrocarbon'havwherein R is a member selected from tthe group con-V ing from'l to 8 carbon atoms; and hydroxya'lkyl having from l te carbon atoms;' Rziis a member selectedfro'm the group consisting of; saturatedaliphat-ic hydrocarbon I having from 1 to 4 carbon atoms and hydroxyallgylhavmg from 1 to 4 carbon atoms and R. is" selected from the group consisting of hydrogen and hydroxyalkyl havf,

ing from 1 to 4 carbon atoms providedthat R is hydroxyallgyl-only when R is 'alsoj hydroXyalkyl and fur- 7 there provided that at least one of R and R is hydrocarbon; and a suflicient quantity of an alkalizing agent to I impart'apH of from aqueous I solutipn.-

ti it out -12 to. the said 19; Apro'c'e's's 'for'dyeiiig living human hair which com- 5 23 prises applying thereto a tinctorially effective quantity of an aqueous solution containing a p-phenylene diamine derivative represented by the following formula:

H--NR- wherein both R and R are alkyl having from 1 to 4 carbon atoms; and a suflicient quantity of an alkalizing agent to impart a pH of about 7.5 to about 12 to said aqueous solution.

20. A process for dyeing living human hair which comprises applying thereto a tinctorially effective quantity of an aqueous solution containing a p-phenylene diamine derivative represented by the following formula:

wherein R is alkyl having from 1 to 4 carbon atoms and R is monohydroxyalkyl having from 1 to 4 carbon atoms; and a sufficient quantity of an alkalizing agent to impart a pH of about 7.5 to about 12 to the said aqueous solution.

21. A process for dyeing living human hair which comprises applying thereto a tinctorially elfective quantity of an aqueous solution containing a p-phenylene diamine derivative represented by the following formula:

wherein R is alkyl having from 1 to 4 carbon atoms and R and R are the same hydroxyalkyl having from 1 to 4 carbon atoms; and a sufi'icient quantity of an alkalizing agent to impart a pH of about 7.5 to about 12 to the said aqueous solution.v a

22. A process for dyeingliving human hair which comprises applying thereto a tinctorially effective quantity of an aqueous solution containing a p-phenylene diamine derivative represented by the following formula:

CHzCHzOH CHBCHZOH wherein R is alkyl having from 1 to 4 carbon atoms; and a suflicient quantity of an alkalizing agent to impart a pH of about 7.5 to about 12 to the said aqueous solution.

23. A process for dyeing living human hair whiehcomprises applying thereto a tinctorially effective quantity of an aqueous solution containing a p-phenylenediamine derivative represented by the following formula:

this wherein R is monohydroxyalkyl having from 1 to 4 car- 1 diamine derivative bon atoms and R is alkyl having from 1 to 4 carbon atoms; and a sufficient quantity of an alkalizing agentto impart a pH of about 7.5 to about 12 to the said aqueous solution.

24. A process for dyeing living'human hair which comprises applying thereto a tinctorially effective quantity of an aqueous solution containing a p-phenylene diamine derivative represented by the following formula:

wherein R is monohydroxyalkyl having from 1 to 4 carbon atoms; and a sufiicient quantity of an alkalizing agent to impart a pH of about 7.5 to about 12 to'the said aqueous solution.

26. A process for dyeing living human hair which comprises applying thereto an aqueous solution containing from about 0.05% to about 5% by weight of p-phenylene diamine derivative having the formula:

wherein R is a member selected from the group consisting of non-olefinic and non-acetylenic hydrocarbon and having from 1 to about 8 carbon atoms, and hydroxyalkyl having from 1 to 4 carbon atoms; R is a member selected selected from the group consisting of hydrogen and hydroxyalkyl having from 1 to 4 carbon atoms, provided that R" is hydroxyalkyl only when R is also hydroxy alkyl and further provided that at least one of R and R is hydrocarbon; and a suflicient quantity ofan ammonium alkalizant to impart a pH of about 8 to about 11 to said aqueous solution; and wherein the Said aqueous solution is at a temperatureof about 20 C. to about 45 C.

27. The process of claim 26 wherein the p-pheny1ene 1S droxyethyl)aminobenzene.

28. The process of claim 26 wherein the p-phenylene diamine derivative is l-methylamino-2-nitro-4-methylaminobenzene. 2

29. The process of claim 26 wherein the p-phenylene diamine derivative is 1-methylamino-2-nitro-4-[bis(2'-hydroxyethyDaminobenzene. q i

30. The process of claim 26 wherein the p-phenylene 1-methylamino-2-nitro-4-(2-hy- 4-methylaminobenzene. r

31. A process for dyeing living human hair which com prises applyingthereto a tinctorially effective quantity of an aqueous solution containing a p-phenylene-diamine derivative represented by the following formula:

RII N RI V v wherein R is a member selected from the group consisting of non-olefinic and non-acetylenic hydrocarbonv having from 1 to 8 carbon atoms, and hydroxyalkyl having from 1 to 4 carbon atoms; R is a-member selected :from the diamine derivative is 1-(2"hydroxyet hyl)amino-Z-nitro- References Cited by the Examiner FOREIGN PATENTS 741,334 11/55 Great Britain.

a V OTHER REFERENCES Chemical Abstracts, vol. 50: 4053-4 (1956).

JULIAN s. LEYlTT, Primary Examiner. r

Claims (1)

1. A COMPOSITION FOR DYEING LIVING HUMAN HAIR COMPRISING AN AQUEOUS SOLUTION OF A TINCTORIALLY EFFECTIVE QUANTITY OF A P-PHENYLENE DIAMINE REPRESENTED BY THE FOLLOWING FORMULA: