DE1901485A1 - Water-insoluble monoazo dyes and process for their preparation - Google Patents

Description

FARBWERKE HOECHST AG. formerly Master Lucius & Brüning

File number: Fw 5447 a

Date: January 10, 1969

Dr.Mü / Blt

Water-insoluble monoazo dyes and process for their preparation

Addition to patent application P 16 44 221.0 (F 52 992 IVb / 22a)

The subject of patent application P 16 44 221.0 (F 52 992 IVc / 22a) are water-insoluble monoazo dyes of the general formula (1)

(1)

in which D denotes the remainder of a diazo component of the benzene series, which is free of water-solubilizing groups, R ^ a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, R- a hydrogen, chlorine or bromine atom or an alkyl group of 1 to carbon atoms, a Alkoxy group of 1 to 4 carbon atoms or an acylamino group of 1 to 4 carbon atoms, R ₃ and R _{4 are} hydrogen atoms or alkyl groups of 1 to 4 carbon atoms, and R _{5 is} an alkyl group of 1 to 4 carbon atoms or a phenyl radical, where the radicals R ₄ and R ₅ can be linked to form an oxazolidinone ring,

009839/1737 _BAD original

190U85

- 2 - Fw 5447 ft

and a process for their preparation by adding aromatic amines of the general formula (2)

D - NH ₂ (2)

in which D has the meaning given above, diazotized and with azo components of the general formula (3)

<> - N-Ch ₂ -CH ₂ -SO ₂ ^ COOR _{5 (3)}

in which R ^, R ", R_, R ₄ and R _{5 have} the meanings given above, combined.

These dyes produce on synthetic fiber materials, such as cellulose triacetate, Cellulose-2 1/2 acetate, polyamide, polyurethane or Polyester fibers, with a very good structure, dyeings and prints, which in addition to very good light and wet fastness properties also characterized by / thermal properties

. , excellent

to draw.

In a further embodiment of this invention, it has now been found that dyes of the aforementioned general formula (1), in which R », instead of a Hydrogen atom or an alkyl group of 1-4 carbon atoms, a ß-oxethyl or ίϊ-cyanoethyl group means, with the same structure, characterized by an even better heat-setting fastness.

The new water-insoluble monoazo dyes of the general formula

009839/1737 bad original

<p 190U85

- 3 - Fw 5447 a

^R l

D-N

in which D denotes the remainder of a diazo component of the benzene series which is free from water-solubilizing groups, R- is a hydrogen atom or an alkoxy group of 1 to 4 carbon atoms, R "is a hydrogen, chlorine or bromine atom or an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms or an acyl amino group of 1 to 4 carbon atoms, R ₃ a β-oxyethyl or Q-cyanoethyl group, R ₄ a hydrogen atom or an alkyl group of 1 to 4 carbon atoms and R ₅ an alkyl group of 1 to 4 carbon atoms or a phenyl radical, where the radicals R. and R- can be linked to form an oxazolidine ring, can be prepared by using aromatic amines of the general formula

D-NH ₂

in which D has the abovementioned meaning, diazotized and with azo components of the general formula

^R 2 H ^R.

in which R-, Rg, R ₃ , R ₄ and R _{5 have} the meanings given above, combined.

009839/1737

190U-85

- 4 - Fw 5447 a

As amines, the diazonium compounds used are based on, for example, 4-nitroaniline, 2-chloro-4-nitroaniline, 2,6-dichloro ~ 4-nitraniline, 2-methylsulfonyl-4-nitroaniline and 2,4,5-trichloroaniline into consideration.

The coupling is normally carried out in an acidic to neutral medium. If necessary, additives are more moisture-binding Agents such as sodium acetate or magnesium carbonate advantageous. The dyes are insoluble and are separated off, for example, by filtration and washed with water freed from adhering electrolytes.

The new water-insoluble monoazo dyes produced according to the process are processed in the customary manner with dispersants to give coloring preparations. On synthetic fibers, such as cellulose triacetate fibers, cellulose 2 1/2 acetate fibers, polyamide fibers, polyurethane fibers or polyester fibers such as polyethylene glycol terephthalate fibers, with a very good structure, these result in dyes and prints of great color strength and very good manufacturing and usage fastness _f among which the light and thermal fastness properties are particularly noteworthy.

For dyeing polyester fiber materials, the new dyestuffs move conveniently in the form of said dyeing preparations in aqueous suspension at temperatures above 100 ° C under pressure or at about 100 ⁰ C with the addition of customary carriers used. Furthermore, strong dyeings are obtained if woven or knitted fabrics made of polyester fiber materials are impregnated with suspensions of the new dyes, dried and then one

009839/1737 bad original

"190U85

- 5 - Fw 5447 a

short-term exposure to heat, for example at 190 ° C to 210 ° C. The dyes are also suitable Excellent for dyeing fiber blends that contain polyester fiber components. When dyeing polyester fiber-wool blends the wool part - with good color yield on the polyester part - is only slightly dyed. The dyeing of wool can easily be removed again by aftertreatment with reducing agents or emulsifiers.

example 1

10 ⁰ C, was added 8 g of 2-chloro-4-nitroaniline and 1 hour at 5 ° C for up to 10 ⁰ C - in a mixture of 75 ml of 96% sulfuric acid and 8.6 ml of 35% sulfuric acid at nitro. 5 The solution is allowed to flow onto 200 g of ice. Then the excess nitrous acid is destroyed by adding a little sulfamic acid. It is then coupled with a solution of 15.8 g of N-β ~ (N-2-oxethyl-N-phenylamino) -ethyl-sulfonyl-N-methyl-carbamic acid methyl ester in 100 ml of glacial acetic acid. The mixture is then stirred for a few hours at 18.degree. C. to 22.degree. C., the precipitated dye is filtered off with suction, washed with water until the filtrate runs free of electrolytes and finally dried at 60.degree. 18 g of the dye of the formula are obtained

CH ₂ -CH ₂ -OH

O ₂ N- / Vn-NZ ^ Vn-CH ₂ -CH ₂ - SO ₂ -N-COO-CH ₃ Cl CH ₃

in fora of a red powder. In finely divided form results this dye on polyester fibers has a red dyeing with very good heat-setting fastness properties.

The following table contains further examples of procedural equipment dyes that can be produced, the last column indicating the shade that is used when dyeing on polyester tissue receives. 009839/1737

BATH

Cl

190U85

- 6 - Fw 5447 a

CH ₂ -CH ₂ -OH

2) Cl- / VN = N- / Vn-CH ₀ -CH ₀ -SO ₀ -N-COO-CH ₀ "clear νγ W 2 2 2," 3 _yellow

C ₁

CH ₀ -CH ₀ -OH

3) O ₀ NZ Vn = N- / Vn-CH ₀ -CH ₀ -SO ₀ -N-COO-CH ₀ pale V- / Y_ / 2 2 2, "3 _blue _

π » _rT T CE, stichiges

^bü 2 ~ ^CH 3. ^ Red

Cl
4)

Cl ^CH 3

° o ^N - (V ^{N == N} - <V ^N -CH _O -CH _O - SO ₀ -N-COO-CH ₀ clear V- / V- / 2 2 2, "3 red-brown

Cl

CH ₂ -CH ₂ -OH

5) C; - / Vn = N- / Vn-CH ₂ -CH ₂ -SO ₂ -N-COO-CH ₃ golden yellow Cl ^CH 3 ^CH 3

CH ₂ -CH ₂ -OH

blue-

prickly

^Red

) O ₂ NZ ~~ \ -N = NZ ^r ~ \ -N-CH ₂ -CH ₂ - SO ₂ -N-COO-CH ₃

Cl CH ^0-3 . ^aoJ - f

Cl

Cl ^^ 3

009839/1737

190U85

Fw 5447 a - 7 -

Cl

^ CHg-CHg-CN

8th)

"'"' CH ₂ -CHg-SOg-N-COO-CH ₃ yellow

CH ₃

CHg-CHg-CN

9)

^ CH ₂ -CHg-SOg-N-COO-CHg brilliant

10) 0LM- ( > -M-M- (Vh blue-

V-γ V- / ^ CH ₂ -CH ₂ -SOg-N-COO-CH ₃ stiediges

. CH ₃ ^RED

Cl

CH ₂ -CH ₂ -CN

11) OlH- (> -H-N- / VH clear

Y- / * ^ CH ₂ -CHg-SO ₂ -N-COO-CHg brown

^CH 3

009839/1737

Claims (6)

190U85 - 8 - Fw 5447 a Claims IX / Water-insoluble monoazo dyes of the general formula R- in which D is the residue of a diazo component of the benzene series which is free of water-solubilizing groups, R- is a hydrogen atom or an alkoxy group of 1 to 4 carbon atoms, R _{2 is} a hydrogen, chlorine or bromine atom or an alkyl group of 1 to 4 carbon atoms , an alkoxy group of 1 to 4 carbon atoms or an acylamino group of 1 to 4 carbon atoms, R _{3 is} a ß-oxethyl or ß-cyanoethyl group, R _{4 is} a hydrogen atom or an alkyl group of 1 to 4 carbon atoms and R- is an alkyl group of 1 to 4 Mean carbon atoms or a phenyl radical, where the radicals R ₄ and R ₅ can be linked to form an oxazolidinone ring, 2) Water-insoluble monoazo dye of the formula CH ₂ -CH ₂ -OH CH ₂ -CH ₂ - SO ₂ -N-COO-CH ₃ 009839/1737 190U85 - 9 - Fw 5447 a 3) Water-insoluble honoazo dye of the formula Cl CH-CH-OH ^{z 2} Cl CH ₃ CH ₂ -CH ₂ -SO ₂ -N-COO-CH ₃ CH ₃ 4) Water-insoluble monoazo dye of the formula Cl rl y-, CH-CH-OH O ₉ N- / Vn = N / V ^{δ l} Cl CH ₃ CH ₃ 5) Water-insoluble monoazo dye of the formula CH ₂ -CH ₂ -CN O ₉ N- / Vn = N- / Vn ^A \ -f N- / - CH ₂ -CII ₂ -SO ₂ -N-COo-CH ₃ Cl 6) Process for the preparation of -water-insoluble monoazo dye en according to patent application P 16 44 221.0 (F 52 992 IVc / 22a) characterized in that the aromatic amines of the general formula mentioned there D-NH ₂ wherein D is the remainder of a diazo component of the benzene series 009839/1737 190U85 - ίο - means that is free of water-solubilizing groups, diazotized and here with azo components of the general formula ^R 4 in which R- is a hydrogen atom or an alkoxy- ™ group of 1 to 4 carbon atoms, R "a hydrogen, chlorine or bromine atom or an alkyl group of 1 to .4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms or an acylamino group of 1 to 4 carbon atoms, R ₃ a β-oxethyl - Or ß-cyanoethyl group, R, a hydrogen atom or an alkyl group of 1 to 4 carbon atoms and R _{5 is} an alkyl group of 1 to 4 carbon atoms or a phenyl radical, where the radicals R ₄ and R- can be linked to form an oxazolidinone ring, couples . 009839/1737