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Publication numberUS3826608 A
Publication typeGrant
Publication dateJul 30, 1974
Filing dateSep 24, 1970
Priority dateOct 2, 1969
Also published asCA923041A, CA923041A1, DE1949750A1, DE1949750B2, DE1949750C3
Publication numberUS 3826608 A, US 3826608A, US-A-3826608, US3826608 A, US3826608A
InventorsE Wiskott
Original AssigneeTherachemie Chem Therapeut
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process and composition for dyeing of human hair
US 3826608 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent US. Cl. 810.1 10 Claims ABSTRACT OF THE DISCLOSURE A process for the dyeing of living human hair consisting essentially of treating human hair at a temperature of from about 10 C. to 40 C. with an aqueous solution containing a nitropyridine having the formula wherein'X and Y are amino or substituted amino groups, and aqueous dyestutI compositions containing said nitropyridines.

THE PRIOR ART OBJECTS OF THE INVENTION object of the present invention is the development of a process for the dyeing of living human hair consisting essentially of treating human hair at a temperature of from 10 C. to 40 C. with an aqueous dyestufi composition containing, as sole dyestutf ingredient, from 0.3% to by weight of a nitropyridine having the formula NH Y Y wherein Y is selected from the group consisting of NH;; and

wherein R is a member selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxyalkyl having 2 to 8 carbon atoms, hydroxylalkyl having 2 to 8 carbon atoms, aminoalkyl having 2 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, dialkylaminoalkyl having 3 to 12 carbon atoms, alkylaminoalkyl having 2 to 8 carbon atoms, dialkanolaminoalkyl' having 5 to 12 carbon atoms and alkanolaminoalkyl having 3 to 8 carbon atoms; R is a member selected from the group consisting of hydrogen and -=R and R and R taken together are selected from the group consisting of alkylene having 4 to 5 carbon atoms, ethoxyethylene and ethylaminocthylene, and rinsing said hair.

A further object of the present invention is the development of an aqueous composition for dyeing living 3,826,608 Patented July 30, 1974 human hair consisting essentially of at least by weight of water, from 0.5% to 55% by weight of customary dyestuif adjuvants, no chemical oxidizing agents and from 0.3% to 5% by Weight of a nitropyridine having the formula NH Y wherein Y is selected from the group consisting of -NH;; and

where R, is a member selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxyalkyl 2' to 8 carbon atoms, hydroxyalkyl having 2 to 8 carbon atoms, ,aminoalkyl having 2 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, dialkylaminoalkyl having 3- to 12 carbon atoms, alkylaminoalkyl having 2 to 8 carbon atoms, dialkanolaminoalkyl having 5 to 12 carbon atoms and alkanolaminoalkyl having 3 to 8 carbon atoms; R is a member selected from the group consisting of hydrogen and R and R and R taken together are selected from the group consisting of alkylene having 4 to 5 carbon atoms, ethoxyethylene and ethylaminocthylene, said aqueous composition having a pH of from about 8 toabout 10.

A yet further object of the present invention is the obtention of a 3-amino-5-nitropyridine having the formula NO N H:

N-Rr \N Rl wherein R and R are members selected from the group consisting of alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 2 to 4 carbon atoms, and when taken to: gether, alkylene having 4 to 5 carbon atoms.

These and other objects of the present invention will become more apparent as the description thereof proceeds.

DESCRIP'I'IONQETHEINVEN'I'ION The drawbacks of the prior art have been overcome and the objects of the invention have been achieved by the present invention. It has now been found that certain nitropyridine compounds can be used with excellent results for the dyeing of human hair in the absence of chemical oxidizing agents and other developer or coupling components.

N 1 wherein X and Y are amino or substituted amino groups, possibly heterocyclic with the nitrogen atom.

The substituents X and Y can be identical ordifferent. In particular, substituted amino groups of the formula can be used where R denotes an alkyl radical with 1 to 8, preferably 1 to 4 carbon atoms, which contains, preferably terminal alkoxy, amino or amino group substituted by alkyl or alkanol radicals, and where the alkyl radical or the alkanol can contain 1 to 4 carbon atoms, and where R, denotes a hydrogen atom or a radical as indicated for R R and R; can, together with the nitrogen atom, also represent a heterocyclic ring.

Specifically the following groups are mentioned as amino groups for X and Y The two amino groups can be identical or different. Suitable substituted amino groups according to the compounds of formula I which contain heterocyclic rings are the pyrolidino, pipen'dino, or morpholino groups.

Among the compounds of formula I, preferably a nitropyridine having the formula wherein Y is selected from the group consisting of -NH, and

R: wherein R is a member selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxyalkyl having 2 to 8 carbon atoms, hydroxyalkyl having 2 to 8 carbon atoms, aminoalkyl having 2 to 8 carbon atoms, cycloalkyl having to 8 carbon atoms, dialkylaminoalkyl having 3 where Z denotes an aminoor a substituted amino group, which likewise form a heterocyclic ring. In particular,

these novel compounds are S-amino-S-nitropyridines having the formula NO NH wherein R and R are members selected from the group consisting of alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 2 to 4 carbon atoms, and, when taken together, alkylene having 4 to 5 carbon atoms.

The following compounds are mentioned specifically: 2 dimethylamino-5-nitro-3aminopyridine, 2-pyrrolidine- 5-nitro-3-aminopyridine and 2-piperidino-5-nitro-3-aminopyridine. These compounds give excellent dyeing effects on human hair.

The nitropyridines used can be produced in various ways. For example, monohalogen pyridines can be reacted in the presence of dimethyl sulfoxide with the corresponding amines or alkanol amines. Subsequently, two nitro groups are introduced by nitration, of which one is converted to an amino group by reduction, for example, with ammonium sulfide. The corresponding amino halogen-pyridines can also be utilized as starting material, where the amino groups can be substituted, if necessary. These compounds are subsequently reacted with the corresponding amines or alkanol amines and the compounds obtained are nitrated or first, the amino halogen pyridines are nitrated and then reacted with amines or alkanol amines.

Other production possibilities consist in nitrating hydroxyaminopyridines substituted on the amino-function, if necessary, chlorinating the hydroxy group with phosphorus oxychloride to obtain nitro-chloro-aminopyridines, and converting the latter as above, for example, in dimethyl sulfoxide with amines or alkanol amines to the desired susbtituted diarnino nitropyridines. The introduction of nitro groups can also be effected in some cases with advantage by nitrosating and subsequent oxidation with ammoniacal hydrogen peroxide.

The dye treatment of the living human hair is preferably for a period of 10 minutes to 1 hour followed by a rinsing of the hair.

The hair dyeing compositions may be applied in the form of aqueous solutions, but especially in the form of creams or emulsions. For this purpose, the nitropyridine compounds are mixed with an optional wetting agents or washing compositions, especially anionic or non-ionic substances. Suitable wetting and washing agents are especially alkylbenzenesulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid ethanolamides, products of addition of ethylene oxide to fatty acids and fatty alcohols, and fatty alcohol alkyl ether and polyalkyl ether sulfates.

The absorptive capacity of the above-mentioned dyestuffs is also good when they are in admixture with such compositions. Consequently, the hair dyes can be produced in the form of shampoos, especially of cream shampoos, which are much desired in practice.

Further, thickeners such as, for example, methylcellulose, starch, higher fatty alcohols, vaseline, paraflin oil and fatty acids, and also perfume or hair conditioning substances such as, for example, pantothenic acid and cholesterol, may be admixed with the compositions of the invention.

The added substances are used in the amount customary for these purposes. Suitable added amounts of wetting agents are, especially, 0.5% to 30% by weight, and of thickeners, are 0.1% to 25% by weight, referred in each case to the total composition. The concentration of the dyestufi components is, to a certain extent dependent on the purpose of use and'a'mounts, from 0.3% to 5% by weight, preferably 0.5% to 2.5% by weight. These quantities are also with reference to the total composition.

The hair dyes are adjusted so that they are alkaline, preferably to a pH value of 8 to 10. The dyeings obtained with the hair dyes described above have good properties with respect to light, washing and rubbing.

The present invention will be further described by way of reference to the following specific examples. These however are not to be deemed limitative of the practice of the invention.

EXAMPLE I Production of Z-dimethylamino-S-nitro-3-aminopyridine parts by weight of Z-dimethylamino-pyridine were dissolved in 350 parts by volume of concentrated sulfuric acid. Subsequently, a mixture of 134 parts by volume of concentrated sulfuric acid and 114 parts by volume of nitric acid (specific gravity 1.52) was added dropwise to the solution at a temperature maintained below 5 C. The mixture was stirred for one hour while cooling with ice. Then the reaction product was poured into 2500 parts by volume of ice water. The yellow needles obtained were vacuum filtered, washed with water. until neutrality, and recrystallized from ethanol. The 2-dimethylamino-3,5-dinitropyridine produced had a melting point of 125 to 126 C..Yield: 110 parts by weight. 30'partsby weight of the amino-com ound were stirred for. hours at room temperature in 1440 parts, by volume of methanol and 300 parts by volume of a 40% ammonium sulfide solution and then boiled for 1 hour at reflux and vacuum filtered. The solution was concentrated undervacuum to dryness and extracted with chloroform. The extract .was subject to chromatography on 200 parts by weight of neutral aluminum oxide and eluted with chloroform. Thered fractions yielded on concentration red-brown crystals of Z-dimethylamino-5-nitro-3aminopyridine (ni.p.=118 to 121 C.).

EXAMPLE II Production of 2-pyrrolidino-3-amino-5-nitropyridine 74 parts by weight of 2-pyrrolidinopyridine were nitrated as described in Example 1. After recrystallization from ethanol, 52 parts by weight of 2-pyrrolidino-3,5-dinitropyridine with a melting point of 130 to 132 C. were obtained. 30 parts by weight of the dinitro-compound were reduced with ammonium sulfide (see Example I) and worked up. The red 2-pyrrolidine-3-amino-5-nitropyridine so obtained melted at 115 to 116 C.

EXAMPLE III Production of 2-piperidin0:3-amino-5-nitropyridine By nitrating Z-piperidinopyridine according to the method described in Example I, 2-piperidino-3,5-dinitropyridine (m.p. 147 to 149 C.) was obtained. Subsequently, the production solution was reduced with ammonium sulfide, as in Example I, and worked up. The red Z-piperidino- B-amino-S-nitropyridine so obtained melted at 106 t 109 C.

EXAMPLE IV 4 parts by weight of cetyl alcohol, 4 parts by weight of stearyl alcohol, 3 parts by weight of lauryl alcohol and parts by weight of sodium lauryl ether sulfate were melted together at 70 C., and an aqueous alcoholic solution of 1 part by weight of 2,6-diamino-3-nitropyridine was stirred into this mixture. The cream was brought with hot water to 98 parts by weight, cooled to room temperature, adjusted to a pH of 9.5 with concentrated ammonia, to obtain 100 parts by weight.

The dye cream so obtained dyed grey hair an intense yellow when treated at room temperature over a period of minutes. After the dye treatment, the hair was rinsed with water and shampooed.

EXAMPLE V 5 parts by weight of cetyl alcohol, 4 parts by weight of stearyl alcohol, 1 part by weight of lauryl alcohol and 18 parts by weight of a mixture of fatty alcohol sulfates (C to C were melted at 70 C. and a solution of 1 part by weight of 2-pyrrolidino-3-amino-5- nitropyridine in some ethyl alcohol was stirred in. The cream was brought with hot water to 98 parts by weight, cooled to room temperature and adjusted to a pH of 9.5 with concentrated ammonia, to obtain 100 parts by weight.

The dye cream so obtained dyed grey hair orange when treated at a temperature of 30 C. for 25 minutes.

EXAMPLE VI A hair dyeing cream was produced as in Example 4, but, as a nitropyridine compound 1 part by weight of 2-dimethylamino-3-arnino-5-nitropyridine was utilized. The cream dyed grey hair yellow when treated at room temperature over a period of 30 minutes.

6 EXAMPLE VII A hair dyeing cream was produced as in Example 4, but, as a nitropyridine compound 1 part by weight of Zpiperidino-B-amino-5-nitropyridine was utilized. When grey hair was treated with this dye cream for 30 minutes at 30 C. a light yellow hair color was obtained.

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art may be employed without departing from the spirit of the invention and the scope of the appended claims.

- I claim:

1. A .process for the dyeing of human hair consisting essentially of applying to human hair at a temperature of from 10 C. to 40 C. an etfective amount of an aqeuous dyestuflf composition containing, as sole dyestutf ingredient, from 0.3% to 5% by weight of a nitropyridine having the formula NH Y wherein Y is selected from the group consisting of --NH, and

R: where R, is alkyl having 1 to 8 carbon atoms; R, is a member selected from the group consisting of hydrogen and R or R and R; taken together are alkylene having 4 to 5 carbon atoms, and rinsing said hair.

2. The process of claim 1 wherein said nitropyridine is 2,6-diamino-3-nitropyridine.

3. The process of claim 1 wherein said nitropyridine is a 3-amino-5-nitropyridine having the formula NO NH:

wherein R and R are alkyl having 1 to 4 carbon atoms, or, when taken. together, are alkylene having 4 to 5 carbon atoms.

4. The process of claim 3 wherein R and R taken together represent alkylene having 4 to 5 carbon atoms.

5. The process of claim 3 wherein R and R are methyl.

6. An aqueous composition for dyeing living human hair consisting essentially of at least 40% by weight of water, from 0.5% to 30% by weight of wetting agents, from 0.1% to 25% by weight of thickeners, and, as sole dyestufi ingredient, from 0.3% to 5% by weight of a nitropyridine having the formula NH Y wherein Y is selected from the group consisting of ---NH; and

wherein R is alkyl having 1 to 8 carbon atoms; R; is a member selected from the group consisting of hydrogen and R or R and R taken together are alkylene having 4 to 5 carbon atoms, said aqueous composition having a pH of from about 8 to about 10.

7. The aqueous composition of claim 6 wherein said nitropyridine is 2,6-diamino-3-nitropyridine.

8. The aqueous composition of claim 6 wherein said nitropyridine is a B-amino-S-nitropyridine having the formula N0 NH:

- R taken together represent alkylene having 4 to 5 carbon atoms.

10. The aqueous composition of claim 8 wherein R and R are methyl.

References Cited UNITED STATES PATENTS Schneiderwirth 260-296 R 1 1/ 1934 10/1961 Hunger et a1. 260-496 R X 8/1965 Lange 8-102 7/ 1965 Reinert 424-263 10/1966 Goodhue 424-263 4/1971 Driscoll 424263 FOREIGN PATENTS 9/ 1949 Great Britain 260--296 R 6/1956 Great Britain 260 -296 R ALBERT T. MEYERS, Primary Examiner D. R. ORE, Assistant Examiner US. 01. x1e.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4661115 *Feb 6, 1986Apr 28, 1987Ruetgerswerke AktiengesellschaftHair dyeing agents
US4950302 *Aug 1, 1988Aug 21, 1990Wella AktiengesellschaftProcess for the production of 2,5-diamino-6-nitro-pyridine derivatives, their use in hair dye compositions and new 2,5-diamino-6-nitropyridine derivatives
US4973429 *Feb 15, 1989Nov 27, 1990Ciba-Geigy CorporationOrganic materials with non-linear optical properties
Classifications
U.S. Classification8/423, 546/276.4, 546/307, 546/193
International ClassificationC07D401/04, C07D213/72, A61K8/49, C07D213/74, A61Q5/06
Cooperative ClassificationC07D213/74, A61Q5/065, A61K8/4926
European ClassificationA61Q5/06D, A61K8/49C4, C07D213/74