US3532743A - Novel carboxymethylamino benzenes used in hair dyes - Google Patents
Novel carboxymethylamino benzenes used in hair dyes Download PDFInfo
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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
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- Nitroparaphenylenediamine is a well known ingredient in hair dyeing solutions. This dye, when cold, has an excellent affinity 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 at least one derivative of nitroparaphenylenediamine having the formula:
- R may represent hydrogen, or a methyl radical and R may represent either CH or the radical CH CH OH and n is a whole number falling between 1 and 4 inclusive.
- the dyes defined in this manner make 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.
- Another object of the present invention is to provide the new article of manufacture which consists of the new chemical compound derived from nitroparaphenylenediamine, and responding to the above formula.
- 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 responding to the above formula is applied to the hair, and that after from about 15 to minutes of application the hair is rinsed, shampooed, and dried.
- EXAMPLE 1 Preparation of monohydrochloride of 1-methylamino-2- nitro-4-carboxyrnethylamino benzene
- the method of preparing the above compound is new.
- -It is essentially characterized by the fact that l-rnethylamino-2-nitro-4-amino benzene is reacted with chloroacetamide to obtain 1-methylamino-2-nitro-4-carbamylmethylamino benzene, and that the amide function of the resulting compound is hydrolyzed with hydrochloric acid to yield the monohydrochloride of l-methylarnino-Z-nitro- 4-carboxymethylamino benzene.
- This process may be represented by the following diagram:
- EXAMPLE 2 Preparation of 1 methylamino-2-nitro-4-(N,N-1nethyl carboxymethyl) amino benzene
- 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-methyl-carbamylamino benzene is blocked, using parato-luene 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.
- EXAMPLE 4 Preparation of the monohydrochloride of l-methylamino- Z-nitro-B-carboxyethylamino benzene
- the above compound has been prepared by a new method essentially characterized by the fact that B- chloropropionamide is condensed on l-methylamino 2- nitro-4-amino benzene and that the amino function of the resulting product is hydrolyzed with hydrochloric acid to yield the monohydrochloride of l-methylamino 2- nitro-4-fl-carboxymethylamino benzene.
- This composition is applied to deep blond hair and left in contact therewith for 30 minutes. The hair is then shampooed and rinsed. A light violine 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 is a beige with glints of burnt pearl.
- This composition is applied to bleached platinum blond hair, and left in contact therewith for 15 minutes. The hair is then rinsed, shampooed, rinsed again, and dried. A warm golden beige shade results.
- This composition applied to 100% white hair, for 20 minutes, produces after rinsing, shampooing and drying, a very light blond with a slightly pearlescent glint.
- the method of preparing the monohydrochloride of 1-( ,B-hydroxy-ethylamino)-2-nitro-4-(N ,N methyl-carboxymethyl)amino benzene which comprises the steps of reacting about 3 mols of chloroacetamide with each mol of the secondary amine function in the methylamine group of 1-amino-2-nitro-4-methylarnino benzene under reflux conditions, reacting about 1.2 mols of ,S-chloroethyl chloroformate with each mol of the resulting product under reflux conditions to obtain the ,B-chloroethylic ester of [2-nitro-4-(N,N-methyl carbamylmethyl)amino] phenylcarbamic acid, hydrolyzing the amide function of said ester, hydrolyzing the resulting product in an alkaline solution, and then acidify the resulting product.
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Description
United States Patent Int. Cl. C07c101/44, 101/72 US. Cl. 260-518 7 Claims CH2OH2OH (CH2) "-0 OOH OHzCHzOH (In on;
(CHzh-COOH in which n is 1 to 4.
Nitroparaphenylenediamine is a well known ingredient in hair dyeing solutions. This dye, when cold, has an excellent affinity 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 at least one derivative of nitroparaphenylenediamine having the formula:
RI N in which R may represent hydrogen, or a methyl radical and R may represent either CH or the radical CH CH OH and n is a whole number falling between 1 and 4 inclusive.
The dyes defined in this manner make 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.
Another object of the present invention is to provide the new article of manufacture which consists of the new chemical compound derived from nitroparaphenylenediamine, and responding to the above formula.
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 responding to the above formula is applied to the hair, and that after from about 15 to 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.
EXAMPLE 1 Preparation of monohydrochloride of 1-methylamino-2- nitro-4-carboxyrnethylamino benzene The method of preparing the above compound is new. -It is essentially characterized by the fact that l-rnethylamino-2-nitro-4-amino benzene is reacted with chloroacetamide to obtain 1-methylamino-2-nitro-4-carbamylmethylamino benzene, and that the amide function of the resulting compound is hydrolyzed with hydrochloric acid to yield the monohydrochloride of l-methylarnino-Z-nitro- 4-carboxymethylamino benzene. This process may be represented by the following diagram:
NH-CHz-O O OH Alzalysis.Calcd. for C H O N (percent): C, 48.21; H, 5.35; N, 25.00. Found (percent): C, 48.14-47.99; H, 5.35-5.30; N, 25.19-25.00.
(b) Preparation of monohydrochloride of l-methylamino-2-nitro-4-carboxymethylamino benzene.0.085 mols (19' g.) of l-methylamino, 2nitro-4-carbamylrnethylamino benzene is introduced into 150 cm. of concentrated hydrochloric acid, while stirring it and boiling it to reflux. Reflux is continued for 30 minutes. The mixture is cooled and on drying, yields 16 g. of monohydrochloride of 1- methylamino 2 nitro 4 carboxmethylamino benzene, which, after recrystallization in concentrated hydrochloric acid, melts at between 163 C. and 166 C.
Analysis.Calcd. for C H O N Cl (percent): C, 41.30; H, 4.58; N, 16.06. Found (percent): C, 41.48- 41.51; H, 4.90-4.88; N, 16.12-16.10.
EXAMPLE 2 Preparation of 1 methylamino-2-nitro-4-(N,N-1nethyl carboxymethyl) amino benzene 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-methyl-carbamylamino benzene is blocked, using parato-luene 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 1 methylamino, 2 nitro (N,N,methylcarboxymethyl)- 4-arnino benzene results. The process which has just been described is schematically represented by the following diagram:
mo OHzCONHz rno ornooNrrz (:1) Preparation of para-toluene-l-sulfonylarnino-2- nitro 4-(N,N,methylcarbamylmethyl)amino benzene. 0.953 mols (181 g.) of para-toluene-sulfochloride is added little by little, while stirring to 0.866 mols (194 g.) of 1- amino-2-nitro-4-carbamylmethylamino benzene at 45 C. The mixture is kept at 40 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 para-toluene 1 sulfonylamino-2-nitro-4-(N,N-methylcarbamylmethy1)amino benzene which after recrystallization in alcohol, melts at 181 C.
Analysis.-Calcd. for C H N O S (percent): C, 50.79; H, 4.76; N, 14.81. Found (percent): C, 50.89- 50.88; H, 4.83-4.86; N, 14.97-14.86.
(b) Preparation of N methyl-N'-para-toluene sulfonylamino 2 nitro (N,N,methyl-4-carbamylmethyl) amino benzene-0.945 mols emf) of methyl sulfate is added little by little, at between 35 and 40 C. to a solution of 0.424 mols (160 g.) of para-toluene-l-sulfonylamino 2 nitro-4-(N,N,methyl-carbamylmethyl) amino benzene 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-paratoluene 1 sulfonylamino 2 nitro-4-(N,N,methylcarbamethyl)amino benzene which, after recrystallization in acetic acid, melts at 184 C.
Analysis.-Calcd. for C17H2UN405S (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.
(0) Preparation of 1 methylamino-2-nitro-4-(N,N, methyl carbamylmethyl)amino benzene.0-.294 mols g.) of methyl para-toluene-l-sulfonylamino-2-nitro- 4-(N,N-methyl carbarnylrnethyDamino 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-methyl carbamylmethyl)amino benzene, which melts at 184 C.
Analysis.-Calcd. for C H N O (percent): C, 50.41; H, 5.88; N, 23.53. Found (percent): C, 50.62- 50.45; H, 6.20-616; N, 23.75-23.54.
(d) Preparation of the monohydrochloride of 1- methylamino 2 nitro-4-(N,N,methyl carboxymethyl) amino -be nzene.O.286 mols (68 g.) of l-rnethylamino-Z- nitro-4-(N,N-methyl carbamylmethyl)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-methyl carboxymethyl) amino benzene, which melts and decomposes at C.
AnaIysis.-Calcd. for C H N O Cl (percent); C, 43.55; H, 5.08; N, 15.24. Found (percent): C, 43.53- 43.24; H, 5.115.18; N, 15.38-15.41.
EXAMPLE 3 Preparation of the monohydrochloride of l-(fl-hydroxyethylamino) 2-nitro-4-(N,N,methy1 carboxymethyl) 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 fi-chloroethyl chloroformate is reacted with the resulting l-amino-Z- nitro-4-(N,N,methyl carbzunylmethyl)amino benzene to obtain the ,B-chloroethylic ester of [2-nitro-4-(N,N-
methyl carbamylmethyDamino] 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:
(21) Preparation of 1-amino-2-nitro-4-(N,N-methyl carbamyl-methyl) amino benzene.A mixture of 0.4 mols (66.8 g.) of 1-amino-2-nitro4-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- methyl carbamylmethyl)amino benzene, which after recrystallization in acetic acid, melts at 238 C.
Aanalysis.Calcd. for C H O N (percent): C, 48.21; H, 5.35; N, 25.00. Found (percent): C, 48.58-48.29; H, 5.45-5.50; N, 24.86-24.90.
(b) Preparation of the S-chloroethane ester of [2- nitro 4 (N,N,methyl carbamylmethyl)amino]-phenylcarbamic acid.-1.45 mols (325 g.) of l-amino-2-nitro- 4-(N,N,methyl carbamylmethyl)amino benzene is dissolved in two liters of dioxane. After adding 105 g. of calcium carbonate, 1.7 mols (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 B-chloroethylic ester of [2-nitro-4- (N,N,methyl carbamylmethyl)amino] phenyl-carbamic acid, which, after recrystallization in alcohol, melts at 145 C.
Analysis.-Calcd. for C H O N Cl (percent): C, 43.57; H, 4.54; N, 16.94. Found (percent): C, 44.48- 44.25; H, 4.52-4.67; N, 17.31-17.34.
(c) Preparation of the B-chlOroethylic ester of [2nitro- 4-(N,N,methyl carboxymethyl)amino] phenylcarbamic acid.-0.1 mols of the ,B-chloroethylic ester of [2-nitro-4- (N,N,methyl carboxymethyl)amino] phenylcarbamic acid is introduced, while stirring, into 450 cm. of 5 N hydrochloric acid, while boiling to reflux. When the product is entirely dissolved, reflux is continued for another 15 minutes and the reaction mixture is then poured into 500 cm. of ice water. Drying yields 19 g. of the ,B-chloroethylic ester of [2 nitro 4 (N,N methyl carbamylmethyl)amino1phenyl carbamic acid, which, after recrystallization in a mixture of acetic acid and water, melts at 147 C.
Analysis.Calcd. for C H O N CI (percent): C, 43.43; H, 4.22; N, 12.67. Found (percent): C, 44.05- 4414; H, 4.34-4.25; N, 13.02-13.10.
(d) Preparation of the monohydrochloride of 1 8- hydroxyethylamino 2 nitro 4 (N,N methyl carboxymethyDamiuo benzene.0.034 mols (11.2 g. of ,8 chloroethylic ester of [12 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 mono-hydrochloride of l-fi-hydroxyethylamino-2-nitro-4-(N,N,methyl carbamylmethyl) amino benzene, which, after recrystallation in 2 N hydrochloric acid, melts and decomposes at 135 C.
Analysis.Calcd. 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; C], 11.61- 11.78.
EXAMPLE 4 Preparation of the monohydrochloride of l-methylamino- Z-nitro-B-carboxyethylamino benzene The above compound has been prepared by a new method essentially characterized by the fact that B- chloropropionamide is condensed on l-methylamino 2- nitro-4-amino benzene and that the amino function of the resulting product is hydrolyzed with hydrochloric acid to yield the monohydrochloride of l-methylamino 2- nitro-4-fl-carboxymethylamino benzene.
The above process is schematically illustrated by the following diagram:
(a) Preparation of 1 methylamino 2 nitro-4-B- carboxymethylamino benzene.A mixture of 0.4 mols (64 g.) of 1-methylamino-2-nitro-4-amino benzene with 900 cm. of water and 21 g. of calcium carbonate is heated to reflux. 0.4 mols (43 g.) of fi-chloropropionamide is introduced, little by little, while stirring.
Reflux is continued for two hours. The mixture is filtered while boiling and, after drying and cooling the filtrate, yields 65 g. of the crude product. This, after washing with boiling toluene to eliminate the 1- methylamino-2-nitro-4-amino benzene which has not reacted, and after recrystallization in dioxane, melts at 157 C.
Analysis of end product.Calcd. for C H O N (percent): C, 50.41; H, 5.88; N, 23.52. Found (percent): C, 50.24-50.48; H, 5.99-5.82; N, 23.45-23.41.
(b) Preparation of monohydrochloride of l-methylamino 2 nitro-4-fl-carboxyethylamino benzene-0.021 mol (5 g.) of l-methylamino-2-nitro-4-B-carbamylethylamino benzene is introduced, while stirring, into 25 cm. of concentrated hydrochloric acid diluted with 13 cm. of water. This is brought to reflux, where it is maintained for half an hour. When cooled and dried, the yield is 4.5 g. of the monohydrochloride of l-methylamino-Z- nitro-4-fl-carboxyethylamino benzene which, after recrystallization in dilute hydrochloric acid, melts and decomposes at 170 C.
Analysis of end prduct.Calcd. for C H O N Cl (percent): C, 43.55; H, 5.08; N, 15.24. Found (percent): C, 43.58-43.64; H, 5.09-5.08; N, 15.53-15.48.
EXAMPLE The following composition is prepared:
- G. 1 methylamino 2 nitro-4-(N-methyl-N-carboxymethyl)-amino benzene hydrochloride 0.3 Lauric alcohol oxyethylenated with molecules of ethylene oxide 5 Sodium carbonate, q.s.p., pH=3 Water, q.s.p 100 This composition is applied to golden yellow bleached hair, and is left in contact therewith for 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 20% ammonium lauryl sulfate 5 Sodium carbonate, q.s.p., pH=5 Water, q.s.p 100 This composition is applied to light chestnut hair and left in contact therewith for minutes. The hair is then shampooed, rinsed and dried. The result is a chestnut shade with reddish gold glints.
EXAMPLE 7 The following composition is prepared:
1-( B-hydroxyethyl) -amino 2 nitro-4-(N-methyl-N- carboxymethyl)-amino benzene hydrochloride 0.6
1-hydroxy-2-amino-5-nitrobenzene 0.01
Laurie alcohol oxyethylenated with 12 molecules of ethylene oxide 5 Sodium carbonate, q.s.p., pH=9 Water, q.s.p 100 This composition is applied to chestnut hair, 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:
G. 1-( ,H-hydroxyethyD-Z-amino 4 nitro-(N-methyl-N- carboxymethyl)-amino benzene hydrochloride 0.5 20% lauryl ammonium sulfate 5 Sodium carbonate, q.s.p., pH=8 Water, q.s.p 100 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.
8 EXAMPLE 9 The following composition is prepared:
1 methylamino-2-nitro-4-(N-carboxymethyl)-amino benzene hydrochloride 0.8 Sodium carbonate, q.s.p., pH=9.5 20% lauryl ammonium sulfate 5 Water, q.s.p
This composition is applied to deep blond hair and left in contact therewith for 30 minutes. The hair is then shampooed and rinsed. A light violine chestnut shade results.
EXAMPLE 10 The following composition is prepared:
G. Lauryl alcohol oxyethylenated with 10 molecules of ethylene oxide 1 methylamino-2-nitro-4-(N-carboxymethyl)-amino benzene hydrochloride Sodium carbonate, q.s.p., pH=3 Water, q.s.p 100 This composition is applied to blond hair, and left in contact therewith for 40 minutes. The hair is then shampooed and rinsed. A deep pearly blond shade results.
EXAMPLE 11 The following composition is prepared:
G. 1 methylamino 2 nitro-4-(N-methyl-N-carboxymethyl)-amino benzene hydrochloride 0.14 4-nitro-1,3-phenylenediamine 0.02 20% ammonia, q.s.p., pH=3 Water, q.s.p. 100
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 is a beige with glints of burnt pearl.
EXAMPLE 12 The following composition is prepared:
G. 1-( fl-hydroxyethyl) -2-amino 4 nitro-(N-methyl-N- carboxymethyl)-amino benzene hydrochloride 0.15
4-nitro-1,3-phenylenediamine 0.02 20% ammonia, q.s.p., pH=3 Water, q.s.p. 100
This composition is applied to bleached platinum blond hair, and left in contact therewith for 15 minutes. The hair is then rinsed, shampooed, rinsed again, and dried. A warm golden beige shade results.
EXAMPLE 13 The following composition is prepared:
G. 1- [S-hydroxyethyl -2-arnino-4-nitro (N-methyl, N-
carboxymethyl)-amino benzene hydrochloride 0.24
4-nitro-1,3-phenylenediamine 0.08 20% ammonia, q.s.p., pH=3 Water, q.s.p. 100
This mixture is applied to 100% white hair, and left in contact therewith for 25 minutes. The hair is then rinsed, shampooed, rinsed again, and dried. A violet burnt blond shade results.
This composition, applied to 100% white hair, for 20 minutes, produces after rinsing, shampooing and drying, a very light blond with a slightly pearlescent glint.
EXAMPLE The following composition is prepared:
G. 1-methylamino-2-nitro-4-j8-carboxyethylamino benzene hydrochloride 1 Sodium carbonate, q.s.q., pH:9 lauryl ammonium sulfate 5 Water, q.s.p. 100
(CH2)HCOOH CH2CH2OH N o I I H in which n is 1 to 4.
2. A compound having the formula:
NH(CH2)nC 0 OH CHzCHzOH H in which n is 1 to 4.
3. A compound having the formula:
(CH2) n COOH CH3 in which n is 1 to 4.
4. The method of preparing l-methylamino-2-nitro-4- (N,N-methyl carboxymethyhamino benzene which comprises the steps of blocking the primary amine function of each mol of 1-arnino-2-nitro-4-N,N-methyl carbamylamino benzene with about 1.1 mols of para-toluene sulfochloride at a temperature of about 45 C., reacting the reaction product with about 2.25 mols of methylsulfate per mol of reaction product at about 35-40 C. thereby substituting a methyl radical for the free hydrogen remaining on said primary amine function, eliminating the S0 radical used for blocking purposes, and hydrolyzing the amide function of the resulting composition.
5. The method claimed in claim 4 in which said primary amine function is blocked by reaction with paratoluene sulfochloride and the S0 radical is eliminated by treating each mol of the resulting product with about 15 mols of concentrated sulfuric acid, at a temperature of about 0 to 5 C.
6. The method of preparing the monohydrochloride of 1-( ,B-hydroxy-ethylamino)-2-nitro-4-(N ,N methyl-carboxymethyl)amino benzene which comprises the steps of reacting about 3 mols of chloroacetamide with each mol of the secondary amine function in the methylamine group of 1-amino-2-nitro-4-methylarnino benzene under reflux conditions, reacting about 1.2 mols of ,S-chloroethyl chloroformate with each mol of the resulting product under reflux conditions to obtain the ,B-chloroethylic ester of [2-nitro-4-(N,N-methyl carbamylmethyl)amino] phenylcarbamic acid, hydrolyzing the amide function of said ester, hydrolyzing the resulting product in an alkaline solution, and then acidify the resulting product.
7. The method of claim 6 in which about 22.5 mols of hydrochloric acid are used to hydrolyze each mol of the amide function of said ester and 5 mols of sodium hydroxide is used per mol of reaction product to hydrolyze said reaction product under reflux conditions.
References Cited UNITED STATES PATENTS 3,291,823 12/1966 Kalopissis et al. 260-518 OTHER REFERENCES Chemical Abstracts, vol. 54 (January-February), 1960, pp. 1875i to 1876b relied on.
LORRAINE A. WEINBERGER, Primary Examiner L. A. THAXTON, Assistant Examiner U.S.Cl.X.R.
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FR14482A FR1458155A (en) | 1965-04-23 | 1965-04-23 | New acidic nitrates |
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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 |
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US56756A Expired - Lifetime US3676049A (en) | 1965-04-23 | 1970-07-20 | Dyeing hair with derivatives of nitroparaphenylenediamine |
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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) |
Cited By (8)
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 |
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 |
US5171889A (en) * | 1990-10-31 | 1992-12-15 | Clairol Incorporated | Compositions containing nitroaniline dyes having a carbamide substituent group |
FR2769309A1 (en) * | 1997-10-08 | 1999-04-09 | Oreal | KERATINIC FIBER OXIDATION DYE COMPOSITION COMPRISING AN AMINO ACID DERIVATIVE AS AN OXIDATION BASE AND NOVEL AMINO ACID DERIVATIVES |
EP1739076A1 (en) * | 2005-06-29 | 2007-01-03 | L'oreal | Novel BIS para-phenylenediamines joined by a linker arm substituted with one or more carboxylic radicals and/or derivatives and use in dyeing |
US20070011824A1 (en) * | 2005-06-29 | 2007-01-18 | Stephane Sabelle | Double para-phenylenediamines joined by an aromatic group for dyeing keratin fibers |
US20070011826A1 (en) * | 2005-06-29 | 2007-01-18 | Thierry Bordier | Novel 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 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2290186A1 (en) * | 1974-11-05 | 1976-06-04 | Oreal | TINCTORIAL COMPOSITIONS FOR HUMAN HAIR AND NEW ETHEROXIDES CONTAINED IN THESE COMPOSITIONS |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3291823A (en) * | 1959-04-23 | 1966-12-13 | Oreal | 4-carboxymethylamino-3-nitro-1-methylaminobenzene as a dyeing agent |
-
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
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3291823A (en) * | 1959-04-23 | 1966-12-13 | Oreal | 4-carboxymethylamino-3-nitro-1-methylaminobenzene as a dyeing agent |
Cited By (13)
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 |
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 |
FR2769309A1 (en) * | 1997-10-08 | 1999-04-09 | Oreal | KERATINIC FIBER OXIDATION DYE COMPOSITION COMPRISING AN AMINO ACID DERIVATIVE AS AN OXIDATION BASE AND NOVEL AMINO ACID DERIVATIVES |
EP0908445A1 (en) * | 1997-10-08 | 1999-04-14 | L'oreal | Oxidation dyeing composition for keratin fibres containing an amino acid derivative as oxidation base and aminoacid derivatives |
US6630004B1 (en) | 1997-10-08 | 2003-10-07 | L'oreal S.A. | Oxidation dye composition for keratinous fibers |
EP1739076A1 (en) * | 2005-06-29 | 2007-01-03 | L'oreal | Novel BIS para-phenylenediamines joined by a linker arm substituted with one or more carboxylic radicals and/or derivatives and use in dyeing |
FR2887876A1 (en) * | 2005-06-29 | 2007-01-05 | Oreal | NOVEL DOUBLE PARA-PHENYLENEDIAMINES RELATED BY A BONDING ARM SUBSTITUTED BY ONE OR MORE CARBOXYLIC AND / OR DERIVATIVE RADICALS AND USE IN COLORING |
US20070011824A1 (en) * | 2005-06-29 | 2007-01-18 | Stephane Sabelle | Double para-phenylenediamines joined by an aromatic group for dyeing keratin fibers |
US20070011826A1 (en) * | 2005-06-29 | 2007-01-18 | Thierry Bordier | Novel 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 |
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 |
US7422609B2 (en) | 2005-06-29 | 2008-09-09 | Oreal | Double para-phenylenediamines joined by an aromatic group for dyeing keratin fibers |
Also Published As
Publication number | Publication date |
---|---|
US3676049A (en) | 1972-07-11 |
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 |
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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