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Publication numberUS3576587 A
Publication typeGrant
Publication dateApr 27, 1971
Filing dateJul 1, 1968
Priority dateJul 5, 1967
Also published asDE1768725A1, DE1768725B2, DE1768725C3
Publication numberUS 3576587 A, US 3576587A, US-A-3576587, US3576587 A, US3576587A
InventorsAndree Bugaut, Gregoire Kalopissis
Original AssigneeOreal
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Method for dyeing hair and anthraquinone dyestuff composition
US 3576587 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 54,036 Int. Cl. D06p 1/42; C09b 1/50 U.S. Cl. 8-10 3 Claims ABSTRACT OF THE DISCLOSURE New hair dyeing compound responding to the formula 3) ITIH-(CHz) n-NHC 0 CH2 in which n is a whole number lying between 2 and 6 inclusive and method for making the same as Well as an aqueous solution thereof as a composition for dyeing hair.

The present invention relates to a new chemical compound responding to the following general formula:

in which n is a whole number lying between 2 and 6 inelusive.

In accordance with the invention the compound of Formula I is obtained by brominating l-N-acetylaminoalkylamino anthraquinone responding to the formula:

in which n has the significance hereinbefore indicated. reacting the resulting product with fuming sulfuric acid in the presence of boric acid so as to replace the bromine atom previously attached at position 4 with a hydroxy radical, and then hydrolyzing the product in an acid medi- It should be noted that the dyes of Formula I yield especially valuable results when used to dye keratinic fibers, and particularly human hair. These dyes are, to a substantial extent, soluble in water, and have a remarkable aflinity for keratinic fiber.

Their use in dyeing compositions makes it possible to obtain very intense violet shades with a greater resistance to washing than can be obtained with those anthraquinone dyes having an analagous chemical structure heretofore known, which have a tertiary amine function at the end of the chain attached to position 1 in Formula I.

The present invention relates to a composition for dyeing keratinic fibers, and in particular human hair, which is essentially characterized by the fact that it comprises, in aqueous solution, at least one dye responding to Formula I. In a preferred embodiment of the invention the pH of the dyeing compositions according to the invention lies between 6 and 12, and is preferably about 9.

The concentration of the dyes of Formula I in the dyeing compositions according to the invention may vary within broad limits, but is preferably between 0.01% and 3%.

The dyeing compositions according to the invention may be used at temperatures between 5 and C., but are preferably applied at room temperature.

The dyeing compositions according to the invention may also contain wetting agents, dispersing agents, penetrating agents, perfumes and lacquers, and any other ingredients conventionally included in hair dyeing compositions. They may also contain other dyes than those responding to Formula I, and particularly anthraquinone, azo, and nitro dyes.

The present invention also relates to a method of dyeing keratinic fibers and particularly human hair, essentially characterized by the fact that the hair is impregnated with an aqueous solution containing at least one dye responding to the Formula I for from 5 to 30 minutes, after which it is shampooed, rinsed and dried.

In order that the invention may be better understood, a method of preparing a dye responding to Formula I, and several examples illustrating the use of said dye on hair, will now be described, purely by way of illustration.

EXAMPLE 1 Preparation of 1- -aminopropylamino-4-hydroxy anthraquinone monohydrochloride The preparation may be schematically represented in the following form:

First step: Preparation of 1-'y-acetylaminoproylamino- 4-bromo anthraquinone 0.03 mole (9.66 g.) of l-y-acetylaminopropylamino anthraquinone is dissolved in 100 cc. of acetic acid at um so as to de-acetylate the chain attached at position 1. 50 C. 0.03 mole (2.4 g.) of sodium acetate is added, followed by 0.03 mole (4.8 g.) of bromine, which is added little by little, while stirring. The reaction mixture is kept at 50 C. for 7 hours, and then at 20 C. for 15 hours, and then poured into water. The crude product is dried and washed in hot alcohol. The result is 6.3 g. of 1-'yacetylaminopropylamino-4-bromo anthraquinone which, after recrystallization in methylisobutylketone, melts at 187 C.

Analysis of this product yields the following results:

Analysis.Calculated for C19H17N203Br (percent): C, 56.86; H, 4.24; N, 6.98; Br, 19.95. Found (percent): C, 56.79-56.89; H, 4.43-4.43; N, 7.10-6.96; Br, 19.54-19.32.

Second step: Preparation of l-q acetylaminopropylamino-4-hydroxy anthraquinone 0.0238 mole (9.5 g.) of 1-'y-acetylaminopropylamino-4- bromo anthraquinone is heated for 4 hours at 120 C. in the presence of 95 g. of fuming sulfuric acid and 4.75 g. of boric acid. After cooling, the reaction mixture is poured over cracked ice and neutralized with a sodium hydroxide solution. 10 cc. of of acetic anhydride is added and the mixture heated for 30 minutes at 70 C. After cooling, drying and washing with water yields 7.7 g. of 1 'y acetylaminopropylamino-4-hydroxy anthraquinone which, after recrystallization in chlorobenzene, melts at 198 C.

Analysis of this product yields the following results:

Analysis.--Calculated for C H N O (percent): C, 67.46; H, 5.32; N, 8.28. Found (percent): C, 67.59-67.53; H, 5.49-5.41; N, 8.15-8.10.

Third step: Preparation of 1-'y-aminopropylamino- 4-hydroxy anthraquinone monohydrochloride 0.0133 mole (4.5 g.) of 1-'y-acetylaminopropylamino-4- hydroxy anthraquinone is added to 10 cc. of 50% hydrochloric acid. The mixture is then heated at reflux for two hours and vacuum dried. The residue is redissolved in acetone and drying yields 4.4 g. of 1-y-aminopropylamino- 4-hydroxy anthraquinone monohydrochloride, which, after recrystallization in a mixture of water and isopropanol, melts and decomposes at 269 C.

EXAMPLE 2 The following dyeing composition is prepared:

1-'y-aminopropylamino-4-hydroxy anthraquinone monohydrochloride0.33 g.

Lauric alcohol with 10.5 moles of ethylene oxide-2 g.

2 N solution of Na CO q.s.p.-pH=7 Water, q.s.p.-100 g.

This composition is applied to bright golden chestnut hair, and left to act for 10 minutes, after which the hair is shampooed and rinsed. A violine chestnut is obtained.

EXAMPLE 3 The following dyeing composition is'prepared:

1-'y-aminopropylamino-4-hydroxy anthraquinone monohydrochloride0.17 g.

4 1 N,N dimethylamino 3-5 aminoethylamino-4-nitro benzene-0.11 g. Lauric alcohol with 10.5 moles of ethylene oxide-3 g. Monoethanolamine, q.s.p.-pH=9' Water, q.s.p.- g.

ll 1 0 OH wherein n is an integer of 2-6 inclusive, said dye being present in amounts of about 0.01-3 weight percent of said composition, permitting said composition to remain in contact with said hair for a period of about 5-30 minutes,

washing, rinsing and drying said hair.

2. A composition for dyeing human hair comprising an aqueous solution of an anthraquinone dye having the formula wherein n is an integer of 2-6 inclusive, said dye being present in amounts of about 0.01 weight percent of said composition.

3. The composition of claim 2 having a pH between 6-12.

References Cited UNITED STATES PATENTS 2,659,739 11/1953 Dickey 260380 3,153,059 10/1964 Straley et al. 260-380X 3,442,995 5/ 1969 Kalopissis et al. 8-10X GEORGE F. L'ESMES, Primary Examiner P. C. IVES, Assistant Examiner US. Cl. X.R.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4894451 *Jul 19, 1988Jan 16, 1990The University Of VermontUnsymmetrical 1,4-bis(aminoalkylamino)-anthracene-9, 10-diones and derivatives
US5314505 *Sep 1, 1992May 24, 1994Clairol, Inc.Aminoan thraquinone dyes having a quaternary center with a long aliphatic chain
US9259380Sep 11, 2014Feb 16, 2016Henkel Ag & Co. KgaaMeans for dyeing and/or matting keratinic fibres containing novel 1,4 diaminoanthraquinone dyes
WO2013135503A1 *Mar 1, 2013Sep 19, 2013Henkel Ag & Co. KgaaMeans for dyeing and/or matting keratinic fibres containing novel 1,4 diamino-anthraquinone dyes
U.S. Classification8/405, 552/247, 552/255, 8/426, 552/260
International ClassificationC09B1/515, C09B67/00, C09B1/28, C09B1/50, C09B1/00
Cooperative ClassificationA61K8/355, C09B1/515, A61Q5/065, C09B1/28
European ClassificationC09B1/28, C09B1/515, A61Q5/06D, A61K8/35C