US3531502A - Anthraquinone dyes - Google Patents

Anthraquinone dyes Download PDF

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Publication number
US3531502A
US3531502A US428867A US3531502DA US3531502A US 3531502 A US3531502 A US 3531502A US 428867 A US428867 A US 428867A US 3531502D A US3531502D A US 3531502DA US 3531502 A US3531502 A US 3531502A
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United States
Prior art keywords
hair
hydroxy
methyl
aminoanthraquinone
sulphate
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Expired - Lifetime
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US428867A
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Gregoire Kalopissis
Jack Bertrand
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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A61K8/355—Quinones
    • 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
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
    • C09B1/501—Amino-hydroxy-anthraquinones; Ethers and esters thereof containing onium groups
    • 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
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
    • C09B1/51—N-substituted amino-hydroxy anthraquinone
    • C09B1/514—N-aryl derivatives
    • C09B1/5145—N-aryl derivatives only amino and hydroxy groups

Definitions

  • R is a lower alkyl radical (for instance a methyl, ethyl, propyl or butyl radical); and A- is an anion, such as a halogen or a methylsulphate ion.
  • Examples of two compounds falling within the scope of the above-indicated Formula I are: bis-methyl-[lhydroxy 2,4 (p-trimethylammoniumphenyl)aminoanthraquinone]sulphate, that is the compound of Formula I where R is methyl and A" is methylsulphate, and [1- hydroxy-2,4 (p trimethyl-ammoniumphenyl) aminoanthraquinone] iodide, that is the compound of Formula I where R is methyl and A- is iodide.
  • the quaternary salts of this invention when applied to the hair give attractive grey shades of great intensity for which there is need in the art of hair-dyeing. They also have the advantage that they are very soluble in water over a very wide pH range, the aqueous solutions obtained being, in general, tolerant of all the practical conditions under which hair dyeing is carried out. Moreover, the quaternary salts when applied to hair have a 3,531 ,502 Patented Sept. 29, 1970 high resistance to sunlight, which is a most valuable property for hair dyes, and they also well withstand the presence of ingredients generally incorporated in dyeing compositions, such as hair penetrating and swelling agents, lustre-producing products and thickening agents.
  • 1 hydroxy 2,4 (p-dimethylaminophenyl) aminoanthraquinone can be obtained by the reaction of N,N-dimethyl-p-phenylenediamine with purpurin, that is, 1,2,4- trihydroxyanthraquinone.
  • the quaternary salts of l-hydroxy 2,4 (p dimethylaminophenyl)aminoanthra quinone can be obtained by reacting the latter compound with a quaternising agent such as methyl iodide or methyl sulphate.
  • the present invention also relates to a method of dyeing keratinic fibres, more particularly hair, by applying to the fibres a quaternary salt of this invention, allowing sufficient time to elapse for the said compound to exert its dyeing effect and then removing any unwanted excess of the compound from the hair.
  • the quaternary salt is conveniently used in the form of an aqueous solution that is left in contact with the hair for about 15 to 60 minutes at ambient temperature, after which the hair is rinsed and washed.
  • the invention also comprises dyeing compositions suitable for dyeing keratinic fibres, which may take the form of solutions, emulsions, gels or creams, containing a quaternary salt of this invention.
  • the dyeing composi tions preferably have a pH value of from 3 to 9.
  • the dye compositions of the" invention may be used in combination with other dyestufis which may or may not be quaternary salts of this invention or belong to the family of the anthraquinone dyestuffs.
  • a dyeing solution according to the invention is prepared by mixing:
  • This solution is applied to 100% white hair and left in contact therewith for 20 minutes at ambient temperature, whereafter the hair is washed, rinsed and dried.
  • the coloration thus obtained in the hair is violet-grey.
  • a dyeing solution according to the invention is prepared by mixing: 1-hydroXy-2,4- (p-trimethylammoniumphenyl) arninoanthraquinone] iodide-10 g. Sodium carbonate, q.s. for pH 7 Water, q.s. for 1000 cc.
  • This solution is applied to 100% white hair and left in contact therewith for 20 minutes at ambient temperature, whereafter the hair is rinsed, shampooed, rinsed again and dried.
  • the coloration thus obtained in the hair is blue-grey.
  • a dyeing solution according to the invention is prepared by mixing:
  • N-monomethylnitro-p-phenylenediamine 6.5 l-(v-dimethylaminopropyl)-amino, 2-amino-4- nitrobenzene monohydrochloride 12
  • Sodium carbonate q.s. for pH 8.5. Water, q.s. for 1000 cc.
  • R is a lower alkyl having 1-4 carbon atoms and A* is a halide or methyl sulfate.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • Organic Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Emergency Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

United States Patent 3,531,502 ANTHRAQUINONE DYES Gregoire Kalopissis, Paris, Jack Bertrand, Tremblay-les- 'Gonesses, and Andree Bugaut, born Ormancey, Boulogne-sur-Seine, France, assignors to Societe Anonyme dite: LOreal, Paris, France No Drawing. Filed Jan. 28, 1965, Ser. No. 428,867 Claims priority, appligcation France, Feb. 5, 1964,
Int. 01. e091) 1750; con 97/14 U.S. Cl. 260-380 5 Claims ABSTRACT OF THE DISCLOSURE The new compounds 1-hydroxy-2,4 bis-(p-dimethylaminophenyl)aminoanthraquinone and a quaternary salt of the compound of claim 1, which has the formula:
R1 CH3 in which R is a lower alkyl having 1-4 carbon atoms and A- is an anion; and hair dye compositions containing these compounds.
The process of reacting 1,3,4-trihydroxyanthraquinone with N,N-dimethyl-p-phenylenediamine to (p-dimethylaminophenyl)aminoanthraquinone.
O OH H H R1 GHa NH- 1l/ CH8 R1 cm in which R is a lower alkyl radical (for instance a methyl, ethyl, propyl or butyl radical); and A- is an anion, such as a halogen or a methylsulphate ion.
Examples of two compounds falling within the scope of the above-indicated Formula I are: bis-methyl-[lhydroxy 2,4 (p-trimethylammoniumphenyl)aminoanthraquinone]sulphate, that is the compound of Formula I where R is methyl and A" is methylsulphate, and [1- hydroxy-2,4 (p trimethyl-ammoniumphenyl) aminoanthraquinone] iodide, that is the compound of Formula I where R is methyl and A- is iodide.
The quaternary salts of this invention when applied to the hair give attractive grey shades of great intensity for which there is need in the art of hair-dyeing. They also have the advantage that they are very soluble in water over a very wide pH range, the aqueous solutions obtained being, in general, tolerant of all the practical conditions under which hair dyeing is carried out. Moreover, the quaternary salts when applied to hair have a 3,531 ,502 Patented Sept. 29, 1970 high resistance to sunlight, which is a most valuable property for hair dyes, and they also well withstand the presence of ingredients generally incorporated in dyeing compositions, such as hair penetrating and swelling agents, lustre-producing products and thickening agents.
1 hydroxy 2,4 (p-dimethylaminophenyl) aminoanthraquinone can be obtained by the reaction of N,N-dimethyl-p-phenylenediamine with purpurin, that is, 1,2,4- trihydroxyanthraquinone. The quaternary salts of l-hydroxy 2,4 (p dimethylaminophenyl)aminoanthra quinone can be obtained by reacting the latter compound with a quaternising agent such as methyl iodide or methyl sulphate.
The present invention also relates to a method of dyeing keratinic fibres, more particularly hair, by applying to the fibres a quaternary salt of this invention, allowing sufficient time to elapse for the said compound to exert its dyeing effect and then removing any unwanted excess of the compound from the hair. The quaternary salt is conveniently used in the form of an aqueous solution that is left in contact with the hair for about 15 to 60 minutes at ambient temperature, after which the hair is rinsed and washed.
The invention also comprises dyeing compositions suitable for dyeing keratinic fibres, which may take the form of solutions, emulsions, gels or creams, containing a quaternary salt of this invention. The dyeing composi tions preferably have a pH value of from 3 to 9.
The dye compositions of the" invention may be used in combination with other dyestufis which may or may not be quaternary salts of this invention or belong to the family of the anthraquinone dyestuffs.
The invention is illustrated by the following examples.
EXAMPLE I Preparation of 1-hydroxy-2,4-(p-dimethylaminophenyl) aminoanthraquinone There is heated for 8 hours at C. a mixture consisting of 264 g. of industrial purpurin, 64 g. of boric acid and 1018 g. of N,N-dimethyl(p-phenylenediamine), whereafter the mixture is diluted with 1.5 litres of alcohol and 3 litres of water. The crude product is thereafter separated and recrystallised from chlorobenzene. The product thus obtained has a melting point of 254- 255 C. and the following analysis.
Calculated (percent): C, 73.17; H, 5.69; N, 11.38.
Found'(percent): C, 73.65-73.37; H, 5.80-5.72; N.
EXAMPLE II Preparation of bis-methyl-[1-hydroXy-2,4-(p-trimethylammoniumphenyl)aminoanthraquinone] sulphate This compound is obtained by the action of 11.4 g. of methyl sulphate on a solution of 20 g. of l-hydroxy- 2,4-(p-dimethylaminophenyl)-aminoanthraquinone in 200 cc. of benzone. The quaternary ammonium obtained is separated, and it melts with decomposition at 200-203 C.
EXAMPLE III Preparation of [1 hydroxy-2,4- (p-trimethylammoniumphenyl)-aminoanthraquinone] iodide This compound is obtained by the action of methyl iodide (2.14 g.) on 1 hydroxy 2,4-(p-dimethylaminophenyl) aminoanthraquinone (3.32 g.). It decomposes at 260 C.
EXAMPLE IV A dyeing solution according to the invention is prepared by mixing:
Bis-methyl- 1 hydroxy-2,4- (p-trimethylammoniumphenyl)arninoanthraquinone] sulphateg. Sodium carbonate, q.s. for pH 7 Water, q.s. for 1000 cc.
This solution is applied to 100% white hair and left in contact therewith for 20 minutes at ambient temperature, whereafter the hair is washed, rinsed and dried.
The coloration thus obtained in the hair is violet-grey.
EXAMPLE V A dyeing solution according to the invention is prepared by mixing: 1-hydroXy-2,4- (p-trimethylammoniumphenyl) arninoanthraquinone] iodide-10 g. Sodium carbonate, q.s. for pH 7 Water, q.s. for 1000 cc.
This solution is applied to 100% white hair and left in contact therewith for 20 minutes at ambient temperature, whereafter the hair is rinsed, shampooed, rinsed again and dried.
The coloration thus obtained in the hair is blue-grey.
EXAMPLE VI A solution according to the invention is prepared by mixing:
Methyl- [4-hydroxyl B-methylmorpholinium) ethylaminoanthraquinone] sulphate 1.4 1- -dimethylaminopropyl -amino, 2-amino-4- nitrobenzene monohydrochloride 2.8 Bis-methy1- l-hydroxy-2,4- (p-trimethylammoniumphenyl) arninoanthraquinone] sulphate 8.5 Bis-methyl- 1,5 fl-methylmorpholinium) ethylaminoanthraquinone] sulphate 8.5
Sodium carbonate, q.s. for pH 8.5. Water, q.s. for 1000 cc.
When applied to light chestnut-coloured hair and left for minutes this mixture imparts a pearly-red tinge to the hair, after washing, rinsing and drying.
EXAMPLE VII A dyeing solution according to the invention is prepared by mixing:
N-monomethylnitro-p-phenylenediamine 6.5 l-(v-dimethylaminopropyl)-amino, 2-amino-4- nitrobenzene monohydrochloride 12 Bis-methy1[ 1-hydroxy-2,4- (p-trimethylammonium- 4 phenyl)arninoanthraquinone] sulphate 2 Bis-n1ethy1[ 1,4-(fl-methylmorpholinium) ethylaminoanthraquinone]sulphate 6 Sodium carbonate, q.s. for pH 8.5. Water, q.s. for 1000 cc.
in which R is a lower alkyl having 1-4 carbon atoms and A* is a halide or methyl sulfate.
3. The quaternary salt of claim 2, in which R is methyl.
4. Methy1-[1-hydroxy-2,4 bis (p trimethylammoniumphenyl -aminoanthraquinone] sulphate.
5. [1 hydroxy 2,4 bis (p trimethylammoniumphenyl) aminoanthraquinone] iodide.
References Cited UNITED STATES PATENTS 1,937,531 12/1933 Rogers et a1 260380 3,004,974 10/1961 Grossman et al. 260377 XR 3,192,117 6/1965 Kaiser et a1 167-88 3,368,942 2/1968 Kaiser et al. 167-88 OTHER REFERENCES Kalopississ et al., J. Soc. Cosmetic Chemists, Oxford, England: Pergamin Press Ltd., vol. 15, pages 411422 (1964).
LORRAINE A. WEINBERGER, Primary Examiner R. GERSTL, Assistant Examiner US. Cl. X.R. 810, 10.1, 39
US428867A 1964-02-05 1965-01-28 Anthraquinone dyes Expired - Lifetime US3531502A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR962659A FR1430091A (en) 1964-02-05 1964-02-05 New anthraquinone dyes and new hair dyeing processes using these dyes

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US37903A Expired - Lifetime US3692461A (en) 1964-02-05 1970-05-15 Hair dye composition and method of dyeing human hair therewith

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US (2) US3531502A (en)
AT (2) AT251145B (en)
BE (1) BE659168A (en)
CH (2) CH435507A (en)
DE (1) DE1492073A1 (en)
FR (1) FR1430091A (en)
GB (1) GB1050863A (en)
NL (2) NL6501324A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5314505A (en) * 1991-11-01 1994-05-24 Clairol, Inc. Aminoan thraquinone dyes having a quaternary center with a long aliphatic chain
US20050011012A1 (en) * 2003-03-19 2005-01-20 Regents Of The University Of California Multifunctional antimicrobial dyes
WO2007090799A2 (en) 2006-02-09 2007-08-16 Dystar Textilfarben Gmbh & Co Deutschland Kg Dyestuffs and hair dye compositions
US20080201871A1 (en) * 2003-03-19 2008-08-28 The Regents Of The University Of California Antimicrobial colorants

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4138415A (en) * 1978-05-05 1979-02-06 American Cyanamid Company 1,4-Bis(aminoalkylamino)-anthraquinones and leuco derivatives thereof
LU83177A1 (en) * 1981-02-27 1982-09-10 Oreal USE OF HYDROXYANTHRAQUINONES FOR COLORING HUMAN KERATINIC FIBERS, METHOD AND COMPOSITION USING THE SAME

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1937531A (en) * 1928-06-22 1933-12-05 Nat Aniline & Chem Co Inc Production of anthraquinone dyestuffs
US3004974A (en) * 1958-12-24 1961-10-17 Ciba Ltd Water-soluble salts of anthraquinone dyestuffs
US3192117A (en) * 1961-02-23 1965-06-29 Therachemie Chem Therapeut Hair dye comprising substituted anthraquinones in shampoo base
US3368942A (en) * 1963-09-04 1968-02-13 Therachemie Chem Therapeut Water soluble aminoanthraquinone hair dyes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1937531A (en) * 1928-06-22 1933-12-05 Nat Aniline & Chem Co Inc Production of anthraquinone dyestuffs
US3004974A (en) * 1958-12-24 1961-10-17 Ciba Ltd Water-soluble salts of anthraquinone dyestuffs
US3192117A (en) * 1961-02-23 1965-06-29 Therachemie Chem Therapeut Hair dye comprising substituted anthraquinones in shampoo base
US3368942A (en) * 1963-09-04 1968-02-13 Therachemie Chem Therapeut Water soluble aminoanthraquinone hair dyes

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5314505A (en) * 1991-11-01 1994-05-24 Clairol, Inc. Aminoan thraquinone dyes having a quaternary center with a long aliphatic chain
US20050011012A1 (en) * 2003-03-19 2005-01-20 Regents Of The University Of California Multifunctional antimicrobial dyes
US20080201871A1 (en) * 2003-03-19 2008-08-28 The Regents Of The University Of California Antimicrobial colorants
WO2007090799A2 (en) 2006-02-09 2007-08-16 Dystar Textilfarben Gmbh & Co Deutschland Kg Dyestuffs and hair dye compositions
WO2007090800A2 (en) * 2006-02-09 2007-08-16 Dystar Textilfarben Gmbh & Co Deutschland Kg Hair dye compositions
EP1820826A1 (en) * 2006-02-09 2007-08-22 DyStar Textilfarben GmbH & Co. Deutschland KG Dyestuffs and Hair Dye Compositions
WO2007090800A3 (en) * 2006-02-09 2007-12-21 Dystar Textilfarben Gmbh & Co Hair dye compositions
WO2007090799A3 (en) * 2006-02-09 2008-01-10 Dystar Textilfarben Gmbh & Co Dyestuffs and hair dye compositions
US20090217466A1 (en) * 2006-02-09 2009-09-03 Dystar Textilfarben Gmbh & Co. Deutschland Kg Dyestuffs and hair dye compositions
US20090249564A1 (en) * 2006-02-09 2009-10-08 Dystar Textilfarben Gmbh & Co. Deutschland Kg Hair dye compositions
US7776106B2 (en) 2006-02-09 2010-08-17 Dystar Textilfarben Gmbh & Co., Deutschland Kg Dyestuffs and hair dye compositions

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US3692461A (en) 1972-09-19
FR1430091A (en) 1966-03-04
BE659168A (en) 1965-08-02
CH440558A (en) 1967-07-31
AT251145B (en) 1966-12-12
CH435507A (en) 1967-05-15
DE1492073A1 (en) 1969-05-14
GB1050863A (en)
NL6501324A (en) 1965-08-06
NL125671C (en)
AT269359B (en) 1969-03-10

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