(en)Novel salts of morpholino-(2,3-b)phenoxazonium are prepared by condensing a substituted paranitrosoaniline and a 6-hydroxy phenomorpholine. The novel salts are incorporated into hair dye and hair setting lotion compositions.

1.ApplicationNumber: US-32809173-A
1.PublishNumber: US-3896117-A
2.Date Publish: 19750722
3.Inventor: BUGAUT; ANDREE
LAUDON; MONIQUE

4.Inventor Harmonized: BUGAUT ANDREE()
LAUDON MONIQUE()

5.Country: US
6.Claims:
(en)Novel salts of morpholino-(2,3-b)phenoxazonium are prepared by condensing a substituted paranitrosoaniline and a 6-hydroxy phenomorpholine. The novel salts are incorporated into hair dye and hair setting lotion compositions.

7.Description:
(en)United States Patent Bugaut et al.
SALTS OF MORPHOLINO-(23-MPHEN- OXAZONIUM AND HAIR DYE AND HAIR SETTING LOTION COMPOSITIONS CONTAINING THE SAME Inventors: Andree Bugaut, Boulogne-sur-Seine;
Monique Laudon, Gagny. both of France Assignee: LOreal, Paris, France Filed: Jan. 30, 1973 Appl. No.: 328,091
Related US. Application Data Division of Ser. No. l65 740, July 23. 1971, Pat. Nov 3,824.074.
Foreign Application Priority Data July 31, 1970 Luxembourg 61452 US. Cl 260/242; 260/37 R; 260/246 R; 260/244 R; 8/10; 8/179 July 22, 1975 Int. Cl .4 C09!) 19/00 Field of Search 260/246, 242
References Cited UNITED STATES PATENTS 4/l968 Braun 260/246 Primary Examiner-Harry J. Moatz Attorney. Agent, or FirmCushman Darby & Cushman 2 Claims, No Drawings 1 2 SALTS OF MORPHOLINO-(2,3 B) PI-IENOX and (b) a o-hydroxy phenomorpholine having the for- AZONIUM AND HAIR DYE AND HAIR SETTING mula:
LOTION COMPOSITIONS CONTAINING THE SAME s 1 1 This is a division, of application Ser. No. 165,740 filed July 23, 1971, now U.S. Pat. 3,824,074. N
The present invention relates to salts of morpholino- (2,3-b)phenox azonium having formula ,1
N /n l2\ 1 6 3 N 4 0 5/ N R 1 wherein R, is selected from the group consisting of hywherein 1 to s have the meanings indicated ove. drogen and lower alkyl having l-4 carbon atoms, According to a first method of preparing the com- R, and R each independently are selected from the pounds of this invention equimolecular amounts of a group consisting of alkyl having l-4 carbon atoms, hyparanitroso-aniline of formula (11) and of a o-hydroxy droxylalkyl having 14 carbon atoms, Carbamylalkyl phcnomorpholine of formula (III) are heated under rehaving 1-4 carbon atoms, w-aminoalkyl having 1-4 flux in absolute ethanol, in the presence of an excess of Carbon ammsa d i kl l h i 1-4 carbon anhydrous zinc chloride. The product obtained is a atoms wherein the amino moiety is acylated with a double zinc and indamine chloride having the formula:
monocarboxylic organic acid having the formula R'- which is separated from the reaction mixture by filtra- COOl-l wherein R is selected from the group consisting tion. Generally, the reaction is effected at ambient of alkyl having l-4 carbon atoms and phenyl or pressure and the anhydrous zinc chloride is present wherein said amino moiety is monoor di-substituted usually in amounts ranging from about 1 to 1.5 mole with alkyl having 1-4 carbon atoms, 01' wher n h niper mole of paranitrosoaniline or phenomorpholine. trogen of said amino moiety is included in a heterocycle selected from the group consisting of morpholinyl This compound of formula (IV) is, after isolation and and piperidinyl, and Xrepresents a member selected washing in an alcohol such as a lower alkanol, cyclized from the group consisting of Cl", Br, C10,, and by reflux heating in a mixture of dimethylformamide C1 Zn it being understood that these salts can be pres and acetic acid, the development of the reaction being ent in a tautomeric form of that represented by the followed by chromatography. Once the cyclization is above formula and that in the case in which R or R completed, the reaction mixture is diluted in water and represents an w-aminoalkyl, the amine function can be thereafter, filtered. Acid having the formula XH salified by an acid having the formula HX wherein X wherein X has the meaning given above, or a water solhas the meaning given above. uble salt thereof is then added to the filtration product The above compounds can be obtained in accorin amounts sufficient to precipitate the phenoxazonium dance with two methods using as initial reactants (a) a salt of formula (I), which then is isolated by filtration.
substituted paranitrosoaniline having the formula:
A second process for the production of the com pounds of formula (1) comprises reflux heating in an R alcoholic medium, such as a lower alkanol, either (a) NO a salt, such as the hydrochloride or the hydrobromide, N of a paranitrosoaniline of formula (11) with a o-hydroxy (11) phenomorpholine of formula ([11), or (b) a paranitrosoaniline of formula (ll) with a salt, such as the hy drochloride or the hydrobromide, of a 6-hydroxy phenomorpholine of formula (111). In this alternate pro cess, the nitrosated derivative of formula (II) is generally used in the proportion of l to 1.5 moles per mole of compound (lll). Generally, the reaction is carried out at ambient pressure. The development of the reaction is followed by chromatography, and once the cyclization is completed. the resulting reaction mixture is filtered hot. In certain cases, the phenoxazonium chloride or bromide crystallizes upon cooling of the filtrate. It is then separated by filtration and transformed, if necessary, into the desired phenoxazonium salt. In the other cases, either an acid having the formula HX where X has the meaning given above or a watersoluble salt thereof is added to the filtrate, diluted or not with water.
The compounds of formula (1) constitute dyes of a remarkable ability for the dyeing of keratinous fibers, in particular human hair. They exhibit great solubility in water and in alcohol, such as lower alkanols and they exhibit great dyeing power within a wide pH range, for instance, from about 4.5 to 11.
Consequently, the present invention also relates to a novel dyeing composition for keratinous fibers, in particular human hair, comprising an aqueous solution containing at least one compound of formula (I).
The dyeing compositions according to the invention can contain only the compounds of formula (I), in which case it is found that they impart to white hair shades ranging from blue to green. Advantageously, the application period to achieve such results can be in the order of about three minutes at room temperature, because of the exceptional affinity of the compounds of formula (I) to keratinous fibers. The shades obtained in this manner, which are very luminous, often iridescent, and rich in shimmers or gleams, have the further advantage of masking the red in reddish-brown and auburn hair.
The exceptional affinity of the dyes of this invention for keratinic fibers, together with their excellent solubility in water and alcohols enable these compounds to be incorporated in the compositions according to the invention in extremely small concentrations, which can vary between 0.0005 to 1% in weight and preferably between 0.001 and 0.5% by weight of the composition.
The pH of said compositions generally ranges between about 4.5 and 11 and preferably between and 10.
Further, the compositions according to the invention can also contain other direct dyes, for example, azo dyes, anthraquinone dyes, nitro dyes of the benzene series, indoanilines, indophenols, indamines or other known phenoxazonium salts.
The dyeing Compositions according to the invention are generally in the form of aqueous or aqueous alcoholic solution which can be prepared easily by dissolving in water or in a mixture of water and alcohol one or more of the compounds of formula (I), mixed or not mixed with other direct dyes. The compositions can also contain thickeners and be in the form of creams or gels. Generally lower alkanols such as ethanol and isopropanol are used to form the aqueous alco holic solutions, with the alcohol being present in amounts ranging from about l to 50 weight percent of the total dye composition.
Further, the compositions according to the invention can also contain various ingredients normally used in cosmetics, for example, wetting agents, dispersing agents, swelling agents, penetrating agents, emollients or perfumes. They can also be packaged in aerosol cans or containers under pressure using conventional aerosol propellants such as the chlorofluorohydrocarbons including dichlorodifluoromethane, trichloromonofluoromethane and their mixtures.
The dying of keratinous fibers, in particular human hair, by means of the dyeing compositions according to the invention, is effected in a conventional manner by applying the composition on the fibers to be dyed, with which it is allowed to remain in contact for a period varying between 3 and 30 minutes, said application being followed by rinsing the fibers and by eventually washing and drying the fibers.
The dyes according to the invention can also be used in the form of capillary hair setting lotions.
Thus the present invention also relates to a hair setting lotion composition comprising an aqueous alcoholic solution containing at least one cosmetic filmforming resin and at least one compound of formula The proportion of the compound of formula (I) in the hair setting lotions according to the invention can be extremely small. This proportion generally varies between 0.005 and 1% in weight and preferably between 0.001 and 0.5% by weight of the total composition.
Representative cosmetic film-forming resins which can be used in the hair setting lotion composition of this invention include, for instance, polyvinylpyrrolidone having a molecular weight ranging from about 10,000 to 700,000, the vinyl acetate-crotonic acid copolymers having a molecular weight of about 40,000 to 200,000 wherein the ratio of VA/CA is preferably about 90/10; vinylpyrrolidone-vinyl acetate co polymers wherein the ratio of PVP to VA ranges between 30/70 and /30 and which have a molecular weight ranging between about 40,000 to 160,000; maleic anhydride-butylvinyl ether copolymers, etc. These resins are used generally in an amount from about 1 to 3% by weight of the total composition.
Representative alcohols suitable for the production of the hair setting lotion compositions of this invention are the low molecular weight alcohols, and preferably ethanol or isopropanol, and they are present generally in amounts ranging from about 20 to 50% by weight of the said composition.
The pH of the hair setting lotion composition can vary between about 4.5-11, and, preferably, between about 5l0.
The hair setting lotion compositions of this invention which contain only dyes of formula (I) constitute tinting compositions which impart extremely luminous glints to the hair and which cover up or mask the red of auburn or reddish-brown hair.
These hair setting lotion compositions can also contam other direct dyes, for example. azo dyes or anthraqumone dyes, nitro dyes of the benzene series, indoanilines, indophenols, indamines or other phenoxazonium salts.
EXAMPLE I 4-methyl S-diethylamino morpholino (2,3-b) phenoxazonium perchlorate is prepared as follows:
To a dispersion of 0.045 mole (9.65 g) of paranitroso N,N-diethylaniline hydrochloride in 35 cc of 96 ethanol, there is added 0.03 mole (4.95 g) of 4-methyl 6- hydroxy phenomorpholine. The resulting alcoholic solution is reflux heated for L5 hours and then hot filtered. To the filtrate there are added 35 cc of water, and a resulting very light brown insoluble substance is then eliminated by filtering the reaction medium again. After addition of sodium perchlorate to the hydroalcoholic solution, the expected phenoxazonium perchlorate precipitates and is recovered by filtration yielding about 5 grams thereof. After washing the recovered product with a little ice water and then with ethanol, it melts with decomposition at 235. The product thus obtained is chromatographically pure.
Calculated for C 10 CIN 3 a EXAMPLE 2 4-methyl 8-dibutylarnino morpholino (2,3-b) phenoxazonium perchlorate is prepared as follows:
To 35 cc of absolute ethanol there are added 0.045 mole (l2.l7 g) of p-nitroso N,N-dibutylaniline hydrochloride and 0.03 mole (4.95 g) of 4-methyl G-hydroxy phenomorpholine. The resulting alcoholic solution is brought to reflux for one hour and a half and then hot filtered. cc of water are then added to the filtrate and the reaction mixture is again filtered to eliminate a resulting brown insoluble material. After addition of sodium perchlorate to the aqueous alcoholic solution. the expected phenoxazonium perchlorate precipitates and is removed by filtration, yielding about 4.6 g of the same which. after recrystallization in methanol, melts with decomposition at l8l.
Calculated for Found Analysis 1=i mN.,0..Ci
EXAMPLE 3 0.045 mole (l5 g.) of p-nitroso N,N-(B-piperidinoethyl,ethyl) aniline dihydrochloride and 0.03 mole (4.95 g) of 4-methyl o-hydroxy phenomorpholine are added to 60 cc of 96 ethanol. The resulting alcoholic solution is reflux heated for one hour and hot filtered. Then cc of water are added to the filtrate. After addition of 70% perchloric acid to the hydroalcoholic solution, the above expected phenoxazonium diperchlorate precipi tates and is removed therefrom by filtration, yielding about 8 g of the same which is then washed with ethanol. The resulting product is chromatographically pure and melts with decomposition at 249.
morpholino (2.3-b) phenoxazonium perchlorate is prepared as follows;
1\ CH CH l 3 i F NH-CO- 0.03 mole g) of p-nitroso N,N-(B- benzoylaminoethyl, ethyl) aniline hydrochloride and 0.02 mole (3.3 g) of 4-methyl o-hydroxy phenomorpholine are added to cc of 96 ethanol. The resulting alcoholic solution is heated to reflux for one hour. It is then hot filtered and lOO cc of water are added to the filtrate. The resulting mixture is then filtered again to eliminate a light brown insoluble contained therein.
After addition of 70% perchloric acid to the aqueous alcoholic solution, the phenoxazonium perchlorate precipitates and is removed by filtration yielding about 6 g of the same which is then washed with a little ice water. After crystallization in cc of 96 ethanol. the product is chromatographically pure and melts with de composition at l57.
OH-CI-L-CH.
a 0 \II n v C -Crl On CH 2 Analysis Calculated for 'Found an st 1 t ca 57.51 57.12 51.20 H92 i 4.97 i 5.09 5.06 N7r g [0.33 i032 10.38 CW: 6 61 6.48 6.44
' EXAMPLE 5 4-methyl 8-di-B-hydroxyethylamino morpholino (2,3-b) phenoxazonium perchlorate is prepared as follows:
To 60 cc of 96 ethanol there are added 0.03 mole (7.39 g) of p nitroso N.N-di-B-hydroxyethylaniline hy -amino 25 drochloride and 0.02 mole (3.3 g) of 4-methyl 6- hydroxy phenornorpholine. The resulting solution is heated to reflux for one hour and then cooled. 60 cc of water and 3 cc of perchloric acid are then added, thus precipitating the above phenoxazonium perchlorate which is then filtered, yielding about 3.5 g of the same which melts with decomposition between 263 and 265.
This product is chromatographically pure.
Analysis Calculated for Found C tli n ii fl C7r 50.05 50.20 50.38 H% 4.82 4.97 4.92 N% 9.22 9.36 9.34 Cl7v 7.79 7.85 7.90
EX AM PLE 6 4-methyl S-di-B-hydroxyethylamino r'horpholino (2.3-b) phenoxazonium chloride is prepared as follows:
To 25 cc of absolute ethanol there are added 0.03 mole (7.39 g) of p-nitroso N,N-di-B- hydroxyethylamino hydrochloride and 0.02 mole (3.3 g) of N-methyl fi-hydroxy phenomorpholine. The resulting solution is heated to reflux for 1 hour, and it is then cooled to The above phenoxazonium chlo ride precipitates and is filtered therefrom, yielding about 3.5 g of the same which, after recrystallization in a dioxane-acetic acid mixture, is chromatographically pure and is in the form of bronze green crystals.
EXAMPLE 7 8-(B-piperidinoethy, ethyl) -amino morpholino (2.3- b) phenoxazonium diperchlorate is prepared as follows:
about 8.5 g of the same which, after recrystallization in a mixture of dimethylformamide and methanol, is chromatographically pure and melts with decomposition between 232 and 234.
Analysis Calculated for Found C% 46.54 46.86 46.73 H% 5.05 5.15 5.17 N% 9.44 9.64 9.67
EXAMPLE 8 The double chloride of zinc and 4-methyl 8- dibutylamino morpholino (2,3-b) phenoxazonium is prepared as follows:
. H9 t\ Q To 40 cc of ethanol at 96 there are added 0.045 mole (l2.l7 g) of p-nitroso N.N-dibutylaniline hydro chloride and 0.03 mole (4.95 g) of N-methyl o-hydroxy phenomorpholine. The resulting solution is heated to reflux for one hour and then hot filtered. 100 cc of water are added to the filtrate which is then filtered to eliminate a light brown insoluble contained therein. Zinc chloride is then added to the aqueous alcoholic solution which is cooled in ice. The above zinc and phenoxazonium double chloride precipitates and is filtered therefrom. washed with a little ice water and recrystallized in ethanol. The product obtained is chromatographically pure and is in the form of bronze crystals.
EXAMPLE 9 An alternate process for the preparation of the 4- methyl 8-diethylamino morpholino (2,3-b) phenoxazonium perchlorate described in Example 1 is as fol lows:
To 30 cc of absolute ethanol, there are added 0.03 mole (5.34 g) of p-nitroso N.N-diethylaniline, 0.03 mole (4.95 g) of N-methyl o-hydroxy phenomorpholine and 4.1 g of anhydrous zinc chloride. The resulting alcohol solution is heated to reflux for one half hour. It is then cooled and the following double zinc and indamine chloride crystals of formula:
precipitates which is then recovered by filtration. yielding about 1 1 grams of the same which are then washed with ethanol.
The above salt is then dissolved in 30 cc of dimethylformamide mixed with l2 cc of acetic acid. The resulting solution is heated for one half hour between l30 and Then 200 cc of water are added and 3.2 g of the above zinc salt precipitate and are recovered by filtration. Sodium perchlorate is then added to the filtrate, thus precipitating 2.8 g of the expected phenoxazonium perchlorate which, after recrystallization in methanol, is chromatographically pure and melts with decomposition at 235.
Cl Zn 3 EXAMPLE 10 The double chloride of zinc and 4-ethyl 8- dibutylamino morpholino (2,3-b) phenoxazonium is prepared as follows:
First phase: Preparation of the N-ethyl 6-hydroxy phenomorpholine.
L19 mole (I80 g) of -hydroxy phenomorpholine are dissolved in two liters of 1.25 N sodium hydroxide solution. This solution is heated to 5060C. There are then added to this solution in small amounts, under agitation and simultaneously, by means of two dropping funnels, on the one hand 7.2 moles (580 cc) of ethyl iodide, and on the other hand 300 cc of 2N sodium hy droxide solution. These successive additions last for l8 hours, during which the reaction mixture is maintained at approximately 60.
The reaction mixture is then cooled to One liter of methylisobutylketone is then added thereto under agitation. 128 g of N,N-diethyl fi-ethoxy benzomorpholinium iodide which melts at [86 are then isolated by centrifuging the reaction mixture. On the other hand, the methylisobutylketonic phase is separated by decantation from the aqueous sodium hydroxide phase of the filtrate. After washing with water. drying on anhydrous sodium sulfate and dry evaporation, 145 g of N-ethyl -ethoxy phenomorpholine are obtained. (E 0.7 mm Hg)=l22l23. By dissolving under vacuum the quaternary derivative concurrently obtained (I28 g), an additional 65 grams of Nethyl 6-ethoxy phenomorpholine are produced.
The 210 g (1.0l mole) of N-ethy] 6-ethoxy phenomorpholine thus obtained are than transformed into N- ethyl 6-hydroxy phenomorpholine bromohydrate by heating the same to reflux for 6 hours in 600 cc of hydrobromic acid (d=l.78). After cooling the reaction centrifuge extraction. Molecular weight calculated for C H NO HBr: 260. Molecular weight found by potentiometric quantitative analysis in water by means of a 0.1N sodium hydroxide solution: 261
Analysis Calculated for Found (,.,H, ,N 0 HBr CW1 46.l5 46.06 45.82 5 H% 5.38 5.48 5.5l NVr 5.38 5.35 5.33
[CLZYI 0.021 mole (5.5 g) of N-ethyl o-hydroxy phenomorpholine hydrobromide is dissolved in 20 cc of water. Ammonia (22Be) is added until the solution attains a pH of 7. Then the N-ethyl 6-hydroxy phenomorpholine is extracted by means of benzene. After washing the benzene solution in water and drying on anhydrous sodium sulfate, the solvent is elminated under vacuum and there is obtained in oily form, 2.90 g of chromatographically pure N-ethyl 6-hydroxy phenomorpholine. Molecular weight calculated for c H No 179. Mo lecular weight found by potentiometric quantitative analysis in acetic acid by means of perchloric acid: 176. 2nd phase: Preparation of the double chloride of zinc and 4-ethyl S-dibutylamino morpholino (2,3-b) phenoxazonium.
To 30 cc of absolute ethanol there are added 0.02 mole of N-ethyl fi-hydroxy phenomorpholine (3.58 g) and 0.03 mole of p-nitroso N,N-dibutylaniline hydrochloride (8.2 g). The solution is heated to reflux for 30 minutes. It is then hot filtered and 75 cc of water and a small amount of animal black are added to the filtrate, which is again filtered. Then zinc chloride is added to the cooled filtrate and the double salt of zinc and phenoxazonium which was expected, precipitates and is filtered therefrom and which after recrystallization in ethanol, is chromatographically pure.
EXAMPLE l l 8-N,N-(ethyl-B-piperidinoethyl) -amino morpholino (2,3-b) phenoxazonium dibromide is prepared as follows:
medium to -30, 198 g of the desired hydrobromide, which melts with decomposition at l, are isolated by To l8 cc of absolute ethanol there are added 0.009 mole (3.8 g) of p-nitroso N,N-(ethyl-B- piperidinoethyl) aniline dihydrobromide and 0.006
13 14 precipitates and is centrifuged therefrom, yielding 0.0073 mole (l.5 g) of p-nitroso N.N-(carbamyl about 1.3 g of the same which after recrystallization in methyl, ethyl) aniline and 0.005 mole l .3 g) of 4-ethyl a water-ethanol solution at 50%, is chromatographi- 6-hydroxy phenomorpholine hydrobromide are added cally pure. to 15 cc of absolute ethanol. The alcoholic solution is 5 heated to reflux for 30 minutes. After cooling and addition of 15 cc of ethyl acetate, the above phcnoxazonium bromide precipitates and is filtered therefrom. The said product melts with decomposition at l95.
Analysis Calculated for Found 2a an 4 2 '2 l0 C /r 49.81 49.78 4933 Analysis Calculated for Found H% 5.41 5.43 5.47 mlhn tQi m1 10.10 9.97 9.99
Ca 53.69 52.97 53.21 1-1 1 5.14 4.98 5.011 Na 1253 12.53 12.71 l
EXAMPLE '2 EXAMPLE l4 4-ethyl8N,N(ethyl-B-piperidinoethyl) -amin The followlng hair dye composition is prepared: h 2 3 b h d Dye of Example I 0.05 g p 0 mo p enoxazomum 1 romide 1s prepare 20 walermqspv )0 g as follows: Ammonia m 22Bc ....q.s.p. pH
i BI ""131 C H o .1 It I C H ca 2 5 l 2 CH I 2 N To cc of absolute ethanol there are added 0.0066 This hair dye composition is applied to 95% naturally mole (2.79 g) of p-nitroso N,N-(ethyl-B- white hair for 10 minutes at ambient temperature and piperidinoethyl) aniline dihydrobromide and 0.0044 imparts thereto after rinsing and shampooing a strong mole (0.8 g) of N-4-ethyl o-hydroxy phenomorpholine. erald green color.
The reaction medium is heated to reflux for one half hour. Then the expected morpholine phenoxazonium dibromide precipitates and is filtered therefrom, yielding about 0.9 g of the same which is then washed with EXAMPLE ethanol. After recrystallization in a 60% ethanol-water A h i d m sition is prepared as follows: solution, the above product is found to be chromatographically pure.
Dye of Example I 0.00l g Analysis Calculated for pound Ethyl alcohol, at 96 20 g O,,,H,.N.O,Br, Water. q.s.p. lOO g Ammonia. q.s.p. pH 10 C% 51.55 51.25 5l.l7 H% 5.84 5.75 5.82 N% 9.62 9.50 9.61
This hair d e com osition is a lied to discolored or EXAMPLE 13 y p pp bleached hair for 10 minutes at ambient temperature 4-ethyl8-(carbamylmethyl, ethyl) -amino (2,3-b) and imparts thereto, after rinsing and shampooing. a
phenoxazonium dibromide is prepared as follows: light emerald-green coloration with iridescent glints.
N O H C Br N O \N l C H H N OC H 0 2 5 A hair setting lotion composition is prepared as follows:
EXAMPLE l6 Dye of Example I (rotonic acid-vinyl acetate copolymcr (90% vinyl acetate. )9? crotonic acid. molecular weight 45.000 to 50.000 Ethyl alcohol. at 96' Water. q.s.p.
Tricthanolaminc. q.s.p.
This hair setting lotion composition is applied to bleached hair and imparts thereto a very intense and very luminous blue-green color.
EXAMPLE l7 3 s 50 g mu g pH 7 The following hair dye composition is prepared:
Dye of Example 1 Ethyl alcohol. at 96 Water. q.s.p.
lZ aqueous lactic acid.q.s.p.
This hair dye composition is applied to hair which is 95% naturally white. After a period of about 5 minutes. the thus treated hair is rinsed and shampooed and the color obtained is a very slightly blueish green with silver glints.
EXAMPLE 18 A hair setting lotion is prepared as follows:
Dye of Example l N-[ 2.4'diamino 5 '-methoxy) phenyll benzoquinonc imine Vinyl acetate-crotonic acid copolymcr molecular weight 45.000 to 50.000]
Ethyl alcohol. at 96 Water. q.s.p.
Triethanolamine, q.s.p.
This hair setting lotion is applied to bleached hair and imparts thereto an iridescent purple-chestnut coloring. 5
EXAMPLE l9 (Vinyl acetate 9(l'7r. crotonic acid lU;
The hair setting lotion composition is prepared:
Dye of Example l Vinyl acetate-crotonic acid copolymer (Vinyl acetate 90%. crotonic acid [0%- molecular weight 45.000 to 50.000)
Ethyl alcohol. at 96 Water. q.s.p. Triethanolamine.q,s.p.
This hair setting lotion is applied to light brown hair and imparts thereto a dark tobacco-brown color with green glints.
EXAMPLE 20 2g 50g 100g pH7 A hair setting lotion is prepared as follows:
Dye of Example 1 N-l(4-hydroxy) phenyl] 3-amino 6-methyl benzoquinone imine Vinyl acetate-crotonic acid copolymer (Vinyl acetate 90%. crotonic acid l0%- molecular weight 45.000 to 50.000)
Ethyl alcohol at 96 Water, q.s.p.
Triethanolamine, q.s.p.
This hair setting lotion is applied to hair which is 95% naturally white and imparts thereto a light bronze color with golden glints.
EXAMPLE 2l The following hair dye composition is prepared:
Dye of Example I 0.25 g
Butylglycol 5 g Lauryl alcohol oxycthylenated with 10.5 moles of ethylene oxide 5 g Water. q.s.p. 100 g This hair dye composition is applied to 60% white hair and imparts thereto after a 20-minute contact period. followed by rinsing and shampooing. a malachite green color with a watered silk or moire effect.
EXAMPLE 22 A hair dye composition is prepared as follows:
Dye of Example 2 0.05 g Ethyl alcohol. 96 20 g Water. q.s p, [00 g Ammonia (22Be). q.s.p. pH l0 25 This hair dye composition is applied to 95% naturally white hair, and imparts thereto after a lO-minute contact period. followed by rinsing and shampooing. a very luminous peacock-blue color.
EXAMPLE 23 The following hair setting lotion is prepared:
Dye of Example 2 0.02 g
N-[(4'-amino) phenyl-I 3-amino bmethyl benzoquinone imine 0. l5 g Vinyl acetate-crotonic acid copolymer (Vinyl acetate 90%. crotonic acid l0'7o-molecular weight 45.000 to 50.000) 2 g lsopropanol alcohol 50 g Water. q.s.p. [00 g Tnethanolamine. q.s.p. pH 7 This hair setting lotion composition is applied to bleached hair and imparts thereto a very light violet tinge.
EXAMPLE 24 A hair dye composition is prepared as follows:
Dye of Example 3 0| g Ethyl alcohol. at 96 20 3 Water. q.s.p. 100 g Ammonia (22Belq.s.p. pH 10 This hair dye composition is applied to naturally white hair and imparts thereto after a lO-minute contact period. followed by rinsing and shampooing, a very luminous turquoise color.
Ammonia (22Be), q.s.p. pH 10 This hair dye composition is applied to 95% naturally Dye of ExamphleI4 3 0.025 g N-(fi-amirioet y l-amino -nitro 4-amino white hair and imparts thereto after a 20 minute benzene hydmbromide 0025 g contact period at normal temperature. followed by E h l l hoLqff 30g I I Water. q.s.p. I g rinsing and shampooing. a dark blue grey color AIIIIIIDIIIII (2205c) IIISIIII PH I0 EXAMPLE 26 This hair dye composition is applied to 60% naturally A dye composltmn prepared as follows: white hair, with which it is allowed to remain in contact for 20 minutes. After rinsing and shampooing. the color obtained is very dark purplish chestnut-brown.
Dye of Example 3 0.1 g 2',4'-diamino-S 'methoxy)phenyi| l0 benzoquirione imine 0.25 g EXAMPLE 3| Eth l alcohol. at 96 25 g I I I I Waier. q.s.p. 100 g The following hair dye composition is prepared; Ammonia (22Be). q.s.p. pH Hi This hair dye composition is applied to 95% naturally vDVye of Example 6 063]] g white hair and imparts thereto after a l5-minute a f g fk z zos In pH contact period. followed by rinsing and shampooing. a P P belge colol" This hair dye composition is applied to bleached hair EXAMPLE 27 and imparts thereto after a 3-minute contact period at I I I I normal temperature, followed by rinsing and shampoo- The following hair setting lotion composition is preingI a pearly "ght green Color pared:
EXAMPLE 32 Dye (If Example 3 0m g A hair setting lotion composition is prepared as foll(3'.5'-dimethyl 4-hydr0xy) phenyl] lOWSZ 2.6-dimethyl benzoquinone imine 0.05 g
Vinyl acetate-crotonic acid copolymer (crotonic acid 107:, vinyl acetate 90% Dye of Example 5 0.1 g 'fx ggggg' g to SO'OOO g Vinyl acetate-crotonic acid copolymer Wa er qs p. i 300 g (as in Example 2 9) 2 g Triethariolamine q s p PH 7 Ehy] alcohol 96 50 g Water, q.s.p. I00 g Tricthanolamine. qsp. pH 7 This hair setting lotion is applied to bleached hair and imparts thereto a Cornflower-blue color. This hair setting lotion is applied to bleached hair and imparts thereto a very luminous lively blue color.
EXAMPLE 28 A hair dye composition is prepared as follows: EXAMPLE 33 The following hair dye composition is prepared:
Dye of Example 3 00:5 g Nitroparaphenylenediamine 0.2 g 40 D f E I l 7 ye 0 Jump e 0075 Ethyl alcohol. 96 40 8 Ethyl alcohol. 96 20 g 8 Water. qsp. II 100 2 Water. qsp. i0() 3 Ammonia B ).q- -p- P Aqueous lactic acid solution l%l q.s.p. pH 5 This hair dye composition is applied to 95% naturally white hair and imparts thereto after a 10-minute 5 contact period at normal temperature, followed by a rinse and a shampoo, a very luminous vivid yellowgreen coloration.
This hair dye composition is applied to 95% naturally white hair and imparts thereto after a 20 minute contact period at ambient temperature and. after rinsing and shampooing, a silvery grey-green color.
EXAMPLE 34 EXAMPLE 29 I I I I A hair dye composition is prepared as follows: The following hair setting lotion composition is prepared:
Dye of Example 8 0.15 g Ethyl alcohol, 96 20 g Water, q.s.p. I00 g Dye of Example 4 0.05 g Vinyl acetate-crotonic acid copolymer (Crotonic acid 10%. vinyl acetate 90%- I I I I I molecular weight 45.000 to 50,000) 2 g This hair dye composition is applied to 95% naturally al zz g g white hair and imparts thereto after a contact period of Triethanolamine. q.s.pi pH 7 20 minutes at ambient temperature and, after rinsing and shampooing. a deep emerald-green color. This hair setting lotion is applied to bleached hair and imparts thereto a very luminous turquoise-blue color EXAMPLE 35 EXAMPLE 30 The following hair setting lotion composition is pre- A hair dye composition is prepared as follows: d;
Dye of Example 10 0.] g Crotonic acid-vinyl acetate copolymcr (as in Example 29) 2 g Ethyl alcohol. 96 50 g Water. qspv 100 g Tricthanolaminc. q.s.p. pH 7 This hair setting lotion is applied to bleached hair and imparts thereto an emerald-green color.
EXAMPLE 36 A hair setting lotion is prepared as follows:
Dyc of Example I l 0.05 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%. crotonic acid l7r molecular weight 45.000 to 50.000] 2 g Ethyl alcohol. 96.q.s.p. 50 Water. qsp. [00 g Tricthanolamine. q.s.p. pH 7 This hair setting lotion is applied to bleached hair and imparts thereto a pearly blue color.
EXAMPLE 37 The following hair dye composition is prepared:
Dye of Example l2 0.2 g Water. q.s.p. 100 g Ammonia (22Be) q.s.p. pH 9 This hair dye composition is applied to 95% naturally white hair and after a 10 minute contact period at room temperature, imparts thereto. after rinsing and shampooing, a very luninous blue color.
EXAMPLE 38 A hair setting lotion is prepared as follows:
Dye of Example l2 0.005 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid l0%- molecular weight 45.000 to 50.000) 2 g Ethyl alcohol. 96. q.s.p. 50 Water. q.s.p. I00 g Triethanolamine. qsp. pH 7 This hair setting lotion is applied to bleached hair and imparts thereto a pearly appearance with pale green glints.
EXAMPLE 39 The following hair setting lotion is prepared as fol lows:
Dye of Example 13 0.025 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%. crotonic acid 10%- molecular weight 45.000 to 50.000) 2 g Ethyl alcohol. 96", q.s.p. 50 Water. q.s.p. 100 g Triethanolamine. q.s.p. pH 7 This hair setting lotion is applied to bleached hair and imparts thereto a pearly pale-green color.
What is claimed is:
l. A phenoxazonium salt having the formula N o /n i2\/ a l 4 6 3 :Nalkyl wherein R and R' are selected from the group consisting of hydrogen and alkyl having l4 carbon atoms with at least one of R" and R being said alkyl and -alkyl has 1-4 carbon atoms, w-aminoalkyl of the formual -ulkyl wherein said alkyl has 1-4 carbon atoms and u-amino alkyl of the formula ON-ulkyl wherein said alkyl has l-4 carbon atoms, and X is selected from the group consisting of Cl, Br, CIO, and Cl -,Zn and the tautomeric forms thereof.
2. A salt of claim 1 wherein at least one of R and R represent w-aminoalkyl having l4 carbon atoms and wherein the terminal amino moiety carries the anion moiety of an acid having the formula HX wherein X is selected from the group consisting of Cl, Br, ClO and Cl Zn.