DE1617693B2 - HAIR DYE PRODUCTS BASED ON 2-NITRO-1,4-PHENYLENEDIAMINE IN AQUATIC SOLUTION - Google Patents

Description

NO,

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 «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 affinity for cold Have keratin fibers, but they have the disadvantage of only delivering red-orange nuances. To the Achieving darker nuances, d. H. Hair dyes tending towards green became substitute products suggested by 2-nitro-1,4-phenylenediamine. It was found that essentially the introduction a methyl group into the amino group of 2-nitro-1,4-phenylenediamine which is in the meta position to the nitro group causes a deepening of the color nuance. 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

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.

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 at Change in pH after the alkaline

. To deliver side colorations with deeper color nuances. 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.
Those in the hair dyes according to the invention

Ao used dyes can be produced in various ways. They can be prepared by first reacting l-amino-2-nitro-4- (N-methyl-N-carbamylalkyl-amino) -benzene, the alkyl radical of which contains 1 to 4 carbon atoms, with p-toluenesulfonyl chloride 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 Cl (CH ₂ ) “CONH _? , where η 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 l-amino-2-nitro-4- (N-methyl-N-carbamylalkylamino) -benzene obtained is with / I-chloroethyl chloroformate to / 3-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 in order to convert the chloroethyl ester group into the /? - 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

NH

NO,

C1 (CH ₂ ) "CONH ₂ ,

R '- N - (CH ₂ ) ,, - COOH

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

3 4

For example example 5

Hair dye for ash blonde with a 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-5 ₁ . _Methylamino . ₂ . _nitro . _{4th (N. carboxy} .

^h y ^{drat ü} ' ^{3 g} methylamino) benzene chlorohydrate ... 0.8 g

with 10 moles of ethylene oxide oxyäthylenierter.

Laurel alcohol 5 a sodium carbonate until achieved

^y , '. '"'. ',. a pH of 9.5 laurylammo-

Sodium carbonate until a _{10th grade is achieved} sodium sulphate (20% / _n ig) 5 g

pH value of 3 and fill with water ^{K lo &) g}

_{to 5 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. I _{wear 5} and makes a light maroon with

dark purple effect. B ei s ρ i e 1 2

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

colored reflections: ₂₀ hair dyes for dark blond with mother-of-pearl

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

N-carboxymethylamino ^ -benzene-chloro- _1,. . .

_{h drat 06} l-methylammo-2-mtro-4- (N-carboxy-

_T,. ''''''"',':''methylamino) benzene chlorohydrate ... 0.8 g

Laurylammonium sulfate (20 ° / ₀ ig) 5 g ₂ , ..

Sodium carbonate until a ^mi } ^1Ο _τ mol of ethylene oxide oxyäthylenier-

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 gives a dark blonde with a mother-of-pearl-like Example 3 effect.

Hair dye for chestnut brown with violet be i s ρ i e 1 7

colored effect:

".. _TT , _,,. . _. Hair dye for beige with strong ashy

l-05-Hydroxyathyl-arnino) _{-2-nitro-colored per} i _mut terartigen reflections:

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

benzene chlorohydrate 0.6 g ⁴ °

l-hydroxy-2-amino-5-nitrobenzene 0.01 g l-methylamino-2-nitro-4- (N-methyl-

M 1 η w 1 χ 1 1 j -Ii · N-carboxymethylammoj-benzene-chloro-

with 10 moles of Athylenoxyd oxyäthylenier- hvHrat η 14 σ

ter lauryl alcohol 5 g ^y ' ^g

Sodium carbonate until reaching 45 4. Nitro-1,3-diamnobenzene ... .... ... 0.02 g

a pH value of 9 and fill with ammonia (20 ° / ₀ ig) until it is reached

Water, to 100 g f ^'nes P ^H -value of 3 and filled 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

nienbraun: "_ .., ..... . ,.

Hair dye for a warm beige gold

l-0? -hydroxyethylamino) -2-nitro- coloring:

4- (N-methyl-N-carboxymethylamino) _-1 . " _Tr , _ .., .-.". ",, _{/ XT}

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

■,. ,.,. "- _n,. . '& 60 methyl-N-carboxymethylammo) -ben-

Laurylammonium sulfate (20 "/ ₀ ig) 5 g zene chlorohydrate 0.15 g

Sodium carbonate until achieved. . _ · ,, ...,, nm

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

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

65 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 is 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 - (carboxymethylamino) 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%) until a pH value of 3 is reached and fills with Water on, to 100 g

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

sulphate (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 NH-R