US3632292A - 1-methylamino-2-nitro-4-(2{40 -hydroxyethyl)-methylaminobenzene for dyeing human hair - Google Patents

1-methylamino-2-nitro-4-(2{40 -hydroxyethyl)-methylaminobenzene for dyeing human hair Download PDF

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US3632292A
US3632292A US508578A US50857865A US3632292A US 3632292 A US3632292 A US 3632292A US 508578 A US508578 A US 508578A US 50857865 A US50857865 A US 50857865A US 3632292 A US3632292 A US 3632292A
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hair
nitro
dyeing
methylaminobenzene
methylamino
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Gregoire Kalopissis
Andree Bugaut
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LOreal SA
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LOreal SA
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B51/00—Nitro or nitroso dyes

Definitions

  • ABSTRACT An improved dye compound l-methylamino-Z- nitro'-4-(2'-hydroxyethyl)-methylaminobenzene and a method of making it.
  • Nitroparaphenylenediamine is a known active ingredient used in dyes for living hair.
  • trihydroxyalkylated derivatives of nitroparaphenylenediamine has been suggested, and especially those trihydroxyethyls having a hydroxyethyl radical on the amino group in the ortho position of the nitro group and two hydroxyethyl radicals on the amino group in the meta position of the nitro group.
  • the object of the present invention is to provide a new nitrated hair dye and the coloring compositions which can be made with this new dye.
  • the new dye is 1-methylamino-2-nitro-4-(2-hydroxyethyl)- methylaminobenzene.
  • the invention also comprises a method of manufacturing this new dye.
  • This process consists in starting with l-amino- 2- nitro-4-methylaminobenzene, transforming this by methylation into l-methylamino-2-nitro-4-methylaminobenzene, and subjecting the resulting product to hydroxyethylation, using a glycol halohydrin.
  • the amine function in position 1 is methylated by blocking the position of the hydrogen atom carried by the amine group in position 4with acetic anhydride, then blocking the position of one of the hydrogen atoms of the amine function in position 1 with paratoluene-sulfochloride, methylating the resulting product with a neutral methyl sulfate, and finally freeing the two previously blocked positions using first sulfuric acid to detach the tosyl group carried by the nitrogen atom in position 1, and then hydrochloric acid to detach the acetyl group carried by the nitrogen atom in position 4.
  • the nitro group is readily hydroxyethylated in the meta position with a commercially satisfactory yield, and without impurities.
  • a methyl group on one of the amine groups may be easily substituted on the initial product, after which a hydroxyethyl group is substituted on the other amino group, a product which will produce constant, reproducible, results is obtained, since there is no contamination by any secondary coloring agent.
  • the hair dyes comprising the composition according to the invention are simple aqueous solutions containing the composition, preferably having an alkaline pH. No oxidizing agent is required to develop the color.
  • Various additives known in the hair-coloring art may be included, such as organic solvents, thickening agents, detergents, and lacquers.
  • the time during which the hair-coloring solutions should be kept in contact with the hair varies within broad limits, but is preferably between 5 and 30 minutes.
  • the temperature of application may also be varied, but in most cases the dye is applied at room temperature.
  • the pH of these solutions is usually between 7 and 10 and preferably between 8 and 9.5.
  • alkaline products which may be used to adjust the pH are ammonia, any organic base, for example and alkylamine, an alkanolamine, or a heterocyclic amine.
  • concentration of the dye may be varied over a wide range, but this concentration is preferably between 0.l and 3 percent.
  • the dye according to the invention may be mixed with other dyes, whether nitrated, azo,
  • anthraquinone or of any other type conventionally used for dyeing hair.
  • EXAMPLE 2 1-methylamino-2-nitr0-4-(2'-hydroxy- This solution is applied to completely white hair. It is left for 15 to 20 minutes, after which the hair is rinsed, shampooed, and dried. A clear copperish chestnut shade is obtained.
  • composition for dyeing hair comprising an aqueous solution containing hair-dyeing amounts of the compound of claim 1.
  • a hair-dyeing composition as claimed in claim 2 having a pH between 8 and 9.5.
  • a hair-dyeing composition as claimed in claim 2 in which the concentration of said compound lies between 0.1 and 3 percent.
  • the method of dyeing human hair which comprises the step of applying thereto a composition containing dyeing amounts of 1-methylamino-2-nitro-4-(2'-hydroxyethyl)- methylaminobenzene.

Abstract

An improved dye compound 1-methylamino-2-nitro-4-(2''hydroxyethyl)-methylaminobenzene and a method of making it. A hair dye composition containing this compound and the method of dyeing hair with this composition.

Description

United States Patent Inventors Gregoire Kalopissis Paris; Andree Bugaut, Boulogne sur Seine, both of France Appl. No. 508,578 Filed Nov. 18, 1965 Patented Jan. 4, 1972 Assignee Societe anonyme dite: LOreal Priority Nov. 19, 1964 Luxembourg 47,385
1-METHYLAMINO-2-NITRO-4-(2'- HYDROXYETHYL)-METHYLAMINOBENZENE [56] References Cited UNITED STATES PATENTS 2,687,431 8/1954 Marschall 260/573 X 2,750,326 6/l956 Eckardt..... l67/88 2,750,327 6/ l 956 Eckardt l67/88 3,168,442 2/ l 965 Brunner et al l67/88 FOREIGN PATENTS 13,956 4/ l 905 Great Britain 260/573 OTHER REFERENCES Wagner et 20., Synthetic Organic Chemistry, John Wiley & Sons, Inc., New York, (l953), pp. 572, 666- 667, 678 and 679.
Noller, Chemistry of Organic Compounds, 2nd Ed., W. B. Saunders Co., Philadelphia, Pa. l957), pp. 478- 479.
Primary Examiner-Albert T. Meyers Assistant Examiner-Vera C. Clarke AttorneyHolcombe, Wetherill & Brisebois ABSTRACT: An improved dye compound l-methylamino-Z- nitro'-4-(2'-hydroxyethyl)-methylaminobenzene and a method of making it. A hair dye composition containing this compound and the method of dyeing hair with this composition.
l-METHYLAMINO-2-NlTRO-4-(2 '-HYDROXYETHYL)- METHYLAMINOBENZENE FOR DYEING HUMAN HAIR Nitroparaphenylenediamine is a known active ingredient used in dyes for living hair.
Various substituted products have been proposed in order to produce deeper shades than those produced by nitroparaphenylenediamine itself, and among these are alkyl groups and hydroalkyl groups.
In particular the use of trihydroxyalkylated derivatives of nitroparaphenylenediamine has been suggested, and especially those trihydroxyethyls having a hydroxyethyl radical on the amino group in the ortho position of the nitro group and two hydroxyethyl radicals on the amino group in the meta position of the nitro group.
However, it is very difiicult to obtain without tedious purification a commercially satisfactory yield of a trihydroxyethylated derivative of the type in question from nitroparaphenylenediamine, for example, by halohydrin action, for the substitution of the hydroxyethylated groups for the hydrogens of the amine functions leads in practice not to a pure trihydroxyethylated product, but instead to a mixture of mono-, di-, or trisubstituted products, each having a dyeing power of its own, said mixture often comprising also tarry impurities.
Under the operating conditions which prevail during this substitution, the proportions within the resulting mixture vary, and the shades produced when the mixture is used cannot therefore be exactly reproduced.
The object of the present invention is to provide a new nitrated hair dye and the coloring compositions which can be made with this new dye.
The new dye is 1-methylamino-2-nitro-4-(2-hydroxyethyl)- methylaminobenzene.
The invention also comprises a method of manufacturing this new dye. This process consists in starting with l-amino- 2- nitro-4-methylaminobenzene, transforming this by methylation into l-methylamino-2-nitro-4-methylaminobenzene, and subjecting the resulting product to hydroxyethylation, using a glycol halohydrin.
In this process the amine function in position 1 is methylated by blocking the position of the hydrogen atom carried by the amine group in position 4with acetic anhydride, then blocking the position of one of the hydrogen atoms of the amine function in position 1 with paratoluene-sulfochloride, methylating the resulting product with a neutral methyl sulfate, and finally freeing the two previously blocked positions using first sulfuric acid to detach the tosyl group carried by the nitrogen atom in position 1, and then hydrochloric acid to detach the acetyl group carried by the nitrogen atom in position 4.
Applicants have discovered that, under the foregoing conditions, the nitro group is readily hydroxyethylated in the meta position with a commercially satisfactory yield, and without impurities. In this way, since a methyl group on one of the amine groups may be easily substituted on the initial product, after which a hydroxyethyl group is substituted on the other amino group, a product which will produce constant, reproducible, results is obtained, since there is no contamination by any secondary coloring agent.
It has been determined that with l-methylamino-2-nitro-4- (2'-hydroxyethyl)-methylaminobenzene perfectly uniform deep shades of violet are obtained. It should moreover be noted that this dye has an excellent affinity for the keratinic fibers of human hair and that the hair dyes made with it are especially resistant to shampooing, yet have no coloring effect on the scalp.
The hair dyes comprising the composition according to the invention are simple aqueous solutions containing the composition, preferably having an alkaline pH. No oxidizing agent is required to develop the color. Various additives known in the hair-coloring art may be included, such as organic solvents, thickening agents, detergents, and lacquers.
The time during which the hair-coloring solutions should be kept in contact with the hair varies within broad limits, but is preferably between 5 and 30 minutes.
The temperature of application may also be varied, but in most cases the dye is applied at room temperature. The pH of these solutions is usually between 7 and 10 and preferably between 8 and 9.5. Among the alkaline products which may be used to adjust the pH are ammonia, any organic base, for example and alkylamine, an alkanolamine, or a heterocyclic amine. The concentration of the dye may be varied over a wide range, but this concentration is preferably between 0.l and 3 percent.
It should be noted that the dye according to the invention may be mixed with other dyes, whether nitrated, azo,
anthraquinone, or of any other type conventionally used for dyeing hair.
The process of preparing l-methylamino-2-nitro-4(2 hydroxyethyl)-methylaminobenzene in accordance with the invention will now be described, but it will be appreciated that not only bromohydrin, but any other halohydrin of ethanediol, can be used for the hydroxyethylation.
Preparation of 7-amino-2-nitro-4-methylacetaminobenzene.
0.258 moles of l-amino-2-nitro-4-methylaminobenzene (i.e. 43.2 g.) are dissolved in cm. of dioxane and 0.266 moles (25.2 cm) of acetic anhydride are added little by little, while maintaining the temperature at 70 C. After cooling 44.9 g. of an acetylated derivative which melts at 165 C. are obtained by drying.
Preparation of paratoluenel -sulfonylamino-2-nitro-4- methylacetaminobenzene.
0.43 moles (82 g.) of paratoluene-sulfochloride is added to a solution of 0.287 moles (60 g.) of l-amino-2-nitro-4- methylacetaminobenzene at a temperature of 40 to 45 C., little by little, while stirring the mixture. After the addition has been completed, the mixture is kept at 45 C. for 2 hours, emptied into a liter of cold water, after which soda is added to yield the desired product in the form of sodium tosylate. Any of the starting composition which remains untransformed is extracted using methyl isobutyl ketone. The aqueous phase is acidified with hydrochloric acid and, after cooling for several hours, 72 g. of paratoluene-l-sulfonylamino-2-nitr0-4- methylacetaminobenzene is removed by drying. After recrystallization, this product melts at 120 C.
Analysis of the End Product Calculated Found C% 52.89 53.03-52.82 H% 4.68 4.55-4.59 N96 N57 ll.53-ll.70
Preparation of methyl-paratoluene-1-sulfonylamino-2-nitro-4- methylacetaminobenzene.
Analysis of End Product Calculated Found C 54.1 1 54.08-54.04 me 5.04 5064.92 N% n14 11.35-11.30
Preparation of 1-methylamino-2-nitro-4- methylacetaminobenzene.
Analysis of End Product Calculated Found Preparation of l-methylamino-2-nitro-4- methylaminobenzene.
0.05 moles (l 1.2 g.) of l-methylamino-2-nitro-4-methylacetaminobenzene are heated to reflux in 26 cm. of concentrated hydrochloric acid in 26 cm. of water. After cooling, the end product is obtained by drying in the form of a hydrochlorate. The hydrochlorate is dissolved in water and ammonia added to render the pH alkaline. Drying, after cooling, yields 8 g. of 1-methy1amino-2-nitro-4- methylaminobenzene which melts at 1 14 C.
Analysis of End Product Calculated Found C% 53.00 52.67-52.52 H% 6.07 6.056.09 N% 23.21 23.32-23.36
Preparation of 1-methylamino-2-nitro-4-( 2 '-hydroxyethyl)- methylaminobenzene.
Analysis of End Product Calculated Found C% 53.33 53.21-53.24 H% 6.66 6.97-6.85 N% 18.66 18.90-48.66
Two examples will now be given, showing how the dyes according to the invention may be used in a preparation for dyeing the hair.
EXAMPLE 1 The following solution is prepared:
l-methylamino-2-nitro-4-( 2'-hydroxy- I eIhyU-mcthylnminobcnezene l.g. oxyethylated lauric alcohol having 10.5
molecules of ethylene oxide 5 g.
ammonia q.s.p. pH 7 water q.s.p. 100 g.
This solution is applied to completely white hair for 10 minutes. After the waiting period is over, the hair is rinsed, washed, and dried. An intense mauve shade results.
EXAMPLE 2 1-methylamino-2-nitr0-4-(2'-hydroxy- This solution is applied to completely white hair. It is left for 15 to 20 minutes, after which the hair is rinsed, shampooed, and dried. A clear copperish chestnut shade is obtained.
It will of course be appreciated that the processes of preparing the dye and the methods of applying it which have just been described may be modified as to detail without thereby departing from the basic principles of the invention.
What we claim is:
1. l-methylamino-2-nitro-4-( 2 -hydroxyethyl methylaminobenzene.
2. A composition for dyeing hair comprising an aqueous solution containing hair-dyeing amounts of the compound of claim 1.
3. A hair-dyeing composition as claimed in claim pH between 7 and 10.
4. A hair-dyeing composition as claimed in claim 2 having a pH between 8 and 9.5.
5. A hair-dyeing composition as claimed in claim 2 in which the concentration of said compound lies between 0.1 and 3 percent.
6. The method of preparing 1-methylamino-2-nitro-4-(2'- hydroxyethyl)-methylaminobenzene comprising blocking the position of the hydrogen atom carried by the amine group in position 4 of l-amino-2-nitro-4-methylaminobenzene by reacting it with acetic anhydride, and blocking the position occupied by one of the hydrogen atoms of the amine function in position 1 by reacting it with paratoluene-sulfochloride, methylating the resulting product with methyl sulfate, freeing the two blocked positions by reacting the methylated compound first with sulfuric acid and then hydrochloric acid, then reacting the resulting compound with glycol halohydrin to hydroxyethylate the nitrogen atom in position 4.
7. The method claimed in claim 6 in which the halohydrin is glycol bromohydrin.
8. The method of dyeing human hair which comprises the step of applying thereto a composition containing dyeing amounts of 1-methylamino-2-nitro-4-(2'-hydroxyethyl)- methylaminobenzene.
2 having a

Claims (7)

  1. 2. A composition for dyeing hair comprising an aqueous solution containing hair-dyeing amounts of the compound of claim 1.
  2. 3. A hair-dyeing composition as claimed in claim 2 having a pH between 7 and 10.
  3. 4. A hair-dyeing composition as claimed in claim 2 having a pH between 8 and 9.5.
  4. 5. A hair-dyeing composition as claimed in claim 2 in which the concentration of said compound lies between 0.1 and 3 percent.
  5. 6. The method of preparing 1-methylamino-2-nitro-4-(2''-hydroxyethyl)-methylaminobenzene comprising blocking the position of the hydrogen atom carried by the amine group in position 4 of 1-amino-2-nitro-4-methylaminobenzene by reacting it with acetic anhydride, and blocking the position occupied by one of the hydrogen atoms of the amine function in position 1 by reacting it with paratoluene-sulfochloride, methylating the resulting product with methyl sulfate, freeing the two blocked positions by reacting the methylated compound first with sulfuric acid and then hydrochloric acid, then reacting the resulting compound with glycol halohydrin to hydroxyethylate the nitrogen atom in position 4.
  6. 7. The method claimed in claim 6 in which the halohydrin is glycol bromohydrin.
  7. 8. The method of dyeing human hair which comprises the step of applying thereto a composition containing dyeing amounts of 1-methylamino-2-nitro-4-(2''-hydroxyethyl)-methylaminobenzene.
US508578A 1964-11-19 1965-11-18 1-methylamino-2-nitro-4-(2{40 -hydroxyethyl)-methylaminobenzene for dyeing human hair Expired - Lifetime US3632292A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3619228A1 (en) * 1985-06-10 1986-12-11 L'oreal, Paris COLORING AGENT FOR KERATINE FIBERS BASED ON HALOGENATED M-PHENYLENE DIAMINES
US4637821A (en) * 1981-10-08 1987-01-20 L'oreal Tinctorial composition for keratin fibres, based on nitrated benzene dyestuffs

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2519251B1 (en) * 1982-01-05 1985-11-22 Oreal TINCTORIAL COMPOSITION BASED ON PRECURSORS OF OXIDATION DYES AND N-SUBSTITUTED ORTHONITRANILINES COMPRISING AN ALCANOLAMINE AND SODIUM BISULFITE AND THEIR USE IN DYEING KERATIN FIBERS
LU85098A1 (en) * 1983-11-21 1985-07-17 Oreal TINOTORIAL COMPOSITION FOR KERATINIC FIBERS COMPRISING AT LEAST ONE NITRO-2 N-SUBSTITUTED PARAPHENYLENEDIAMINE AND METHODS FOR DYEING KERATINIC FIBERS

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB190413956A (en) * 1904-06-20 1905-04-13 James Yate Johnson Improvements in the Manufacture and Production of Hydroxy-ethylaniline and of Derivatives thereof.
US2687431A (en) * 1950-12-20 1954-08-24 Gen Aniline & Film Corp Process of preparing nitro phenylenediamines
US2750327A (en) * 1953-06-01 1956-06-12 Lever Brothers Ltd Process of dyeing animal fibers and dyes and dyeing compositions therefor
US2750326A (en) * 1951-02-07 1956-06-12 Lever Brothers Ltd Process and composition for dyeing hair
US3168442A (en) * 1964-06-12 1965-02-02 Clairol Inc Compositions and methods of dyeing human hair with nitro-p-phenylenediamines

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB190413956A (en) * 1904-06-20 1905-04-13 James Yate Johnson Improvements in the Manufacture and Production of Hydroxy-ethylaniline and of Derivatives thereof.
US2687431A (en) * 1950-12-20 1954-08-24 Gen Aniline & Film Corp Process of preparing nitro phenylenediamines
US2750326A (en) * 1951-02-07 1956-06-12 Lever Brothers Ltd Process and composition for dyeing hair
US2750327A (en) * 1953-06-01 1956-06-12 Lever Brothers Ltd Process of dyeing animal fibers and dyes and dyeing compositions therefor
US3168442A (en) * 1964-06-12 1965-02-02 Clairol Inc Compositions and methods of dyeing human hair with nitro-p-phenylenediamines

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Noller, Chemistry of Organic Compounds, 2nd Ed., W. B. Saunders Co., Philadelphia, Pa. (1957), pp. 478 479. *
Wagner et al., Synthetic Organic Chemistry, John Wiley & Sons, Inc., New York, (1953), pp. 572, 666 667, 678 and 679. *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4637821A (en) * 1981-10-08 1987-01-20 L'oreal Tinctorial composition for keratin fibres, based on nitrated benzene dyestuffs
DE3619228A1 (en) * 1985-06-10 1986-12-11 L'oreal, Paris COLORING AGENT FOR KERATINE FIBERS BASED ON HALOGENATED M-PHENYLENE DIAMINES
JPS61286313A (en) * 1985-06-10 1986-12-16 ロレアル Dye composition for keratin fiber
GB2176212A (en) * 1985-06-10 1986-12-17 Oreal Dyeing compositions for keratinic fibres
US4725283A (en) * 1985-06-10 1988-02-16 L'oreal Dyeing compositions for keratinic fibres, based on halogenated meta-phenylenediamines
GB2176212B (en) * 1985-06-10 1989-07-05 Oreal Dyeing compositions for keratinic fibres
JPH0432045B2 (en) * 1985-06-10 1992-05-28

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NL6514989A (en) 1966-05-20
GB1061515A (en) 1967-03-15
BE672400A (en) 1966-05-16
NL131840C (en) 1971-06-16
NL7019082A (en) 1971-03-25
LU47385A1 (en) 1966-05-20
DE1569806C3 (en) 1975-07-03
DE1569806A1 (en) 1970-07-09

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