DE1617693A1 - Hair dyes - Google Patents

Description

Hair dyes

It is known to use 2-nitro-1,4-phenylenediamine as an active ingredient in color solutions for hair and other keratin fibers. A It is also known that these dyes have a good affinity in the cold for keratin fibers, but that they have the disadvantage of only providing shades of red-orange. Substitution products of 2-nitro-1, A-phenylenediamine have been proposed to achieve darker shades, ie hair colorations which tend towards green. It was found that substantially caused the introduction of a methyl group into the receptacle located in meta-position to the nitro group of the amino group of 2-nitro-l ₉ 4-p "henylendiamins a deepening of the color shade. The products thus obtained can, however, only be used in a relatively limited pH range in the vicinity of the neutral point.

The invention aims to avoid these disadvantages, which is achieved by means of dyes of the general formula

NH-R

-NO ₂

1098 17/1900

R ♦ -K- (CH ₂ ) _n -C00H

-Z-

in which RCH. or (3H ₂ CH ₂ OH, R hydrogen or CH ₃ and η denote an integer between 1 and k inclusive, is made possible, which can achieve even darker shades of color tending towards blue, and in a wide pH range from acidic pH Values, preferably between pH 3 and pH 10, are applicable «

The invention relates to a means for dyeing keratin fibers, in particular of human hair, because it is characterized in that it contains at least one of the aforementioned dyes Formula, preferably in an aqueous solution, as well as any other additives customary for hair dyes, such as penetrants, thickeners, swelling and softening agents, shine agents, Fragrances or the like contains. The agent according to the invention can also contain other dyes known for dyeing hair contain «The pH value of the solution is preferably 3 - 10.

The coloring agent of the new hair dye can be manufactured in various ways. So it can be won in such a way that first by reacting l-amino-2-nitro-4- (N-methyl- N-carbamylalkyl-amino) -benzene, where the alkyl radical has 1-4 carbon atoms may contain, with pr-toluene sulfochloride, the primary amino group is blocked · Then the free hydrogen of this amino group, for example by the action of dimethyl sulfate in Low-base milieu, replaced by the methyl radical. The tosyl radical introduced in the first stage is then activated by the action of

109817/1900

concentrated sulfuric acid and finally through HydroIyse.mi * concentrated hydrochloric acid split off the acid amide group.

You can also win it so that by reacting l-amino-2-nitro - ^ - methylaminobenzene with a chloroacylamide of the formula Cl (CH ₀ ) CONHo, where ^{n is} 1 ^{to 2} ^, such as chloroacet- μ amide or ß -Chlorpropionamid, in the secondary amino group in the 4-position a carbamylalkyl radical, such as, for example, a carbamylmethylbzw. Carbamyläthylrest, is introduced. The resulting 1-amino-2 »nitro-4- (N-methyl-N-carbamylalkylamino) -benzene is treated with β-chloroethyl chloroformate to form the β-chloroethyl ester of the corresponding N-carbamylalkyl compound, such as 2-nitr o-k- (N-methyl-N-carbamylmethyl or -N-carbamyl-ethylamino) -phenyl-carbamic acid, implemented. The amide group is then split off by hydrolysis with hydrochloric acid and the compound obtained is subjected to alkaline hydrolysis to convert the chloroethyl ester group into the β-oxyethyl group. The monochlorohydrate of the desired compound is then obtained by acidification with hydrochloric acid.

Another production possibility is that, for example, l-methylamino-2-nitro-4-aminobenzene with a chloroacylamide of the formula Cl (CH ₂ ) _n CONH ₂ , where η is 1 to h , such as chloroacetamide or ß-chloropropionamide, for reaction brought

109817/1900

and in the resulting N-carbamylalkyl compound, such as, for example, B, l-methylamino-2-nitro-4-carbamylmethyl-aminobenzene or h- (ß-carbamylethylamino) -benzene, the amide group is split off by hydrolysis with hydrochloric acid «

Example 1:

Hair dye for ash blonde with mother-of-pearl effect:

l-methylamino-2-nitro-4- (N-methyl-. N-carboxymethylaminoJ-benzene chlorohydrate 0.3 g

lauryl oxyäthylenated with 10 moles of ethylene oxide

alcohol 5 g

Sodium carbonate up to a pH ¥ ¥ ertes v _f 3 and make up to 100 g with water

This coloring solution applied to golden yellow bleached hair results in an ash blonde with a mother-of-pearl effect.

Example 2:

Hair dye for chestnut brown with golden beetle colored reflections

1-methylamino-2-nitro-4- (N-methyl-N-carboxymethylamino) benzene chlorohydrate 0.6 g

Laurylammonium sulfate (20%) 5 g

Sodium carbonate until a pH value of v is reached. 5

and make up to 100 g with water

This dye solution applied to light auburn hair results in a maroon with golden beetle-colored reflections.

109 8 17/1900

1617893

B e i s ρ i e 1 3:

Chestnut hair dyes with a violet effect;

1- (β-Hydroxyethyl-amino) -2-nitro-4- (N-methyl-N-carboxymethylamino) -benzene-chlorohydrate 0.6 'g

l-Hydroxy - ^ - amino - ^ - nitrobenzene O ₁ Ol g

With 10 moles of ethylene oxide oxyäthylenierter lauryl alcohol 5 g of sodium carbonate until a pH value of 9 is reached and make up to 100 g with water

This dye solution applied to chestnut brown hair results in M a chestnut brown with a violet-colored effect «

B is ρ ie 1 ht .

Hair dye for an asymmetrical light chestnut brown »

1-Xβ-Hydroxyethylamino) -2-nitro-4- (N-methyl-N-carboxymethylamino) benzene chlorohydrate 0.5 S

Lyurylammonium Sulphate (20 $ ig) 5 p

Sodium carbonate until a pH value of v.8 is reached and make up to 100 g with water

This solution is applied to light natural brown hair and results in an ash-colored light chestnut brown

Example 5 *

Hair dye for a light maroon with dark purple Effect.

1-methylamino-2-nitro-4- (N-carboxymethylamino) - benzene chlorohydrate 0.8 g

Sodium carbonate until a pH value of V. 9 # 5 is reached Laurylammonium sulfate (20 #ig) 5g

109817/1900

and make up to 100 g with water

-G-

This solution is applied to dark blonde hair and results in a light chestnut brown with a dark purple effect.

Example 6t

Hair dye for dark blonde with a pearly effect:

1-methylamino-2-nitro-4- (N-carboxymethylamino) -fc benzene chlorohydrate 0.8 g

lauryl alcohol 5 S oxyäthylenated with 10 moles of ethylene oxide

Sodium carbonate until a pH value of v. 3 and w * £ S4ii * Mxwith water to 100 g

This solution is applied to blonde hair and results in a dark blonde with a ρer! Mother-like effect,

Example 7:

Hair dye for beige with bold ash-colored pearlescent Reflexent

l-methylamino-2-nitro - ^ - (K-methyl-N-carboxymethy-

lamino) benzene chlorohydrate 0.14 g

4-nitro-1,3-diaminobenzene 0.02 g

Ammonia (20%) until a pH value of% 3 is reached

and make up to 100 g with water

This solution is applied to straw blonde bleached hair and results in a beige with strong ash-colored mother-of-pearl-like Reflexes *

109817/1900

EXAMPLE:

Hair dye for a warm beige-gold color:

1- (ß-hydroxyethylamino) -2-nitro-4- (2i-methyl-N-carboxymethylamino) benzene chlorohydrate 0 _t 15 g

^ -Nitro-l ^ -diaminobenzene 0.02 g

Ammonia (20 #) until a

pH value of 3

and make up to 100 g with water

This solution is applied to platinum yellow bleached hair and results in a warm beige-gold color,

Example 9:

Hair dye for an ash blonde coloration with violet Effect.

1- (β-Hydroxyethylamino) -2-nitro-4- (N-methyl-K "carboxymethylajnijao) -benzene-chlorohydrate 0.24 g

4-nitro-1,3-diaminobenzene 0.08 g

Ammonia (20 fiig) until a ™ is reached

pH value of 3

and make up to 100 g with water

This mixture is applied to white hair and results

an ash-blonde color with a violet-colored effect.

Example 10i

Hair dye for a very light blonde with a light one pearlescent

l-methylamino ^ -nitro-Jl - (carboxymethy lamino) -

benzene chlorohydrate 0.1 g

^ -Nitro-1,3-diaminobenzene 0.00 ** g

Acetochihon Violet Lumiere N 0.03 g

Acetoquinone Yellow Lumiere RZ 1 0 9 8 17/1900 0.03 g

Ammonia (20 $ ig) until one is reached

pH value of 3

and make up to 100 g with water

This solution is applied to white hair and results in a very light blonde with a slight pearlescent shade

Example 11t

Hair dye for a beige-pink coloring:

1-methylamino — 2 — nitro— k— (ß-carboxyethylamino) -

benzene chlorohydrate 1 g

Sodium carbonate until a pH value of v is reached. 9

Lauryl ammonium sulfate ($ 20). 5 g

drop to 100 g

This solution is applied to blonde hair and results in a beige-pink color

109817/1900

Claims (1)

Claims 1 »Hair dye, characterized in that it is at least a dye of the formula -R R «-N- (CH ₂ ) _n -C00H in which R is CH "or CH ₂ CHpOH, R ^{1 is} hydrogen or CH" and η is an integer between 1 and h inclusive, preferably in aqueous solution. 2 »Means according to claim 1, characterized in that it In addition, other additives customary for hair dyes, such as penetrants, thickeners, swelling and softening agents, Contains brighteners, fragrances or the like, 3. Means according to claims 1 and 2, characterized in that it also contains other dyes known for dyeing hair. k \ Agent according to the preceding claims., characterized in that it has a pH value of 3 to 10 « 10 9 817/1900