Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3578386 A
Publication typeGrant
Publication dateMay 11, 1971
Filing dateFeb 16, 1968
Priority dateFeb 22, 1967
Also published asDE1719377A1, DE1719377B2, DE1719377C3, DE1794404A1, DE1794404B2, DE1794404C3
Publication numberUS 3578386 A, US 3578386A, US-A-3578386, US3578386 A, US3578386A
InventorsBugaut Andree, Kalopissis Gregoire
Original AssigneeOreal
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Dyeing human hair with benzothiazole azo compounds
US 3578386 A
Images(3)
Previous page
Next page
Description  (OCR text may contain errors)

United States Patent 3,578,386 DYEING HUMAN HAIR WITH BENZOTHIAZOLE AZO COMPOUNDS Gregoire Kalopissis, Paris, and Andree Bugaut, Boulognesur-Seine, France, assignors to LOreal, Paris, France No Drawing. Filed Feb. 16, 1968, Ser. No. 705,925 Claims priority, application (lguxembourg, Feb. 22, 1967,

Int. Cl. Afilk 7/12 US. Cl. 8-10 3 Claims ABSTRACT OF THE DISCLOSURE This invention relates to methods of dyeing and dyes for keratinic fibers, especially human hair with benzothiazole compounds corresponding to one of the following formulae:

In each of these formulae R, R and R may be lower alkyl radicals, but in some of the formulae they may be H or acyl radicals instead, as set forth in detail in the specification. Preferably R and R are combined with an adjacent N- to form a heterocyclic radical falling within the group consisting of morpholino, piperidino and pyrrolidino radicals.

The object of the present invention is to provide a new dyeing composition for keratinic fibers and more particularly for human hair, essentially characterized by the fact that it contains in solution at least one compound taken from the group consisting of:

(a) the compounds having the general formula:

' 3,578,386 Patented May 11, 1971 (b) the mono-quaternary compounds having the general formula:

in which R, R and n have the significances indicated above, and R represents a lower alkyl radical having from 1 to 4 carbon atoms or an acyl radical but cannot be a lower alkyl radical when R represents a hydrogen atom; R and R may be included with the nitrogen in heterocyclic ring falling within the group consisting of morpholino, piperidino and pyrrolidino radicals, R represents a lower alkyl radical and X a halogen atom or a SO,CH radical, it being undestood that in the latter case R may represent only a methyl group:

(c) the bis-quaternary compounds having the general formula R i X l T l- 1 J Ilit Rz (III) in which R, R and X have the signficances indicated above, R and R each represent a lower alkyl radical having from 1 to 4 carbon atoms or may constitute part of a heterocyclic ring including nitrogen and falling within the group consisting of morpholino, piperidino and pyrrolidino radicals.

Certain of the compounds described above have already been described in French Pat. No. 1,443,251, in which it was shown that they could be used to dye polyacrylic fibers. The applicants have found that, surprisingly enough, use of the compounds yields particularly worthwhile results in the dyeing of keratinic fibers and, more particularly, for dyeing hair, due to the notable intensity, brilliance and fastness of the desired shades, which range from red to blue black. The blue shades obtained from the quaternary compounds are especially stronger than the blue shades heretofore obtained on hair by means of cationic anthraquinone dyes.

It should be made clear that the dyeing compositions according to the invention may be used in a relatively wide pH range, but that the pH of these compositions should preferably be between 5 and 8.

The length of time that the dyeing compositions according to the invention should be in contact with the hair may vary greatly, but should preferably fall between 5 and 30 minutes. The application temperature of these dyeing compositions may also vary, but in most cases, they should preferably be used at room temperature.

The concentrations of dyes responding to Formulas I, II and III may vary significantly in the dyeing compositions according to the invention, but this concentration is preferably between 0.01% and 3%.

It should be noted that the dyes according to the invention may be mixed with each other or with other dyes normally used in dyeing hair, such as benzene, anthraquinone or azo dyes.

Moreover, the dyeing compositions according to the invention may contain ingredients normally used in cosmetics, such as dispersing or wetting agents, thickeners, detergents, emollients or perfumes.

Another object of the present invention is to provide a process for dyeing keratinic fibers and particularly human hair essentially characterized by the fact that the hair is impregnated with a dyeing composition according to the invention, such as those described above, and that the composition is allowed to act for 5 to 30 minutes after which the hair is shampooed, rinsed and then dried.

Another object of the present invention is toprovide the new articles of manufacture consisting of those new chemical compounds having the Formulas I, II and III which are not described in the French Pat. No. 1,443,251, that is to say the new compositions consisting of those chemical compounds having the general Formula I, II or III, in which the radicals R and R form with the adjacent nitrogen atom a heterocyclic ring belonging to the group consisting of piperidino, morpholino and pyrrolidino radicals.

The previously known compounds having the Formulas I, II and 111 may be prepared as shown in the French Pat. No. 1,443,251.

The new compounds described above may be prepared by condensing a diazonium salt obtained by diazotation of Z-aminobenzothiazole on an N,N-disubstituted aniline having the general formula:

in which R and n have the significances hereinbefore indicated; R and R form with the adjacent nitrogen atom a heterocyclic ring belonging to the group consisting of morpholino, piperidino and pyrrolidino radicals; the final mono or bis-quaternization being carried out with methyl sulfate or a halide of a lower alkyl with or without an appropriate solvent.

In order that the invention may be better understood, several examples will now be described, purely by way of illustration.

EXAMPLE 1 Preparation of azo (Z-aminobenzothiazoleN-ethyl- N-B-piperidinoethyl-aniline) 0.2 mole (30 g.) of Z-aminobenzothiazole is diazotized in solution in 300 cm? of phosphoric acid by the amount of nitrosyl acid sulfate which can be obtained from 0.2 mole (13.8 g.) of sodium nitrite and 115 cm. of sulfuric acid (density d.=1.83). To the diazonium salt solution is added 200 cm. of ice Water and, little by little, at between 5 C. and C., 0.2 mole (46.4 g.) of (N-ethyl- N-fi-piperidinoethyl)-ani1ine in solution is 50 cm. of acetic acid and 50 cm. of Water. The reaction mixture is left for two hours at 0 C. and overnight at the ambient temperature. The mixture is partially neutralized to a pH of 4 to 5 by means of a 3 N sodium hydroxide solution, and cooled overnight at 0 'C., after which drying yields the azo compound in the form of a salt. The precipitate is suspended in one liter of Water at 80 C.; rendered alkaline by means of a N sodium hydroxide solution; and cooled; after which drying yields 55 g. of the desired azo compound, which, after recrystallization in alcohol melts at 130 C.

Analysis of the product yields the following results:

Analysis (percent) Calculated Found Product N S N S CzzH27N5S 17. 81 3. 14 17. 56-17. 64 8. 04-8. 17

EXAMPLE 2' hydrate are obtained which, after recrystallization in alcohol at melts with decomposition at between 250 and 255 C.

Analysis of the product yields the following results:

Analysis (percent) Calculated Found Product N S N S C2|1H41N5S309 10.55 14.48 10. 27-10. 51 14.69-14.83

EXAMPLE 3 The following dyeing composition is prepared:

Azo (Z-aminobenzothiazole-a N-ethyl N fi-aminoethyl-aniline) 0.15 Iso-octylphenyl-polyethoxy-ethanol 5 20% citric acid solution q.s.p. (pH=8). Water q.s.p. 100

This composition is applied to brown hair and left thereon for 15 minutes. The hair is then rinsed and shampooed.

A deep mahogany shade results.

EXAMPLE 4 The following dyeing composition is prepared:

Dimethosulfate of the bis-quaternary compound corresponding to the azo (2-arninobenzothiazo1e- N- ethyl-N-piperidinoethyl-aniline) 0.65 Laurie alcohol oxyethylenated with 10.5 moles of ethylene oxide Na CO solution at 2 N, q.s.p. (pH=7). Water q.s.p. 100

This composition is applied to chestnut hair and left thereon for 15 minutes. The hair is then rinsed and shampooed.

A deep ash brown results.

EXAMPLE 5 The following dyeing composition is prepared:

G. Methosulfate of the mono-quaternary compound corresponding to the azo (Z-aminobenzothiazole N-ethyl-N-formarnido-ethyl-aniline) 0.48 Lauric alcohol oxyethylenated with 10.5 moles of ethylene oxide 2 Na CO solution of 2 N, q.s.p. (pl-1 :7). Water q.s.p. 100

This composition is applied to chestnut hair and left thereon for 15 minutes. The hair is then rinsed and sham- This composition is applied to White hair and left for 15 minutes, after which the hair is rinsed and shampooed.

A dull ash grey shade results.

This composition is applied to 90% white hair and left thereon for 15 minutes. The hair is then rinsed and shampooed.

A dull ash chestnut results.

It will be appreciated that the foregoing examples are merely representative of the many possible ways of carrying out the invention, and may be modified as to detail without thereby departing from the basic principles thereof.

What is claimed is:

1. A composition for dyeing human hair which comprises an aqueous solution of a compound selected from the group consisting of (a) a compound having the formula wherein R represents lower alkyl having 1-4 carbon atoms; n is a number between 2-6 inclusive; and R and R form, in combination with the nitrogen atom to which they are attached, piperidino;

(b) a compound having the formula CHih-N wherein R, and n have the meanings given above, R and R form, in combination with the nitrogen atom to which they are attached, piperidino; R represents lower alkyl and X represents a member selected from the group consisting of halogen and CH SO with the proviso that when X is CH SO R is methyl; and (c) a compound having the formula wherein R, R X and n have the meanings given above, and R and R form, in combination with the nitrogen atom to which they are attached, pi-

peridino, said compound being present in amounts from 0.01-3 weight percent of the total composition.

2. The composition of claim 1 having a pH between 5-8 inclusive.

3. A method for dyeing human hair comprising impregnating said hair with a composition comprising an aqueous solution of a compound selected from the group consisting of (a) a compound having the formula wherein R represents lower alkyl having from 1 to 4 carbon atoms; n is a number between 2 and 6 inclusive, R represents a member selected from the group consisting of hydrogen and lower alkyl having from 1 to 4 carbon atoms, R is selected from the group consisting of hydrogen, lower alkyl having 1 to 4 carbon atoms and formyl, and R and R may form, in combination with the nitrogen, piperidino;

(b) a compound having the formula:

CH2)n-N wherein R, R and n have the meanings given above, R represents a member selected from the group consisting of lower alkyl having 1 to 4 carbon atoms and formyl, with the proviso that R is not lower alkyl when R is hydrogen, and R and R may form, in combination with the nitrogen atom to which they are attached, piperidino; R represents lower alkyl and X represents a member selected from the group consisting of halogen and CH SO with the proviso that when X is CH SO R is methyl; and (c) a compound having the formula:

wherein R, R X and n have the meanings given above; R and R each independently represent lower alkyl having 1 to 4 carbon atoms and may form, in combination with the nitrogen atom to which they are attached, piperidino, said compounds being present in amounts from 0.01 to 3 weight percent of said composition, said composition being applied to the hair in amounts to effectively dye said hair, leaving said composition in contact with the hair for 5 to 30 minutes, and then washing, rinsing and drying said hair.

References Cited UNITED STATES PATENTS 3,414,559 12/1968 Sartori 260158 FOREIGN PATENTS 5/1966 France 260-158 ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US. Cl. X.R.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3933787 *Jan 12, 1973Jan 20, 1976Sandoz Ltd., (Sandoz Ag)Dyeing and printing paper
US3988311 *Apr 9, 1974Oct 26, 1976Ciba-Geigy AgPolyester textiles
US4051084 *Jan 9, 1975Sep 27, 1977Bayer AktiengesellschaftBenzothiazole
US4714606 *Aug 13, 1985Dec 22, 1987Cytocolor IncorporatedMethod of staining and identifying cells and compositions thereof
US5879412 *Dec 19, 1997Mar 9, 1999L'orealCompositions and processes for dyeing keratin fibers with an oxidation base, a coupler, a cationic direct dye, and an oxidizing agent
US5919273 *Dec 19, 1997Jul 6, 1999L'orealReady-to-use composition dyes hair giving uniform color; oxidation base in combination with a substituted meta-aminophenol coupler, cationic direct dye and oxidizing agent; multicompartment dye kit
US5993490 *Dec 19, 1997Nov 30, 1999L'orealComposition for the oxidation dyeing of keratin fibers containing a cationic direct dye and dyeing process using this composition
US6001135 *Dec 19, 1997Dec 14, 1999L'orealCompositions and processes for dyeing keratin fibers with cationic direct dyes, oxidation bases, and oxidizing agents
US6371994 *May 28, 1999Apr 16, 2002L'oreal S.A.Dye composition for keratin fibers, with a cationic direct dye and a polyol or polyol ether
US6436153 *May 28, 1999Aug 20, 2002L'ORéAL S.A.Free of oxidases and oxidoreductases; hair dye
US6712861 *Oct 7, 1998Mar 30, 2004L'oreal S.A.Composition for dyeing keratin fibers and dyeing method using same
US7060110Apr 3, 2002Jun 13, 2006L'orealChromatic direct dyes
US7172631Jun 7, 2002Feb 6, 2007L'oreal S.A.Applying mixture to fibers, hair; washing, rinsing
US7172633Jun 16, 2004Feb 6, 2007L'ORéAL S.A.For dyeing keratin fibers, in particular human keratin fibers such as the hair, in particular to obtain good shampoo resistance
US7189266Jun 10, 2002Mar 13, 2007L'oreal, S.A.Dyeing composition for human keratinous fibres with direct dyes and dicationic compounds
US7201779Jun 16, 2004Apr 10, 2007L'oreal S.A.For dyeing keratin fibers
US7261743Jun 7, 2002Aug 28, 2007L'orealDicationic compounds for dyeing human keratin fibers, and compositions comprising them
US7300471Feb 28, 2005Nov 27, 2007L'oreal S.A.Composition comprising at least one mixed dye based on at least one chromophore of azo or tri(hetero) arylmethane type, dyeing process and mixed dyes.
US7326259Jun 22, 2005Feb 5, 2008L'oreal S.A.Use of polycationic compounds in the dyeing of keratinous fibres
US7488354Oct 14, 2005Feb 10, 2009L'oreal S.A.Dyeing composition comprising at least one disulphide dye and method of dyeing human keratin fibers using this dye
US7513916Feb 16, 2007Apr 7, 2009The Procter & Gamble CompanyAgents for coloring keratin fibers
US7513917Feb 16, 2007Apr 7, 2009The Procter & Gamble CompanyFor the simultaneous lightening and coloring of keratin fibers; oxidizing agent, and azo dye; such as 2-[{4-[(4,5-dimethyl-1,3-thiazol-2-yl) diazenyl ]phenyl}(ethyl)amino]-N,N,N-trimethylethanaminium bromide
US7582122Aug 28, 2006Sep 1, 2009L'oreal S.A.Mixed cationic dyes comprising at least one anthraquinone chromophore and their use in methods of hair dyeing
US7658770Feb 26, 2009Feb 9, 2010The Procter & Gamble CompanyAgents for coloring keratin fibers
US7658771Feb 26, 2009Feb 9, 2010The Procter & Gable CompanyColoring agents for keratin fibers
US8038731Mar 23, 2007Oct 18, 2011L'oreal S.A.hair dyes contains naphthylimide thiol or disulphide groups; resistant and visible lightening effect on dark keratin fibres; cosmetics
US8038732Mar 23, 2007Oct 18, 2011L'oreal S.A.Fluorescent entity, dyeing composition containing at least one fluorescent entity, and method for lightening keratin materials using said at least one fluorescent entity
US8562693Nov 19, 2012Oct 22, 2013L'orealMethod of dyeing and lightening keratin materials in the presence of a reducing agent comprising a fluorescent deisulphide dye
US8685114Oct 10, 2013Apr 1, 2014L'orealComposition for dyeing and lightening keratin materials comprising a fluorescent deisulphide dye compound
CN101384302BFeb 9, 2007Apr 3, 2013宝洁公司Agents for coloring keratin fibers
EP1618865A1 *Jun 22, 2005Jan 25, 2006L'orealUse of polycationic compounds for dyeing keratin fibres
EP1820536A1 *Feb 18, 2006Aug 22, 2007Wella AktiengesellschaftColoring agents for keratin fibers
EP1820537A1 *Feb 18, 2006Aug 22, 2007Wella AktiengesellschaftAgents for coloring keratin fibers
WO2002080869A2 *Apr 3, 2002Oct 17, 2002David HerveNovel dyeing composition for dyeing keratinous fibres comprising a particular dicationic monoazo dye
WO2002100365A1 *Jun 7, 2002Dec 19, 2002OrealUse of dicationic compounds for dyeing human keratinous fibres and compositions containing same
WO2002100366A2 *Jun 7, 2002Dec 19, 2002OrealDyeing composition for human keratinous fibres with oxidation dyes and dicationic compounds
WO2002100367A1 *Jun 10, 2002Dec 19, 2002OrealDyeing composition for human keratinous fibres with direct dyes and dicationic compounds
WO2007093943A1 *Feb 9, 2007Aug 23, 2007Procter & GambleColoring agents for keratin fibers
WO2007097930A1 *Feb 9, 2007Aug 30, 2007Procter & GambleAgents for coloring keratin fibers
Classifications
U.S. Classification8/426, 534/611, 534/589, 534/603, 534/788
International ClassificationA61Q5/06, D06P1/41, C09B29/033, D06P1/42, C09B29/00, A61K8/49, C09B39/00, A61K8/30, D06P3/04, D06P3/18
Cooperative ClassificationA61K8/49, A61Q5/065
European ClassificationA61K8/49, A61Q5/06D