DE1569809A1 - Nitro dyes and processes for their preparation - Google Patents

Description

8. "January 1970 Munich,
H / 8206

Nitro Dyes and Processes
for their production

The invention relates to new nitro dyes of the general formula

R «-N- (CH ₂ J _n -COOH

9828/1413. - - *

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in which R CII ₃ or CH ₂ CH ₂ OH, R ^{1 is} hydrogen or CH ₃ and η is an integer between 1 and 4 inclusive, and a process for their preparation.

The inventive method is carried out in such a way that, for example, l-methylamino-2-nitro-4-aminobenzene with a chloroacylamide of the formula Cl (CH ₅ ) CONH-, where η is 1 to 4, such as chloroacetamide or 8-chloropropionamide for Reaction is brought and in the resulting N-carbamylalkyl! Compound, such as l-methylamino-2-nitro-4-carbaraylmethyl-aminobenzene or 4- (ß-carbamylamino) -benzene, the amide group is split off by hydrolysis with hydrochloric acid.

In this case, the reaction proceeds according to the following »scheme:

NH-CH.

Cl- (CH ₂ J _n -CO-NH ₂

NH-CH

NH-CH-

- NO.

, HCl

-CONH ₀ NH- (CH ₀ ) -COOH 1

The new dyes can be used with advantage wherever the use with nitro-carbate substances is

0 0 9 8 2 8 / U 1 3

BATH ORIGINAL

15698Q9

is common, i.e. preferably for dyeing keratin-containing materials, for example it is known 2-Nitro-1,4-phenylenediarain as an active ingredient in color solutions to be used for hair and other keratin fibers. It is also known that these dyes have a good affinity in the cold for keratin fibers, but that they only show the disadvantage to deliver red-orange nuances. To achieve darker shades, i.e. hair colors that are against tend green, were substitution products of 2-nitro-1,4-phenylenediarain suggested. It was found that essentially the introduction of a Methyl group in the raeta position to the nitro group located amino group of 2-nitro-1,4-phenylenediamine causes a deepening of the color nuance. However, the products obtained in this way can only be used in a proportionate manner limited pH range close to the neutral point.

The aim of the new dyes is to avoid these disadvantages, they leave even darker ones with a tendency towards blue Achieve color nuances and are in a wide pH range of acidic pH values, preferably between 3 and 10, applicable.

0 0 9 ° 2 8/1 L 1 3

example 1

Production of l-methyl-amino-Z-nitro-4-carboxymethylarainobenzene monochlorohydrate

A mixture of 0.2 mol (33.4 g) of l-methylamino-2-nitro-

3
4-aiainobenzene, 450 cm of water and 10 g of calcium carbonate are heated to the boil under reflux cooling. Gradually, with stirring, 0.214 mol (20 g) of chloroacetamide are added and refluxing is continued for one hour. After cooling, 1-methylamino-2-nitro-4-carbamylmethylaminobenzene is separated off in an amount of 40 g; after recrystallization from acetic acid and dioxane, the product melts at 167 ° C.

analysis calculated for found

C ₉ H 12 ° 3 ^N 4 48, 14 - 47 , 99 % * fO 48 , 21 5, 35 - 5 , 3o TT q / 5 , 35 25, 19 - 25th , 00 N% 25th , 00

0.085 mol (19 g) of the l-methylamino-2-nitro-4-carbamylmethylaminobenzene thus obtained are stirred and

0 0 9 B 2 8 ' 1 L 1 3 BAD ORfQiNAL

reflux concentrated in 150 cm Hydrochloric acid entered. After refluxing for a further 30 minutes, the mixture is cooled and the Monochlorohydrate of l-methylamino - ^ - nitro - ^ - carboxymethylaminobenzene separated in an amount of 16 g. After recrystallization from concentrated hydrochloric acid the product melts between 163 - 166 ° C with decomposition.

Analysis calculated for found

C% H % N %

41 , 30 41, 48 - 41. 51 4th , 58 4, 90 - 4, 88 16 , 06 16, 12th - 16, 10

Example 2

Production of l-methylamino- ^ - nitro- ^ (ß-carboxyäthy amino) benzo1 monochlorohydrate.

A mixture of 0.4 mol (64 g) of l-methylamino-2-nitro-4-arainobenzene, 900 cm of water and 21 g of calcium carbonate are heated to boiling under reflux cooling. To and after are 0.4 mol (43 g) of S-chloropropionamide under

009828 / UI 3

Stir added. The refluxing is done maintained for 2 hours, then the reaction mixture is filtered boiling. After cooling down of the filtrate, 65 g of the crude product obtained are separated off, which after washing with boiling Toluene, for the purpose of removing the unreacted 1-methylamino-2-nitro-4-aminobenzene, and after Uinkrystallisierung from dioxane melts at 157 ° C.

analysis calculated for 50,
5, q found ^C lo ^H 14 ° 3 ^N 4 C %
II % 50.41
5.88 24-5O, 48
99-5.82

With stirring, 0.021 mol (5 g) of the obtained

3

Product in 25 cm concentrated hydrochloric acid, which was diluted with 13 cm water, entered. It is then heated under reflux for 1/2 hour, the reaction mixture is then cooled and the monochlorohydrate of 1-methylamino-2-nitro-4- (ß-carboxyäthylamino) benzene separated off in an amount of 4.5 g, which is separated off after recrystallization from dilute hydrochloric acid melts ^{at 170 ° C. with decomposition.}

BATH 009828/1 A 13

analysis calculated for q found ^C 10 ^H 14 ° 4 ^N 3 ^C1 C % 43.55 43.58 - H % 5.08 5.09 - N % 15.24 15.53 - - 43.64 ■ 5.08 • 15.48

BATH 212 / V.

O O S ': 2 S / U 1 3

Claims (3)

Claims 1. Dyes of the general formula NH-R - NO. R * -N- (CH ₀ ) -COOH in which R is CH ₃ or CH ₂ CH ₂ OH, ^{Rt is} hydrogen or CH- and η is an integer between 1 and inclusive. 2. 1-methyl-amino ^ -nitro ^ -carboxymethylarainobenzene monochlorohydrate. 3. Process for the preparation of dyes of the general formula - NO, R «-N- (CH ₂ ) _n -COOH 009828/14 in which R is CH ₃ or CH ₂ CH ₂ OH, R 'is hydrogen or CH ₃ and η is an integer between 1 and 4 inclusive, characterized in that 1-methylamino-2-nitro-4-aitiinobenzene with a chloroacylamide of the formula Cl (CH ₂ ) CONH ₂ , in which η is 1 to 4, such as, for example, chloroacetamide or ß-chloropropionamide, is reacted and in the N-carbamylalkyl compound thus obtained, such as, for example, l ~ methylamino-2 ~ nitro-4-carbamylmethylaminobenzene or 4- (ß-carbamylethylamino) benzene splits off the acid amide group by hydrolysis with hydrochloric acid. BADORIGtNAL 0 0 9 i 2 ZI H13 '