DE1617693C3 - Hair dye based on 2-nitro-1,4-phenylenediamine in aqueous solution - Google Patents

Description

R '- N - (CH ₂ ), - COOH

where R is the group CH ₃ or CH ₂ CH ₂ OH, R 'is hydrogen or CH ₃ and η is an integer between 1 and 4 inclusive, and other additives customary for hair dyes and has a pH of 3 to 10. 2. Composition according to claim 1, characterized in that it additionally contains other dyes known for dyeing hair.

The present invention relates to a hair dye based on 2-nitro-1,4-phenylenediamine in aqueous solution.

It is known that 2-nitro-1,4-phenylenediamine is used as an active ingredient in color solutions for hair and others Use keratin fibers. It is also known that these dyes have good cold affinity for keratin fibers, but they have the disadvantage show only delivering red-orange nuances. To achieve darker nuances, i. H. Hair coloring, those with a tendency towards green, substitution products of 2-nitro-1,4-phenylenediamine have been proposed. Included it was found that essentially the introduction of a methyl group in the meta-position to the nitro group The amino group of the 2-nitro-1,4-phenylenediamine that is present causes a deepening of the color shade. However, the products obtained in this way can only be used in a relatively limited pH range near the neutral point.

From the German patent specification 928 909 is a method for dyeing animal fibers and in particular known from human hair without the aid of oxidizing agents, in which certain nitrophenylenediamine dyes Find application. Other nitrated p-phenylenediamine derivatives are in the British Patent 955,743. Another group of nitrated phenylenediamine derivatives is known from Dutch patent specification 98 216.

The hair dye according to the invention of the type described at the beginning is characterized in that that it consists of at least one dye of the formula

NH-R

wherein R is the group CH ₃ or CH ₂ CH ₂ OH, R 'is hydrogen or CH ₃ and /; an integer between 1 and 4 inclusive, and other additives customary for hair dyes and has a pH of 3 to 10.

In a further embodiment of the invention, the present hair dye additionally contains other dyes known for dyeing hair.
Experiments have shown that the inventive

ίο Hair dye has the beneficial property of delivering dyes with deeper color nuances when the pH value changes to the alkaline side. This advantageous property is not present in the hair dyes according to the above prior art, which contain structurally related dyes, so that the person skilled in the art could in no way foresee this advantage of the hair dye according to the invention.
The in the invention. Dyes used in hair dyes can be prepared in various ways. They can be prepared by first reacting l-amino-2-nitro-4- (N-methyl-N-carbamylaIkyl-amino) benzene, the alkyl radical of which contains 1 to 4 carbon atoms, with p-toluenesulfo-

a5 chloride the primary amino group is blocked. Then the free hydrogen of this amino group is replaced by the methyl radical, for example by the action of dimethyl sulfate in a basic medium. The tosyl radical introduced in the first stage is then split off by the action of concentrated sulfuric acid and finally the amide group is split off by hydrolysis with concentrated hydrochloric acid.
The dyes used according to the invention can also be prepared by reacting l-amino-2-nitro-4-methylaminobenzene with a chloroacylamide of the formula C1 (CH ₂ ) "CONH ₂ , where π has the meaning 1 to 4, such as, for example, chloroacetamide or / 3-chloropropionamide, a carbamylalkyl radical, such as, for example, a carbamylmethyl or carbamylethyl radical, being introduced into the secondary amino group in the 4-position. The resulting l-amino-2-nitro-4- (N-methyl-N-carbamylalkylamino) benzene is treated with / 3-chloroethyl chloroformate / tf-chloroethyl ester of the corresponding N-carbamylalkyl compound, such as. B. 2-nitro-4- (N-methyl-N-carbamylmethyl- or -N-carbamylethylamino) -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 / 9-oxyethyl group. The monohydrochloride of the desired compound is then obtained by acidification with hydrochloric acid.

Another production possibility is that, for example, l-methylamino ^ -nitro ^ -aminobenzene with a chloroacylamide of the formula

Cl (CHa) _n CONH ₂

R '- N

COOH

wherein / 1 has the meaning 1 to'4, such as. B. chloroacetamide or / 9-chloropropionamide, for implementation is brought and in the resulting N-carbamylalkyl compound, such as B. 1-methylarino-2-nitro-4-carbamylmethylaminobenzene or -4 - (/? - carbamyläthylamino) -benzene, the acid amide group is split off by hydrolysis with hydrochloric acid.

3 4

For example B ei s ρ iel 5 ·;

Hair dye for ash blonde with mother-of-pearl effect: Hair dye for a light chestnut brown with

l-methylamino-2-nitro-4- (N-methyl- dark purple effect:

N-carboxymethylamino) -benzene-chloro- S l-methylamino-2-nitro-4- (N-carboxy-

hydrate 0.5 g methylamino) benzene chlorohydrate ... 0.8 g

with 10 moles of ethylene oxide oxyäthylenierter. _T,, . . ,

Lauryl alcohol 5 g sodium carbonate until achieved

_XT . ,,. _. ,. a pH of 9.5 laurylammo-

Sodium carbonate until a _{10th grade is achieved niumsu} i _{fat (2Ο} ο / _ο ΐ ₈ ) 5 g

pH 3 and fill with water

up to 100 g ^and fill up with water to 100 g

This coloring solution on golden yellow bleached hair This solution is applied to dark blonde hair.

applied results in an ash blonde with a mother-of-pearl effect. ₁₅ wear and results in a light maroon with

dark purple effect. B e i s ρ i e 1 2

Hair dye for chestnut brown with gold beetle B e i s ρ i e 1 6

colored reflections: _ao hair dye for dark blond with mother-of-pearl

l-methylamino-2-nitro-4- (N-methyl-like effect:

N-carboxymethylaminoVbenzene-chloro- _Λ ,,,,. ". . .._,

hvdrat 0 6 ε l-methylamino-2-nitro-4- (N-carboxy-

_r , ········ ■ ····· · · ■ ■ · · '& methylaminoVbenzene chlorohydrate ... 0.8 g

Lauryl ammonium sulfate (20 ° / ₀ ig) 5 g _a. ^J .. ^{J b}

Sodium carbonate until an oxyäthylenier- with 10 moles of ethylene oxide is reached

pH value of 5 and fill with water ^ter lauryl alcohol 5 g

on, on 100 g of sodium carbonate until reaching

a pH of 3 and fills with

This dye solution on light auburn hair 30 water on 100 g

applied results in a chestnut brown with golden beetle-colored reflections. This solution is applied to blonde hair

and results in a dark blonde with a mother-of-pearl

Example 3 effect.

Hair dye for chestnut brown with violet ³⁵ B eis ρ ie 1 7

colored effect:

... _TTJ ..... . . . Hair dye for beige with strong ashy

l - ^ - Hydroxyethyl-amino) -2-nitro- _{colored per} i _mother-like reflexes:

4- (N-methyl-N-carboxymethylamino) -

benzene chlorohydrate 0.6 g ⁴ °

l-Hydroxy-2-aimno-5-nitrobenzene 0.01 g l-methylamino-2-mtro _: 4- (N-methyl-

., -., ... ,,, ..... N-carboxymethylammoj-benzene-chloro-

with 10 mol Äthylenoxyd oxyäthylenier- hvdrat 014 fiter lauryl alcohol 5g ^y

Sodium carbonate until reaching 45 t ^^ 'where ^ ⁰ ^ ⁰¹ ' ^ "- V" ° '° ^{2g of} a pH value of 9 and fill with ammonia (20 »/ ₀ ig) until it is reached

Water on, to 100 g ^e ' ^nes pH-value of 3 and fills with

⁶ water to 100 g

This coloring solution applied to auburn hair results in a maroon with violet 50 This solution is bleached on straw blonde hair colored effect. applied and results in a beige with strong

ash-colored pearlescent reflections. Example 4

Hair dye for an ash-colored light chestnut ₅₅ Examples

white brown: _TT ..........,. ,.

Hair dye for a warm beige gold

l - (/? - Hydroxyäthylamino) -2-nitro- coloring:

4- (N-methyl-N-carboxymethylamino) - "," _TT . .... . ".,. _{/ xr}

benzene chlorohydrate ................ 0.5 g , l - (^ Hydroxyathylammo) -2-mtro-4- (N-

_T , · ,,. / - _Λη / ν c ° methyl-N-carboxymethylammo) -ben-

Laurylammonium sulfate (20 "/ _o ig) ...... 5 g zol-chlorohydrate 0.15 g

Sodium carbonate until achieved. .... "", .. _{,, nM}

a pH value of 8 and fills with 4-nitro-1,3-diaminobenzene 0.02 g

Water on, on 100 g ammonia (20% / ₀ ig) until it is reached

6g with a pH of 3 and fills with

This solution is applied to light natural brown hair on-water based on 100 g

brought and results in an ash-colored light chestnut brown. This solution will be used on platinum yellow bleached hair

applied and gives a warm beige-gold color.

Example 9

Hair dye for an ash blonde coloration with a violet effect:

l - (/? - Hydroxyäthylamino) -2-nitro-4- (N-methyl-N-carboxymethylamino) -ben-

zol hydrochloride 0.24 g

4-nitro-1,3-diaminobenzene 0.08 g

Ammonia (20 ° / ₀ ig) until a pH value of 3 is reached and make up with water to 100 g

This mixture is applied to white hair and gives an ash blonde coloration with violet Effect.

Example 10

1 - methylamino -2-nitro-4- (carboxyme-

ethylamino) benzene chlorohydrate 0.1 g

4-nitro-1,3-diaminobenzene 0.004 g

Acetoquinone Violet Lumiere N 0.03 g

Acetoquinone Yellow Lumiere RZ 0.03 g

Ammonia (20 _^0/0 solution) until reaching a pH of 3 and make up with water to 100 g

This solution is applied to white hair and gives a very light blonde with a light pearlescent reflex.

Example 11 Hair dye for a beige-pink coloration:

1 - methylamino - 2 - nitro -4- (β- carboxyäthylamino) benzene chlorohydrate ..... Ig

Sodium carbonate until a pH of lauryl ammonium sulfate is reached (20%) 5 g

and fill up with water to 100 g

Hair dye for a very light blonde with a This solution is applied to blonde hair

slight pearlescent reflex: 25 and gives a beige-pink color.

Claims (1)

Patent claims: 1. Hair dye based on 2-nitro-1,4-phenylenediamine in aqueous solution, characterized in that it consists of at least one dye of the formula NO,