DE1270711B - Process for the preparation of water-insoluble azo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C09b

German KL: 22a-l

Number: 1270 711

File number: P 12 70 711.8-43

Filing date: October 24, 1963

Opening day: June 20, 1968

It has been found that new, valuable azo dyes of the general formula can be obtained

CH ₂ - CH ₂ NHCOR ₂

in which A is the residue of an aromatic-isocyclic diazo component, X is a hydrogen atom, a methyl group or an alkoxy group having 1 to 4 carbon atoms, Y is a hydrogen atom, a methyl group, an alkoxy group having 1 to 4 carbon atoms, a chlorine atom, a bromine atom or an acylamino group at most 4 carbon atoms, Ri is an alkyl group with 1 to 4 carbon atoms, a hydroxyethyl group, a dihydroxypropyl group, an acetoxyethyl group or a fully or partially acetylated dihydroxypropyl group and R _{2 is} a methyl group, a cyanomethyl group, a chloromethyl group or a trichloromethyl group is obtained when diazo compounds are obtained from Amines of the formula A - NH ₁ ? with compounds of the formula

CH ₂ CH ₂ CH ₂ - NHR

couples, where R is a hydrogen atom or an acyl radical - COR ₂ and A, X, Y, R ₁ and R _{2 have} the meaning given above and, in the event that R is a hydrogen atom, the coupling products obtained by reaction with acylating agents the dyes of the formula I completed.

As a diazo component !! diazotizable aminobenzenes, ζ in particular, are used to produce the new dyes. B. aniline and its nonionic radicals, such as halogen atoms, nitro, alkyl, cyano, acylamino, alkylsulfone, trifluoromethyl, alkoxy or carbalkoxy group-containing derivatives, into consideration. The following are mentioned in detail: aniline,! -Amino-4-nitrobenzene, 1-amino-Z-cyano ^ -nitroben / .ol, 1-amino ^ -chloiM-nitrobenzene. 1 -Amino method of manufacture
water-insoluble azo dyes

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, 6700 Ludwigshafen

Named as inventor:

Dr. Erwin Hahn, 6806 Viernheim;

Dr. Hans-Günter Wippel,

Dr. Günter Lange, 6700 Ludwi ^ shafen

2-trifluoromethyl-4-nitrobenzene, 1-amino-2-methoxy-4-nitrobenzene, 1-amino ^ -methylsulfonyl ^ -nitrobenzene, l-amino-2,4-dinitrobenzene, l-amino-2,4-dinitro - 6 - bromobenzene, 1 - amino - 4 - chlorobenzene, 1-amino-2,6-dibromobenzene, 1-amino-2-methylsulfonyl-4-nitro-6-bromobenzene.

Examples of coupling components for the production of the new dyes are: N - methyl - N - acetaminopropylaniline, N - methyl-N - acetaminopropyl - m - toluidine, N - ethyl -N - acetaminopropyl - m - toluidine, N - butyl - N - acetaminopropylaniline, N-butyl-N-cyanoacetaminopropylaniline, N -Butyl- N - acetaminopropyl-m-toluidine, N-acetoxyethyl-N-acetaminopropyl-m-toluidine, N-hydroxyethyl-N-acetaminopropyl-m-toluidine, N-methyl-N - acetaminopropyl - m - chloraniline, N - diacetoxypropyl-N-acetaminopropyl-m-toluidine, N-acetoxyethyl - N - acetaminopropyl - N '- acetyl - m - phenylenediamine.

The diazotization and coupling are carried out by processes which are customary per se.

The dyes obtainable according to the invention are eminently suitable, especially in finely divided form. for dyeing textile materials made of acetyl cellulose, polyamides and especially linear polyesters. The dyeings obtained are distinguished by good wet fastness properties and thermal stability. The in many cases very good exhaust gas fastness should also be emphasized.

From the German patent specification 963 457 dyes are already known which act as coupling components contain anilines substituted on the nitrogen by carbonamidoethyl groups. Compared to these The closest comparable dyes are those available according to the invention, deism at the nitrogen atom % o 430

Coupling component, surprisingly, dyes substituted by carbonamidopropyl groups thanks to better thermal fastness properties on polyester fabrics and, in particular, better perspiration fastness on polyamide fabric.

The parts given in the examples are parts by weight, percentages relate to Percentages by weight, parts of space relate to parts by weight like the liter to the kilogram Normal conditions.

example 1

A mixture of 13.8 parts of 1-amino-4-nitrobenzene is stirred, 40 parts of concentrated hydrochloric acid and 40 parts of water for 2 hours at room temperature, add 200 parts of ice and leave a solution of 6.1 parts of sodium nitrite in 20 parts at 0 to 5 ° C Pour in water. The mixture is stirred for 20 minutes, removed

IO any excess nitrite present by adding aminosulfonic acid and filtering the diazo solution. The filtrate is gradually added to a solution of 22.0 parts of N-ethyl-N- (3-acetaminopropyl) aminobenzene, 50 parts of water and 5 parts of concentrated hydrochloric acid. After 2 hours, 35 parts of anhydrous sodium acetate are added to this mixture, the whole is stirred for 1 hour and the reaction product is filtered off. It is washed with water and dried at about 50 ° C. under reduced pressure. A dye is obtained which dyes polyethylene glycol terephthalate in bright red shades of good fastness to rubbing and heat setting. In the same way, dyes with similar properties are obtained if the compounds in the table below are used as coupling components instead of N-ethyl-N-acetaminopropylaminobenzene.

example

Coupling component = propylene-1,3

Hue of staining

on 2 '/ ₂ acetate

on polyethylene glycol terephthalate

Red

Red

Red

Red

Red

Red

C ₃ H ₆ NH-C-CH ₃

O O

C ₂ H ₄ OC-CH ₃

C ₃ H ₆ NH-C-CH ₃

OC ₂ H ₄ OCH ₃

C ₃ H ₆ NH-C-CH ₃

O OCOCH ₃

I Il

CH ₂ - CH - CH ₂ - OC - CH ₃

C ₃ H ₆ NH-C-CH ₃ O

Red

Red

Red

Red

Red

Red

Other similar dyes with a bluish red hue are obtained if, instead of 1-amino-4-nitrobenzene 16.8 parts of l-amino-2-methoxy-4-nitrobenzene, 17.3 parts of l-amino-2-chloro-4-nitrobenzene or 20.6 parts of 1-amino-2-trifluoromethyl-4-nitrobenzene are used. '

the same

Cl

O, N

example Diazo component O Coupling component
C ₃ H ₆ = propylene-1.3 / CH ₃ / C ₂ H ₄ OH Hue of staining
on cellulose acetate OCH ₃ \ .l: ^m ::, y 8th O ₂ N - <fV- NH ₂ V ₃ H ₆ NH-C-CH ₃
O ^ C ₃ H ₆ NH - C - CH ₃
Il Red ^ C ₃ H ₆ NHC - CH ₃
Il / CH ₃ O O CH ₃ ^ C ₃ H ₆ NHC - CH ₃
O 9 the same / C ₄ H ₉ Red O- Cl ^ C ₃ H ₆ NH - C - CH ₃
O 10 the same A S / C ₂ H ₅ Red O Γ
CH ₃ ^ C ₃ H ₆ NHC - CH ₃
Ii 11 the same / s. O Red O 12th the same Red /, \ O 13th the same Red /
- '^^ /
\ -n ' -n ' -N -N

NH,

X ₂ H ₄ OCH ₃

^ C ₃ H ₆ NH - C - CH ₃ O

, C ₂ H ₅

^ C ₃ H ₆ NH-C-CH ₃ O

Red

ruby

continuation

example Diazo component Coupling component
C ₃ H ₆ = propylene-1,3 \ x ~ "" N ^ / ^ N ^ C ₃ H ₆ NH - C - CH ₃
Il / -C ₂ H ₄ OH _{/ v} / CH ₃ ^ C ₃ H ₀ NHCOCH ₃ Hue of staining
on cellulose acetate Cl / C ₄ H ₉ ^ C ₃ H ₆ NH - C - CH ₃
Il O 16 O ₂ N- / jj ^ -NH ₂ \ ^{= /} ^ ^ C ₃ H ₆ NHC - CH ₃
CH ₃ Il
O O ^ C ₃ H ₆ NH - C - CH ₃ r "^ ^ C ₃ H ₆ NH - C - CH ₃
CH ₃ ■ Ii
O ruby / C ₂ H ₅ / C ₂ H ₄ OCOCH ₃ O OCOCH ₃ 17th the same \ ^ ~ ^N / CH ₂ - CH - CH ₂ OCOCH ₃ Scarlet fever \ ^{= /} ^ ^ C ₃ H ₆ NH - C - CH ₃
Cl -Il
O / C ₂ H ₄ OCH ₃ ^ C ₃ H ₆ NH - C - CH ₃ 18th the same Il
O ruby Coupling component of Examples 15 to 22 / CoHs
<f VN 19th the same X ruby 20th the same ruby 21 the same ruby 22nd the same ruby CF ₃ 23 to 30 O ₂ N - ^ \ _ \ - ^NH 2 ruby CN 31 O ₂ N - / S _{- NH 2} ruby

continuation

32

34

35

36

Diazo component

O, N-

- NH ₂

Ο, Ν

NH,

Ο, Ν

Ο, Ν

O, N

Coupling component
C, H "= propylene-1.3

/ C ₂ H ₅
C ₃ H <, NHC0CH,

the same

the same

the same

The same color tone of the dye on cellulose acetate

violet

Brown

Brown

violet

violet

The diazo compounds of the amines of Examples 32 to 36 are coupled with those in Examples 16 to 22 described coupling components, this gives dyes that contain cellulose acetate or Dye polyethylene glycol terephthalate in brown-ruby-violet shades and in many cases very good fastness properties.

Example 37

50

To a mixture of 35 parts of nitrosylsulfuric acid (with a content of 12.1% nitrous oxide) and 25 parts of concentrated sulfuric acid are added at OC with stirring, 24 parts of 1-amino-4-nitrobenzene-2-methylsulfone. After 12 hours, the diazo solution is poured onto 200 parts of ice, filtered and the filtrate is left in a solution of 22.0 parts N - ethyl - N - (3 - acetaminopropyl) - aminobenzene, 50 parts of water and 5 parts of concentrated hydrochloric acid flow in. After stirring for 4 hours, the crystalline dye is filtered off and washed with water and dried at 40 ° C. under reduced pressure. It dyes cellulose acetate in ruby red Tones of excellent exhaust gas fastness.

If the coupling component mentioned in Examples 16 to 16 is used instead of the above-mentioned coupling component 22 coupling components listed, dyes with similar properties are obtained.

Claims (1)

Claim: Process for the preparation of water-insoluble azo dyes, characterized in that diazo compounds of amines of the formula A - NH ₂ , in which A denotes the radical of an aromatic-isocyclic compound, with compounds of the formula CH2 CH ₂ CH ₂ NHR wherein X is a hydrogen atom, a methyl group or an alkoxy group having 1 to 4 carbon atoms, Y is a hydrogen atom, a methyl group, an alkoxy group having 1 to 4 carbon atoms, a chlorine atom, a bromine atom or an acylamino group with a maximum of 4 carbon atoms, Ri is an alkyl group with 1 to 4 carbon atoms, a hydroxyethyl group, a methoxyethyl group, a dihydroxypropyl group, an acetoxyethyl group or a fully or partially acetylated dihydroxypropyl 809 560/439 group and R represents a hydrogen atom or an acyl radical —CORo, where R _{2 represents} a methyl group, a cyanomethyl group. a chloromethyl group or a trichloromethyl A-N = N group stands, couples and in the event that R stands for represents a hydrogen atom, the coupling products obtained by reaction with acylating Means to colorants of the general formula , CH ₂ - CH ₂ - CH ₂ - NH - CO - R ₂ in which A represents the radical of an aromatic-isocyclic diazo component and X. Y. Have the meanings given above, completed. and R ₂ the Documents considered: German Patent No. 963 457. When the application was announced, a coloring table with explanations was laid out.