US3676049A - Dyeing hair with derivatives of nitroparaphenylenediamine - Google Patents
Dyeing hair with derivatives of nitroparaphenylenediamine Download PDFInfo
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- US3676049A US3676049A US56756A US3676049DA US3676049A US 3676049 A US3676049 A US 3676049A US 56756 A US56756 A US 56756A US 3676049D A US3676049D A US 3676049DA US 3676049 A US3676049 A US 3676049A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/418—Amines containing nitro groups
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
- A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
Definitions
- a hair dye composition comprising a solution having a pH of 3 to 10 containing an effective amount of a hair dye selected from the group having the formula:
- n 1 to 4 and the method of dyeing hair with this composition.
- Nitroparaphenylenediamine is a well known ingredient in hair dyeing solutions. This dye, when cold, has an excellent afiinity for keratinic fibers, but is incapable of producing any colors other than red-orange shades.
- the purpose of the present invention is to alleviate this difiiculty by providing new dyes which produce even deeper shades, that is to say, tending more toward the blue, which may be used over a wider range of acid pH values.
- the object of the invention is therefore to provide a new article of manufacture which consists of a dye for keratinic fibers and especially for hair, which dye is essentially characterized by the fact that it contains an eifective dyeing amount of at least one derivative of nitroparaphenylenediamine selected from the group having the formula:
- n 1 to 4
- pH 3 to 10.
- a further object of the present invention is to provide a new method of dyeing keratinic fibers, and especially human hair, which method is essentially characterized by the fact that an aqueous solution comprising at least one dye of this invention is applied to the hair, and that after from about 15 to 40 minutes of application the hair is rinsed, shampooed, and dried.
- methylcarbamylmethyl)amino benzene is dissolved in 250' cm? of concentrated hydrochloric acid. This is brought to reflux for 45 minutes. After cooling, drying yields 72.5 g. of the monohydrochloride of 1-methylamino-2-nitro-4- (N,N-methylcarboxymethyl)amino benzene, which melts and decomposes at C.
- This composition is applied to bleached hair and left in contact therewith for 30 minutes.
- the hair is then shampooed and rinsed. A roseate lilac shade is obtained.
- This composition is applied to golden yellow bleached hair, and is left in contact therewith for 20 minutes. The hair is then shampooed and rinsed. A pearly ash blond shade is obtained.
- This composition is applied to light chestnut hair and left in contact therewith for 40 minutes.
- the hair is then shampooed, rinsed and dried.
- the result is a chestnut shade with reddish gold glints.
- EXAMPLE 7 This composition is applied to chestnut hair, 50% of which has turned white, and left in contact therewith for 20 minutes. The hair is then shampooed and rinsed. The result is a maroon violet chestnut.
- This composition is applied to naturally light chestnut hair, and left in contact therewith for 35 minutes. The hair is then shampooed and rinsed. A light burnt chestnut shade results.
- This composition is applied to bleached straw-colored hair, and left in contact therewith for 15 minutes.
- the hair is then rinsed, shampooed, and rinsed again. After drying, the result if a beige with glints of burnt pearl.
- This composition is applied to hair bleached platinum blond, and left in contact therewith for minutes. The hair is then rinsed, shampooed, rinsed again and dried. A warm :golden beige shade results.
- a hair dye composition comprising an aqueous solution having a pH of 3 to 10 which contains an effective dyeing amount of a compound selected from the group having the formula:
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Abstract
A HAIR DYE COMPOSITION COMPRISING A SOLUTION HAVING A PH OF 3 TO 10 CONTAINING AN EFFECTIVE AMOUNT OF A HAIR DYE SELECTED FROM THE GROUP HAVING THE FORMULAF IN WHICH N IS 1 TO 4 AND THE METHOD OF DYENG HAIR WITH THIS COMPOSITION.
Description
United States Patent Int. (:1. $61k 7/12 US. Cl. 8-10 6 Claims ABSTRACT OF THE DISCLOSURE A hair dye composition comprising a solution having a pH of 3 to 10 containing an effective amount of a hair dye selected from the group having the formula:
in which n is 1 to 4 and the method of dyeing hair with this composition.
SUMMARY OF THE INVENTION This application is a continuation-in-part of application Ser. No. 544,079, filed Apr. 21, 1966, which is now US. Pat. 3,532,743 dated Oct. 6, 1970.
Nitroparaphenylenediamine is a well known ingredient in hair dyeing solutions. This dye, when cold, has an excellent afiinity for keratinic fibers, but is incapable of producing any colors other than red-orange shades.
On the other hand, in order to produce deeper shades,
that is to say, shades tending toward green, the use of substituted derivatives of nitroparaphenylenediamine has been suggested. In particular, it has been found that the introduction of a CH radical on the amine function in the meta position with respect to the N0 radical of nitroparaphenylenediamine deepens the shade. However, the products obtained in this manner can be used only within a relatively restricted range of pH values on either side of the neutral point.
The purpose of the present invention is to alleviate this difiiculty by providing new dyes which produce even deeper shades, that is to say, tending more toward the blue, which may be used over a wider range of acid pH values. The object of the invention is therefore to provide a new article of manufacture which consists of a dye for keratinic fibers and especially for hair, which dye is essentially characterized by the fact that it contains an eifective dyeing amount of at least one derivative of nitroparaphenylenediamine selected from the group having the formula:
in which n is 1 to 4, having a pH of 3 to 10.
Use of the dyes of this invention makes it possible to obtain deep shades in the blue portion of the spectrum over a wide range of acid pH values and especially between pH 3 and pH 10.
A further object of the present invention is to provide a new method of dyeing keratinic fibers, and especially human hair, which method is essentially characterized by the fact that an aqueous solution comprising at least one dye of this invention is applied to the hair, and that after from about 15 to 40 minutes of application the hair is rinsed, shampooed, and dried.
In order that the invention may be better understood, several embodiments thereof will now be described, purely by way of example.
3 EXAMPLE 1 Prparation of 1-methylamino-2-nitro-4- (N,N-methylcarboxymethyl) aminobenzene The above compound is prepared by a new method essentially characterized by the fact that the primary amine function of 1-amino-2-nitro-4-N,N-methylcarbamylmethylamino benzene is blocked, using para-toluene sulfochloride, for example, after which a methyl radical is substituted for the free hydrogen remaining on this primary amine function, using for example methyl sulfate in a basic medium. The tosyl radical fixed in the first step of the process is then eliminated, using concentrated sulfuric acid, for example. The amide function of the resulting compound is then hydrolyzed with concentrated hydrochloric acid, for example and the monohydrochloride of l methylamino 2-nitro-4-(N,N-methylcarboxymethyl) amino benzene results. The process which has just been described is schematically represented by the following diagram:
IiIHI ens-4020] 1130 ore-coma,
HNSOQCH3 s 04cm 11.0 CHgCONH:
H30 so. -cn3 @N02 SOHa H3O CHBC ONH:
mo u u e H No: He] NO; I
I mo CHz-CONH; n crnooon (a) Preparation of para-toluene-1sulfonylamino2-nitro- 4- (N,N-methylcarbamylmethyl) aminob enzene 0.953 mol (181 g.) of para-toluene-sulfochloride is added little by little, while stirring to 0.866 mol (194 g.) of 1 amino-2-nitro-4-carbamylmethylamino benzene at 45 C. The mixture is kept at 45 C. for 4 hours and then poured into 4 liters of ice water to which 525 cm. of concentrated hydrochloric acid has been added. When dried, a crude product is yielded which is then redissolved in an 0.5 N solution of sodium hydroxide. The solution is then filtered to eliminate any of the initial product which remains uncombined. After the filtrate has been acidified with hydrochloric acid it yields on drying 229 g. of paratoluene-1-sulfonylamino-2-nitro-4-(N,N-methylcarbamylmethyl)amino benzene which after recrystallization in alcohol, melts at 181 C.
Analysis.-Calculated for C H N O S (percent): C, 50.79; H, 4.76; N, 14.81. Found (percent): C, 50.89- 5038; H, 4.83-4.86; N, 14.97-14.86.
(b) Preparation of N'-methyl-N'-para-toluene sulfonylamino 2 nitro 4-(N,N-methyl-4-carbamylmethyl) amino benzene 0.945 mol cmfi) of methyl sulfate is added little by little, at between 35 and 40 C. to a solution of 0.424 mol (160 g.) of para-toluene-l-sulfonylamino-2-nitro-4- (N,N-methylcarbamylmethyl)aminobenzene in 1250 cm. of 0.5 N sodium hydroxide, while simultaneously adding 800 cm. of 0.5 N sodium hydroxide to keep the solution sufficiently alkaline. After cooling and drying, the yield is 162 g. of methyl-para-toluene-l-sulfonylamino-Z-nitro- 4 (N,N methylcarbamylmethyl)aminobenzene which, after recrystallization in acetic acid, melts at 184 C.
Analysis.Calculated for C H N O S (percent): C, 52.04; H, 5.10; N, 14.29. Found (percent): C, 52.02- 52.17; H, 5.25-5.20; N, 14.41-14.39.
(c) Preparation of 1-methylamino-2-nitro-4-(N,N-methylcarbamylmethyl aminobenzene 0.294 mol g.) of methyl-para-toluene-l-sulfonylamino-2-nitro-4-(N,N-methylcarbamylmethyl)amino benzene is added little by little, while stirring vigorously, to 230 cm? of concentrated sulfuric acid, while maintaining the temperature between 0 and 5 C. After leaving the reaction mixture for four hours at this same temperature, it is poured over two kg. of cracked ice. After neutralization with ammonia, drying yields 68 g. of 1- methylamino 2 nitro-4-(N,N-methylcarbamylmethyl) amino benzene, which melts at 184 C.
Analysis.-Calculated for C H N O (percent): C, 50.41; H, 5.88; N, 23.53. Found (percent): C, 50.62- 50.45; H, 6.20-6.16; N, 23.75-23.54.
(d) Preparation of the monohydrochloride of l-methylamino-2nitro 4 (N,N-methylcarboxymethyl)amino benzene 0.286 mol (68 g.) of 1-methylamino-2-nitro-5-(N,N-
methylcarbamylmethyl)amino benzene is dissolved in 250' cm? of concentrated hydrochloric acid. This is brought to reflux for 45 minutes. After cooling, drying yields 72.5 g. of the monohydrochloride of 1-methylamino-2-nitro-4- (N,N-methylcarboxymethyl)amino benzene, which melts and decomposes at C.
Analysis.-Calculated for C H N O.,Cl (percent): C, 43.55; H, 5.08; N, 15.24. Found (percent): C, 43.53- 4324; H, 5.11-5.18; N, 15.38-15.41.
EXAMPLE 2 Preparation of the monohydrochloride of l-(p-hydroxyethylamino)-2-nitro 4 (N,N-methylcarboxymethyl) amino benzene The above compound has been prepared by a new method essentially characterized by the fact that chloroacetamide is caused to act on the secondary amine function in the meta position relative to the nitro group of 1-amino-2-nitro-4-methylamino benzene and fl-chloroethyl chloroformate is reacted with the resulting l-amino- 2-nitro-4-(N,N-methylcarbamylmethyl)amino benzene to obtain the ,B-chloroethylic ester of [2-nitro-4-(N,N- methylcarbamylmethyl)amino]phenyl carbamic acid. The amide function of this ester is hydrolyzed with hydrochloric acid and the resulting compound is subjected to an alkaline hydrolysis followed by acidification with hydrochloric acid. The above process is illustrated by the following diagram:
(a) Preparation of 1-arnino-2-nitro-4-(N,N-methylcarbamylmethyl)amino benzene A mixture of 0.4 mol (66.8 g.) of 1-amino-2-nitro-4- methylamino benzene, 800 cm. of water and 80 g. of calcium carbonate is brought to reflux. 1.2 mols (112.5 g.) of chloroacetamide is added little by little, while stirring. Reflux is continued for an hour after this addition has been completed. The mixture is then cooled and acidified to pH 3 with hydrochloric acid. Drying yields 86 g. of 1-amino-2-nitro-4-(N,N-methylcarbamylmethyl) amino benzene, which after recrystallization in acetic acid, melts at 238 C.
Analysis.-Calculated for C H O N (percent): C, 48.21; H, 5.35; N, 25.00. Found (percent): C, 48.58- 4829; H, 5.45-5.50; N, 24.86-24.90.
(b) Preparation of the ,S-chloroethyl ester of [2-nitro-4- (N,N methylcarbamylmethyl)amino]-phenylcarbamic acid 1.45 mols (325 g.) of 1-amino-2-nitro-4-(N,N-methylcarbamylmethyl)amino benzene is dissolved in two liters of dioxane. After adding 105 g. of calcium carbonate,
1.7 mol (244 g.) of chloroethylchloroformate is introduced little by little, at reflux and while stirring. Reflux is continued for three hours. The mixture is filtered while boiling to eliminate the mineral salts and the filtrate is refrigerated overnight. Drying yields 320 g. of the [3- chloroethyl ester of [2-nitro-4-(N,N-methylcarbamylmethyl)amino]-phenylcarbamic acid, which, after recrystallization in alcohol, melts at 145 C.
Analysis.Ca1culated for C H O N Cl (percent): C,
43.57; H, 4.54; N, 16.94. Found (percent): C, 44.48-
(c) Preparation of the B-chloroethyl ester of [2-nitro-4- (N,N-methyl-oarboxymethyl)amino] phenylcarbamic acid 0.1 mol of the B-chloroethyl ester of [2-nitro-4-(N,N- methylcarboxymethyl)amino]-phenylcarbamic acid is introduced, while stirring, into 450 cm. of 5 N hydrochloric acid, while boiling to reflux. When the product is entirely (d) Preparation of the monohydrochloride of l-B-hydroxyethylamino 2 nitro 4 (N,N-methyl-carboxymethyl)amino benzene 0.034 mol (11.2 g.) of fi-chloroethyl ester of [2-nitro- 4 (N,N methylcarboxymethyl)amino]phenylcarbamic acid is dissolved in 58.5 cm. of 3 N sodium hydroxide, and brought to reflux for an hour. It is then cooled and acidified with 17 cm. of concentrated hydrochloric acid. Drying yields 6.5 g. of the monohydrochloride of l-fi-hy- 20 droxyethylamino 2 nitro 4 (N,N-methylcarbamylmethyl)-amino benzene, which, after recrystallization in 2 N hydrochloric acid, melts and decomposes at 135 C. Analysis.-Calculated for C H N O Cl (percent): C, 43.20; H, 5.24; N, 13.75; Cl, 11.62. Found (percent): C, 43.48-43.37; H, 5.39-5.35; N, 13.58-13.64; Cl, 11.61- 11.78.
EXAMPLE 3 Preparation of l-(fl-hydroxy-ethyiamino) 2-nitro-4-(N carboxymethyl) amino benzene monohydrochloride The process used is illustrated by the following example:
I NH:
NH-CHz-CHzOH IIIH-CIL-C H2OH (a) Preparation of 1-amino-2-nitro-4- acetylamino benzene 0.6 mol (9 2 gr.) of 2-nitro-1,4-.phenylene diamine was dissolved in 380 cm. of dioxane while being stirred and heated to reflux. 0.66 mol (62.6 cm?) of acetic anhydride was then added drop by drop. The heating at reflux and stirring was continued for 20 minutes. The mixture was then cooled and dried, yielding 100 gr. of dry l-amino- 2-nitro-4-acetylamino benzene, which melts at 188 C., after recrystallization in dioxane.
(b) Preparation of fi-chloroethyl ester of (2-nitro-4- acetamino) phenyl carbamic acid 0.4 mol (78 gr.) of l amino-2-nitro-4-acetylamino benzene was dissolved in 1 liter of dioxane. After addition of 29 gr. of calcium carbonate, 0.48 mol (68.6 gr.) of fi-chloroethyl chloroformate was introduced drop by drop, while heating to reflux and stirring. Heating to reflux was continued for 3 hours. The mixture was filtered while boiling to eliminate the mineral salts and the filtrate was cooled overnight. After drying, 82 gr. of dry 5- chloroethyl ester of (2-nitro-4-acetamino) phenylcarbami-c acid results. After recrystallization in alcohol this product melts at 167 C.
(c) Preparation of fi-chloroethylester of (2-nitro-4- amino) phenylcarbamic acid 0.187 mols (56.5 gr.) of fi-chloroethylester of (2-nitro- 4-amino) phenylcarbamic acid was introduced while stirring into .a hot mixture 0.76 mol (64 emfi) of concentrated hydrochloric acid, 35 cm. of glacial acetic acid and 170 cm. of water. This was heated to reflux for 2 hours. The mixture was then cooled and dried. The resulting precipitant was suspended in 250 cm. of water and neutralized with ammonia. After drying, washing with water, and redrying, the yield was 30 gr. of B-chloroethylester of (2-n-itro-4-amino) phenylcarbamic acid, which melts at 83 C.
((1) Preparation of l-(fl-hydroxyethyl) amino 2-nitro-4-amino benzene 0.075 mol (19.5 gr.) of fl-chloroethylester of (2-nitro- 4-amino)phenylcarbamic acid was introduced into a hot mixture of 0.30 mo] (20 gr.) of potash in tablet form and 180 cm. of absolute alcohol while bubbling in nitrogen. Heating at reflux was continued for 90 minutes. The mixture was then poured, while being agitated, over 700 gr. of ice. After drying, washing with water, and drying again, the yield was 12 gr. of l-(p-hydroxyethyl) amino- 2-nitro-4-amino benzene. After recrystallization in ethyl acetate the product melts at 126 C.
(e) Preparation of l-(fl-hydroxyethyl) amino-Z-nitro- 4-(N-carbamylmethyl) amino benzene A mixture of 0.04 mol (7.88 gr.) of l-(fi-hydroxyethyl) amino 2-nitro-4-amino benzene, 90 cm. of water and 2 gr. of calcium carbonate was heated to reflux.
0.043 mol (4 gr.) of chloroacetamide was added drop by drop while stirring. Heating to reflux was continued for 2 hours after this addition. The mixture was then cooled. After drying, washing with water, and drying again, 5.4 gr. of l-(B-hydroxyethyl) amino 2-nitro-4-(N- carbamylmethyl) amino benzene were obtained. This product when recrystallized in water melts at 186 C.
Analysis-Calculated for C H O N (percent): C, 47.3; H, 5.5; N, 22.0. Found (percent): C, 47.24-47.16; H, 5.61-5.65; N, 21.89-22.19.
(f) Preparation of 1 ,3 hydroxyethylamino 2 nitro- 4 (N carboxymethyl) amino benzene monohydrochloride 0.01 mol (2.54 g.) of l-(fl-hydroxyethyl) amino-2- nitro-4-(N-carbamylmethyl) amino benzene was introduced, while stirring, into 20 cm. of concentrated hydrochloric acid. The mixture Was heated to 100 C. for 30 minutes. After cooling, drying, washing with hydrochloric acid, and again drying, the yield was 1.5 gr. of 1-,8-hydroxyethylamino 2 nitro-4-(N-carb0xymethyl) amino benzene hydrochloride which melts at 126-127 C.
8 EXAMPLE 4 The following composition is prepared:
1 ,6 hydroxyethylamino 2 nitro 4-(N-carboxymethyl) amino benzene monohydrochloride-O.3 gr.
Lauric ether polyoxyethylenated with 4 mols of ethylene oxide-5 gr.
Sodium carbonate, q.s.p.-pH 8.
Water q.s.p.l00 gr.
This composition is applied to bleached hair and left in contact therewith for 30 minutes.
The hair is then shampooed and rinsed. A roseate lilac shade is obtained.
EXAMPLE 5 The following solution is prepared:
1 methylamino 2 nitro-4-(N-methyLN-carboxymethyl)-amino benzene hydrochloride-0.3 g.
Laurie alcohol oxyethylenated with 10 molecules of ethylene oxide-5 g.
Sodium carbonate, q.s.p.--pI-I=3 Water, q.s.p. g.
This composition is applied to golden yellow bleached hair, and is left in contact therewith for 20 minutes. The hair is then shampooed and rinsed. A pearly ash blond shade is obtained.
EXAMPLE 6 The following composition is prepared:
1 methylamino 2 nitro 4 (N-methyl,N-carboxymethyl)-amino benzene hydrochloride-0.6 g.
20% ammonium lauryl sulfate-5 g.
Sodium carbonate, q.s.p.pH=5
Water, q.s.p.100 g.
This composition is applied to light chestnut hair and left in contact therewith for 40 minutes. The hair is then shampooed, rinsed and dried. The result is a chestnut shade with reddish gold glints.
EXAMPLE 7 This composition is applied to chestnut hair, 50% of which has turned white, and left in contact therewith for 20 minutes. The hair is then shampooed and rinsed. The result is a maroon violet chestnut.
EXAMPLE 8 The following composition is prepared: 1 (p3 hydroxy-ethyl)-amino-2-nitro-4-(N-methyl, N-
carboxymethyl)-amino benzene hydrochloride0.5 g. 20% lauryl ammonium sulfate5 g. Sodium carbonate, q.s.p.-pH=8 Water, q.s.p.100 g.
This composition is applied to naturally light chestnut hair, and left in contact therewith for 35 minutes. The hair is then shampooed and rinsed. A light burnt chestnut shade results.
EXAMPLE 9 The following composition is prepared:
1 methylamino-2-nitro-4-(N-methyLN-carboxymethyl)- amino benzene hydrochloride0.14 g.
4-nitIo-1,3-phenylenediamine0.02 g.
20% ammonia, q.s.p.ph=3
Water, q.s.p.100 g.
This composition is applied to bleached straw-colored hair, and left in contact therewith for 15 minutes. The hair is then rinsed, shampooed, and rinsed again. After drying, the result if a beige with glints of burnt pearl.
EXAMPLE The following composition is prepared:
1 ()3 hydroxyethyl) -amino-2-nitro-4-(N-methyl, N-carboxymethy1)-amino benzene hydrochloride0.15 g.
4-nitro-l,3-phenylenediamine-0.02 g.
20% ammonia, q.s.p.-pH=3 Water, q.s.p.100 g.
This composition is applied to hair bleached platinum blond, and left in contact therewith for minutes. The hair is then rinsed, shampooed, rinsed again and dried. A warm :golden beige shade results.
EXAMPLE 11 The following composition is prepared:
1 (B hydroxyethyl)-amino-2-nitro-4-(N-methyl, N-carboxymethyl)-amino benzene hydrochloride-0.24 -g.
4-nitro-1,3-phenylenediamine0.08 g.
% ammonia, q.s.p.--pH=3 Water, q.'s.p.l00 g.
This mixture is applied to 100% white hair, and left in contact therewith for minutes. The hair is then rinsed, shampooed, rinsed again, and dried. A violet burnt blond shade results.
The foregoing methods of carrying out the invention have been given purely by way of example and may be modified as to detail without thereby departing from the basic principles of the invention.
Similar improved dye colorations are obtained when the (CH ),,COOH group of Formulas I to III is a carboxymethyl, carboxyethyl, carboxypropyl or carboxybutyl group.
What is claimed is:
1. A hair dye composition comprising an aqueous solution having a pH of 3 to 10 which contains an effective dyeing amount of a compound selected from the group having the formula:
(CH3) n-C OOH (II) n (CHQr-COOH N02 /H N omonzon (III) 0 Hz References Cited UNITED STATES PATENTS 3,291,823 12/1966 Kalopissis et a1. 8--10.1 X
OTHER REFERENCES Chemical Abstracts, vol. 54: 1875i to 1876b, (1960).
JEROME D. GOLDBERG, Primary Examiner V. C. CLARKE, Assistant Examiner US. Cl. X.R.
8-l0.l; 260-411, 518 R, 519, 556, 558
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR14482A FR1458155A (en) | 1965-04-23 | 1965-04-23 | New acidic nitrates |
Publications (1)
Publication Number | Publication Date |
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US3676049A true US3676049A (en) | 1972-07-11 |
Family
ID=8577186
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US544079A Expired - Lifetime US3532743A (en) | 1965-04-23 | 1966-04-21 | Novel carboxymethylamino benzenes used in hair dyes |
US56756A Expired - Lifetime US3676049A (en) | 1965-04-23 | 1970-07-20 | Dyeing hair with derivatives of nitroparaphenylenediamine |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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US544079A Expired - Lifetime US3532743A (en) | 1965-04-23 | 1966-04-21 | Novel carboxymethylamino benzenes used in hair dyes |
Country Status (7)
Country | Link |
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US (2) | US3532743A (en) |
BE (1) | BE679760A (en) |
CH (4) | CH496444A (en) |
DE (4) | DE1569809A1 (en) |
FR (1) | FR1458155A (en) |
GB (1) | GB1076915A (en) |
NL (1) | NL6605333A (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3836326A (en) * | 1970-11-18 | 1974-09-17 | Gillette Co | Dyeing hair with nitro-substituted phenylene compounds |
FR2290186A1 (en) * | 1974-11-05 | 1976-06-04 | Oreal | TINCTORIAL COMPOSITIONS FOR HUMAN HAIR AND NEW ETHEROXIDES CONTAINED IN THESE COMPOSITIONS |
US5171889A (en) * | 1990-10-31 | 1992-12-15 | Clairol Incorporated | Compositions containing nitroaniline dyes having a carbamide substituent group |
US5164110A (en) * | 1991-02-21 | 1992-11-17 | Nalco Chemical Company | Method of retarding corrosion of metal surfaces in contact with boiler water systems which corrosion is caused by dissolved oxygen |
FR2769309B1 (en) | 1997-10-08 | 2001-06-15 | Oreal | KERATINIC FIBER OXIDATION DYE COMPOSITION COMPRISING AN AMINO ACID DERIVATIVE AS AN OXIDATION BASE AND NOVEL AMINO ACID DERIVATIVES |
FR2887876B1 (en) * | 2005-06-29 | 2007-08-31 | Oreal | NOVEL DOUBLE PARA-PHENYLENEDIAMINES RELATED BY A BONDING ARM SUBSTITUTED BY ONE OR MORE CARBOXYLIC AND / OR DERIVATIVE RADICALS AND USE IN COLORING |
US7413580B2 (en) * | 2005-06-29 | 2008-08-19 | L'oreal S.A. | Double para-phenylenediamines joined by a linker arm substituted with one or more carboxylic radicals and/or derivatives and use in dyeing |
US20070011828A1 (en) * | 2005-06-29 | 2007-01-18 | Stephane Sabelle | Novel double para-phenylenediamines joined by a branched aliphatic group and method of dyeing keratin fibers |
US7422609B2 (en) * | 2005-06-29 | 2008-09-09 | Oreal | Double para-phenylenediamines joined by an aromatic group for dyeing keratin fibers |
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NL275277A (en) * | 1959-04-23 |
-
1965
- 1965-04-23 FR FR14482A patent/FR1458155A/en not_active Expired
-
1966
- 1966-04-20 BE BE679760D patent/BE679760A/xx unknown
- 1966-04-21 CH CH580066A patent/CH496444A/en not_active IP Right Cessation
- 1966-04-21 US US544079A patent/US3532743A/en not_active Expired - Lifetime
- 1966-04-21 CH CH1603367A patent/CH457481A/en unknown
- 1966-04-21 NL NL6605333A patent/NL6605333A/xx unknown
- 1966-04-21 CH CH1603467A patent/CH457482A/en unknown
- 1966-04-21 CH CH1603267A patent/CH457480A/en unknown
- 1966-04-23 DE DE19661569809 patent/DE1569809A1/en active Pending
- 1966-04-23 DE DE19661569811 patent/DE1569811A1/en active Pending
- 1966-04-23 DE DE1617693A patent/DE1617693C3/en not_active Expired
- 1966-04-23 DE DE19661569810 patent/DE1569810A1/en active Pending
- 1966-04-25 GB GB18078/66A patent/GB1076915A/en not_active Expired
-
1970
- 1970-07-20 US US56756A patent/US3676049A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CH496444A (en) | 1970-09-30 |
DE1617693C3 (en) | 1974-01-24 |
CH457480A (en) | 1968-06-15 |
DE1569810A1 (en) | 1970-07-09 |
CH457481A (en) | 1968-06-15 |
NL6605333A (en) | 1966-10-24 |
DE1619612B2 (en) | 1976-03-18 |
DE1569811A1 (en) | 1970-07-09 |
GB1076915A (en) | 1967-07-26 |
DE1617693A1 (en) | 1971-04-22 |
DE1617693B2 (en) | 1973-06-20 |
US3532743A (en) | 1970-10-06 |
CH457482A (en) | 1968-06-15 |
DE1569809A1 (en) | 1970-07-09 |
DE1619612A1 (en) | 1970-09-17 |
FR1458155A (en) | 1966-03-04 |
BE679760A (en) | 1966-10-20 |
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