DE1544369A1 - Process for the preparation of water-insoluble monoazo dyes - Google Patents

Description

} Ludwigshafen / Rhein, January 22nd, 1965

Process for the preparation of water-insoluble monoazo dyes

The invention relates to new water-insoluble monoazo dyes general formula

-N = NAN ² I,

SOR ₁ ->

in which R, and Rp optionally substituted alkyl radicals, R, a Hydrogen atom or an optionally substituted alkyl radical and A is an optionally substituted p-phenylene radical, where the dyes of ionogenic water-solubilizing groups, such as free sulfonic acid or carboxylic acid groups, should be free.

The new dyes are produced in a manner known per se by condensation or azo coupling obtained, preferably by coupling the diazo compounds of amines of the formula

with compounds of the formula

0R ₁

/ R ₂
HAN ^d III

where R ₁ , R 1, R, and A have the meanings given above.

Of the dyes obtained according to the invention, there are technical ones .Base those preferred that of the general formula

809828 / U90 -2-

-2-. O.Z. 25 464

where Y is a hydrogen atom, an alkyl or alkoxy group with 1 to 4 carbon atoms, a trifluoromethyl group, an acylamino group with at most 4 carbon atoms or a halogen atom, Z is a hydrogen atom, an alkyl or alkoxy group with at most 4 carbon atoms and R ₁ , R ₂ and R ^ have the meanings given above.

Substituted or unsubstituted radicals in particular come as R. low molecular weight alkyl radicals, especially the methyl, ethyl, propyl or butyl radical * as radicals Rp and R ^, equally low molecular weight Alkyl radicals, which may have substituents, for example nitrile, halogen, hydroxy, alkoxy, acyloxy and carbalkoxy groups, included, into consideration

For example, the following radicals may be mentioned for Rp and R ^: Methyl, ethyl, propyl, butyl, ß-cyanoethyl, ß-hydroxyethyl, ß, Jf-dihydroxypropyl, ß-hydroxy- jf-chlorpropyl, carbomethoxyethyl, Carboethoxyethyl, carbomethoxypropyl, acetoxyethyl, methoxypropyl, Ethoxyethyl, ethoxypropyl, methoxyethyl, ß-chloroethyl, butan-3-on-1-yl.

Coupling components of the formula III for the preparation of the new dyes are, for example;
N-ethylaminobensol,
N-butylaminobenzene,
N-cyanoethylaminobenzene,

N-methoxyethyl-5-methylbenzene,

909828 / U90

-3- ■. ο.ζ.

Ν, Ν-diethylaminobenzene,

N-ethyl-N-ß-hydroxyethylaminobenzene, N-ethyl-N-ß-cyanoäthylamlnobenzol, N-ß-HydroxySthyl-N-ß-cyanoethylaminobenzene, N-ethyl ~ N-ß-acetoxyethylaminobenzene, N-fithyl-N-ß-methoxyethylaminobenzene, N-ß-acetoxyethyl-N-ß-cyanoäthylaminobenzene, N, N-di- (ß-hydroxyethyl) aminobenzene, N-ß-carbomethoxyethyl-N-ß-hydroxySthylaminobenzene, N-ß-acetoxyethyl-N-ß-hydroxyethylaminobenzene, N-ß-methoxyethyl-N-ß-hydroxyethylaminobenzene, N-ß-methoxyethyl-N-ß-cyanoethylaminobenzene, W-ß-methoxyethyl-N-ß-carbomethoxyethylaminobenzene, N-ß-methoxyethyl-N-ß-aoetoxyäthylaminobenzene, N-ß-Methoxyäthy1-N- (butan-3-on-1-yl) -aminobenzene, N-ethyl-N-ß-cyanoethyl-3-methylaminobenzene, N-ethyl-N-ß-hydroxyethyl-3-methylaminobenzene, N-Ethyl-N - ^ - acetylarninopropyl-3-methylamino benzene, N, N-Di- (ß-hydroxyethyl) -3-methylaminobenzene, N-ß-cyanoethyl-N-ß-hydroxyethyl-3-methylaniinobenzene, N-ß-cyanoethyl-N-ß-methoxyethyl-3-methylaminobenzene, N-ß-cyanoethyl-N-butyl-3-methylaminobenzene, N-ß-hydroxyethyl-N-butyl-3-methylaminobenzene, N-ß-chloroethyl-N-butyl-3-methylamlnobenzene, N-ß-chloroate: '. Yl-N-ß-methoxyethyl-3-methylaminobenzene, N, N-di ~ (ß "-hydroxyethyl) -3-chloraminobenzene, N-ß-hydroxyethyl-N-ß-cyanoäthyl - ^ - ohloraminobenzol,

909828 / 1-4 90

-4- O.Z. 25th

N, N-di- (ß-hydroxyethyl) -> - acetylamino - aminobenzene, N-ß-hydroxyethyl-N-ß-cyanoäthyl -> - acetylamino-aminobenzene, N, N-di - (.ß-hydroxyethyl) -2-methoxy-5-acetylamino-aminobenzene, N-ß-hydroxyethyl-N-ß-cyanoethyl ^ -methoxy - ^ - acetylamino-aminobenzene.

The diazo component]! of formula II are new compounds. she are known per se, for example by nitrating alkyl (2-acylaminopheny 1-) sulfoxide [Th. Zincke and G. Siebert, Ber. 48, 1242 (1915) 3 and saponification of the acetylamino group obtain.

The dyes obtainable according to the invention are particularly suitable in finely divided form, ideal for dyeing structures such as fibers, threads, flakes, woven and knitted fabrics made from acetyl cellulose (2 1/2 and triacetate), synthetic linear polyesters and synthetic linear polyamides.

The new dyes are characterized by good fastness properties and good Pulling power off. In particular, in many cases, the excellent ones are To emphasize the wet, light, exhaust gas and thermal fastness properties of the dyeings obtained with the new dyes

The parts given in the examples are parts by weight and percentages relate to percentages by weight; Parts of space relate to parts by weight like the liter to the kilogram under normal conditions.

example 1

In a mixture of 14.5 parts of nitrosylsulfuric acid (with a content of 13.1 % dinitrogen trioxide) and 22 parts of concentrated

909828 / U90 ~ ⁵ ~

O.Z. 23 464

Sulfuric acid is carried at 0 to 5 C with stirring, 10 parts of 1-amino-2-methylsulfinyl-4-nitrobenzene a. After stirring for 12 hours, the mixture is poured onto 200 parts of ice and the diazo solution is filtered while stirring in a solution of 8.5 parts of N-ethyl-N, ß-hydroxyethylaminobenzene in 25 parts of water, 100 parts of ice, 1 part of sulfamic acid and β parts by volume of concentrated hydrochloric acid. A solution of IJO parts of anhydrous sodium acetate in 600 parts is then left Flow in water, stir for a further 12 hours and sucks off the crystalline dye.

The dye obtained, washed with water and ^{dried at 50 °} C. under reduced pressure, dyes acetate silk in ruby-red shades of very good lightfastness.

Valuable dyes are obtained in the same way if one is used as Coupling components used the compounds given in the table below.

Example coupling component dye gate of dyeing on No. acetate polyamide polyester

' ^C 2 ^H 5

scarlet purple red scarlet

• -N

Red

violet red red

Red

violet red red

scarlet red
909828 / U9Ü

Red

-6-

O.Z. 23

1 5AA369

Example coupling component 'hue of the coloring

No. Acetate polyamide polyester

red purple red red

red purple red red

8 f \ V _N - * - <* ruby violet violet red

scarlet red

Scarlet fever

io C / \ Vn

.C ₂ H ₄ CN scarlet red

Red

red ruby red

^ C ₂ H ₄ O ₂ CCH ₃ red ruby red

red purple red red

909828/1490

-7-

O.Z. 25 464

15U369

Example coupling component hue of the coloring

No, acetate. Polyamide polyester

C "H _r

15th

, H ^ NHCOCH,

.C ₂ H ₄ OH

CH,

19 (/ Vn ²

V = / ^ C ₀ H ₁₁ OCH, CUf ^{2 4} >

/ C ₀ Hj ₁ Cl

C. "f

CH-

22 <'^ N

CI

violet-red violet-red red

red-violet red-violet red red

violet red red

red-violet red-violet red-violet red-violet blue-violet red-violet

violet red red

Red Red

Red

red-violet red-violet

red red-violet red-violet

909828 / U 90 -8-

. Ο, Ζ. 23 464

Example coupling component hue of the coloring

Nr ₈ acetate polyamide polyester

23

Red

purple red

24

Cl scarlet red

Scarlet fever

25 ν [/ - ^Ν ( ^σ 2 ^Η 4

HNCOCH, red-violet violet

red-violet

26th

HNCOCH. rub in

violet red red

0ΠΗ-

C ₂ H ₄ OH

/ TV _n ^ " ² ^

COCH violet reddish violet blue

28 </ VN (C ₂ H ₄ OH) ₂

COCH-reddish blue blue

violet

yellow

brown-yellow brown-yellow

ff -NHC ₂ H ₄ CN yellow

orange

yellow-orange

909 8.2 8/1490

-9-

O. Z. 23,464

15U369

Example coupling component 'hue of the coloring

No. Acetate polyamide polyester

yellow

brown-yellow brown-yellow

brown red violet brown violet

Brown

yellow

Brown

brownish yellow

909 8 28/149 0

-10-

Claims (1)

-10-> O.Z. 23 464 15U369 claims 1. Process for the production of water-insoluble monoazo dye fen the general formula O ₂ NZ ^- VN = NAN ^ SOR ₁ ? in which R and R _{2 are} optionally substituted alkyl radicals, R ^, a hydrogen atom or an optionally substituted alkyl radical and A is an optionally substituted p-phenylene radical, the dyes being free of ionogenic water-solubilizing groups, characterized in that these dyes are in produced in a manner known per se by condensation or azo coupling, preferably by coupling the diazo compounds of amines of the formula 'OpN-Z ~ VNH _p SOR ₁ with compounds of the formula HAN ² , where R ₁ , R ₂ , R, and A have the meanings given above 2 · Process according to Claim 1, characterized in that the coupling components used are compounds of the formula } / \ Vn ^ -11-909828 / U 9 0 -11- O.Z. 23 464 1544363 used in which Y is a hydrogen atom, an alkyl or alkoxy group with 1 to 4 carbon atoms, a trifluoromethyl group, an acylamino group with at most 4 carbon atoms or a halogen atom, Z is a hydrogen atom, an alkyl or alkoxy group with at most 4 carbon atoms and R «And IU have the meanings given in claim 1. 3 · Colorants of the general formula 0 _ο Ν- ('Vn = NAN SOR ₁ where R ,, Rp, R, and A have the meanings given in claim 1 to have. BADISCHE ANILINE- & SODA-FABRIK AO 90 9 8 28 / U90.