DE1569811A1 - Nitro dyes and processes for their preparation - Google Patents

Description

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Munich, October 2, 1969 M / 8210

Nitro dyes and processes for their preparation

! The invention relates to new nitro dyes and a

! Process for their preparation of the general formula

NH-R

R ¹ -N- (CH ₂ Jn-COOH

in which R is CH ₃ or CH ₂ CH ₂ OH, R ^{1 is} hydrogen or CH ₃ and η is an integer between -1 and 4 inclusive.

The new dyes can be used to advantage wherever the use of nitro dyes is common is, so preferably for dyeing keratin-containing materials, it is known, for example, 2-nitro-1,4-pehenylenediamine as an active ingredient in color solutions for hair and other keratin

Documents (Article 78, ^ ,,,, ^ 3 ^^^^^^^ BAD ORIGINAL

use fibers au. It is also known that these dyes have good cold affinity for keratinous fibers have that they have the disadvantage, however, of only delivering red-orange nuances. To achieve darker Shades, i.e. hair colors tending towards green, became substitute products for 2-nitro-1,4-phenylenediamine suggested. It was found that essentially the introduction of a methyl group in the meta position to the nitro group located amino group of 2-nitro-l, 4-phenylenediamine causes a deepening of the color nuanee. However, the products obtained in this way can only be used in a relatively limited pH range near the neutral point.

The aim of the new dyes is to avoid these disadvantages, they allow even darker shades of color tending towards blue to be achieved and they are in a wide pH range of ■ Acid pH values, preferably between pH 3 and pH 10, can be used.

The new process is carried out in such a way that by reacting l-amino-2-nitro-4-methylaminobenzene with a chloroacylamide of the formula Cl (CH ₃ J _n CONH ₂ , where η 1 means 4, such as, for example, chloroacetamide or β-chloropropionamide , 'in the secondary amino group in the 4-position a carbamyl \

0Q9828 / U1S

alkylreit, such as a Carbaraylraethyl- or Carbamyläthylrest, is introduced. The 1-amino-2-nitro-4- (M-methyl-N-carbaraylalkylamino) -benzene obtained is with ß-chloroethyl chloroformate to the ß-chloroethyl ester of the corresponding M-carbamylalkyl compound, such as 2-nitro-4. (H-raethyl-W-carbamylmethyl- or -N-carbamyl-ethylamino) -phenyl-carbamic acid, implemented. The acid amide group is then split off by hydrolysis with hydrochloric acid and the compound obtained is subjected to alkaline hydrolysis for the purpose of converting the chloroethyl ester group into the β-oxyethyl group. Then it is acidified with Hydrochloric acid obtained the monochlorohydrate of the desired compound. The reaction proceeds according to the following scheme:

BATH ORIGINAL

0 0 9 8 2 8 / U 1

NH,

2 e- (CH ₂ ) _n -cc »ni ₂

^H 3 ^C '

ο ο

H CO-CH ₂ -CT ₂ -Cl H, CO-

-O-CH ₀ -

_n -C0NH ₂

CH ₂ -CH ₂ -Cl H

KOH

_n -CONH ₂ H ₃ C (CH ₂ ) _n -COOH H ₃ C

(CH ₂ ) _n -COOH

example

Production of l- (ß-Hydroxyethyl-araino) -2-nitro-4- (N-methyl-N-carboxymethylamino) -benzene-monochlorohydrate.

A mixture of 0.4 mol (66, 8 g) i-amino-2 ~ nitro-4-methylaminobenzene, 800 cm of water and 80 g of calcium carbonate are

009828 / U1 5

BATH ORIGINAL

heated to reflux. While stirring gradually Added 1.2 moles (112.5 g) of chloroacetamide. After the addition is complete, the reflux is stopped maintained for another hour; then the reaction mixture is cooled and down to one pH 3 acidified with hydrochloric acid. The separated l-4lmino-2-nitro-4 ~ (N-methyi-N-carbaraylmethyl-amino) -

benzene is separated?

Yield: 86 g. After recrystallization from acetic acid, the compound thus obtained melts at 238 ° C,

analysis calculated for; 48, aefundern 29 C % 48.21 58 · 50 M% 5.35 24, 45 - 90 N % ■ 25.00 86 - -48, - 5, • 24,

1.45 mol (325 g) of the product thus obtained are poured into 2 liters of dioxane. After the addition of 105 g calcium carfeopat, 1.7 (244 g) ß-chloroethyl chloroformate are gradually added with reflux cooling and stirring. Afterward

009828 / 1A1S

is continued for 3 hours under reflux cooling * hit To remove the mineral salts, the reaction mixture is then filtered at boiling point and the filtrate is filtered left in the refrigerator for a night. The one in one

Amount of 120 g of precipitated β-chloroethyl ester 2-Jf itro-4- (»-aaethyl- ^ l-carbaiByl-niethylamino) -phenyl-cariaamic acid is separated off. After recrystallization from alcohol, the ester melts at 145 ° C

Analysis. calculated for 44, a found 25th ⁰ I ₂ ¹¹ IS ⁰ SV ¹ 4, 67 C % 43, 57 17th 48 · 34 ■ % 4, 54 52 · ν * 16, 94 31 - - 44, ■ V ■ 17,

0.1 mol of this ester are stirred and fts * hiteen entered at reflux in 450 cm 5 N hydrochloric acid When the product is completely dissolved, the problem will come about maintain it under reflux for another 1/4 hour »! at* close4 this reaction mixture is poured into 5OO car lis-

009828 / U15

^8AD

water poured. The separated t-Chlorftthylester 2-Kitro-4- (K-methyl-N-carboxin »ethylasiino) -phenylcarbaric acid - 19 g - melts after recrystallization from dilute acetic acid at 147 ° C.

Analvse calculated 43 fflt 44, a found • 14th ^c iAiV 22nd 3 ^C1 4, - 44, 25th C% 43. 67 13, 05 · ■ 4, 10 *% 4, 34 · • 13, H % 12, 02 -

0.034 NoI (11.2 g) of the ester thus obtained are in 58.5 cm 3 of n-hydroxide solution are dissolved, then the mixture is heated under reflux for one hour. After cooling it will

acidified with 17 cm concentrated hydrochloric acid and the deposited monochlorohydrate of l- (ß-Mydroxyäthylamino) -2 -nitro-4 - (! i-methyl-N-carboxyinethylamino) -benzene separated, which, after recrystallization from 2η hydrochloric acid, begins to melt with decomposition at 135 ° C.

003828/1415 BAD

C. % H % N % Cl %

Analysis calculated for found

^C 12 ^H 14 ° 6 ^N 3 ^C1

43, 20 43, 48 - 43, 37

5, 24 5, 39 - 5 ,. 35

13, 75 13, 58-13, 64

11, 62 11; 61 - 11, 78

009828 / U 1 5

Claims (3)

P a t e η a η proverbs 1. Dyes of the general formula NH-R R ¹ -N- (CH ₂ J _n -COOH in which R is CH ₃ or CH ₂ CH ₂ OH, R ^{1 is} hydrogen or CH and η is an integer between 1 and 4 inclusive. 2. 1- (β-Hydroxyethyl-amino) -2 ~ nitro-4- (N-methyl-N-carboxymethylamino) -benzo1-monochlorohydrate. BAD ORJGIWM. 009828/1 A 1B 3. Process for the preparation of dyes of general formula NH-R R'-N- (CH ₂ ) _n -COOH in which .' CH ₃ or CH ₂ CH ₂ OH ₁ R ^{1 is} hydrogen or CH_ and η are an integer between 1 and 4 inclusive, characterized in that by reacting l-amino-2-nitro-4-methylaminobenzene with a chloroacylamide of the formula Cl (CH ₂ ) CONH ₂ , where η denotes 1 to 4, such as, for example, chloroacetamide or ß-chloropropionamide, a carbamylalkyl radical, such as, for example, a carbamylmethyl or carbamylethyl radical, introduced into the secondary amino group in the 4-position, the l-amino obtained in this way -2-nitro ~ 4- (N-methyl-N-carbamylalkylamino) benzene with ß-chloroethyl chloroformate to ß-Chloräthylester _t of the corresponding N-Carbamylalkyl compound, such as 2-nitro-4- (N-methyl- N-carbamylme £ hyl- or -N-carbamylethyl-amino) -phenyl-carbamic acid, then split off the acid amide group by hydrolysis with hydrochloric acid, the compound obtained for the purpose of converting the chlorine 009828/1 U 5 .BADOWGiNAL - li - Ethyl ester group in the ß-oxyethyl group of an alkaline one Subjected to hydrolysis and then converted into the monochlorohydrate by acidification with hydrochloric acid, 212 / where BAD ORiQ 0098 28/1 A 1 5