CS244721B1 - Azo-dye with 2-azo-4-nitro-1,3,5,-trimethylbenzene-6-sulpho grouping in a molecule and method of theparation - Google Patents

Description

The present invention relates to azo dyes with 2-azo-4-nitro-1,3,5-trimethylbenzene-6-sulfo moiety in the molecule and to a process for their preparation comprising the coupling of diazonium salts prepared from 2-amino-4-nitro-l, 3,5-trimethylbenzene-6-sulfonic acid or sulfonates with passive azo components.

The dyes of the invention are characterized by the general formula

(I) wherein X is hydrogen or a cation, Z is a radical of passive azokomponenty consisting of aliphatic groups -CO-CH-CO-, heterocyclic pyrazolone type or aromatic groups C _g - ^C 10 '

A represents auxochromes -OH, -NH ₂ , -OR, -NHR, -NHAr, -NHSO ₃ , -NHSO ₂ Ar, -NHCH ₂ SO 3, where X is as defined above, R is alkyl of 1 or 2 carbon atoms and Ar is aryl of 6 to 10 carbon atoms, y is 1 to 3.

According to the invention, the process for the preparation of said dyes is characterized by interacting with the diazonium salts of 2-amino-4-nitro-1,3,5-trimethylbenzene-6-sulfonic acid, characterized by the formulas IIa and IIb, respectively.

(Ha)

C »3 ₊ 2 ° ^N '- _x / N = N .YHaC ^^ Y ^ CH (IIb) wherein Y ^- represents the anion of a strong acid, and X is as previously defined, and passive azokomponentami formula Η-Ζ- ( Where Z, A, y are as defined above, at a temperature of 0 to 40 ° C and in an environment where the pH is 3 A6 13.

The diazonium salts of formula (IIa) or (IIb) may be prepared from 2-amino-4-nitro-1,3,5-trimethylbenzene-6-sulfonic acid or sulfonates according to AO 000 000. Aliphatic compounds suitable for use with passive aeocomponents, for example with acetoacetyl from the heterocyclic compounds, especially the 1-aryl-5-pyrazolone derivatives and aromatics, for example, phenols, amoniphenols, aromatic amines, naphthols, aminonaphthols and the like can be used. Coupling of diazonium salts with selected passive azo components can be performed in azochemistry.

In technical practice, it is preferred that the reaction mixture is mixed with the passive azo component solution after diazotization of 2-amino-4-nitro-1,3,5-trimethylbenzene-6-sulfonic acid or the corresponding sulfone and the pH of the reaction mixture is adjusted as desired. addition of alkali or acid. Preferably, the phenols and naphthols may be coupled in an alkaline medium and the aromatic amine coupled in a neutral or weakly acidic medium. High yields of azo dyes are obtained when working at reduced temperatures, with intensive stirring, possibly with a slight excess of passive azo components.

The following examples illustrate embodiments of the invention.

Example 1

A solution of 2-amino-4-nitro-1,3,5-trimethylbenzene-6-sulfonic acid of 150 g / l and pH = 7 to 7,5, prepared by dissolving 7,8 g of 100% substance (0,03 mol) ) in 30 ml of water using 10,9 ml of sodium hydroxide solution of c (NaOH) = 2,5 mol / l and diluted to about 6 ml of water to a volume of 52 ml, is uniformly dosed together with 12 ml of sodium nitrite solution of c ( NaNO2) = 2.5 mol / l (0.03 mol) over 1 h with efficient stirring into a charge of 18 ml of c (HCl) = 5 mol / l (0.09 mol), 80 g of ice and 80 ml of H 2 O at 5 to 10 ° C, the reaction mixture is stirred for 1/2 hour and then any excess NaNO 3 is blunt, the resulting diazonium salt is added as a suspension to a solution prepared from 80 ml of water, 5.42 g % of acetoacetanilide (0.0306 mol) and 17 ml of sodium hydroxide solution c (NaOH) = 2.5 mol / l, cooled below 10 ° C. The resulting suspension is basified to pH = 7 to 7.5 and, if necessary diluted with water, converted to a solution at 80 ° C, the dye is salted out with sodium chloride, the suspension is cooled to 20 ° C with stirring, the solid is filtered off and the filter cake Dry to constant weight at 105 ° C. A yellow azo dye powder of constitution is obtained

Example 2

To a solution of 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-carboxy-5-pyrazolone obtained by dissolving 11.74 g of 92% product (0.0306 mol) in 100 mL of water with 21 mL of solution Sodium hydroxide with a concentration of c (NaOH) = 2.5 mol / l and cooled externally to a temperature below 10 ° C, a suspension of the 2-amino-4-nitro-1,3,5-trimethylbenzene-6-sulfonic acid diazonium salt is slowly added. of the acid prepared from 0.03 mol according to Example 1. After mixing the two components, the pH of the reaction mixture is adjusted with 2.5 mol / l NaOH to give a solution (pH 5) from which it can be darkened if the pH is lowered yellow azo dye constitution

Example 3

Following the procedure described in Example 1, a diazonium salt suspension is obtained from 0.03 moles of 2-amino-4-nitro-1,3,5-trimethylbenzene-6-sulfonic acid and poured slowly into a solution of 2-naphthol prepared in a batch of 0.0306. mole by dissolving 4.41 g of 100% substance in 200 mL of water with 15 mL of NaOH at c (NaOH) = 2.5 mol / L and cooled to 10 ° C. The acidity of the orange suspension obtained is blunted with sodium hydroxide o c (NaOH) = 2.5 mol / l for neutral reaction, and after heating to 80 ° C, 10% by weight of NaCl azo dye of constitution is salted out of the resulting orange solution.

Example 4

7.69 g of 88.8% 1-naphthylamine-6-sulfonic acid (0.0306 mol) are added to 90 ml of water and dissolved in 4.5 ml of sodium hydroxide solution with a concentration of c (NaOH) = 2.5 mol / l. . 242 ml of a suspension of the 2-amino-4-nitro-1,3,5-trimethylbenzene-6-sulfonic acid diazonium salt prepared in a batch of 0.03 mol according to Example 1 is added to the solution at 8 DEG C., the acidity is blunted about 20 ml sodium hydroxide solution c (NaOH) = 2.5 mol / l to pH = 6-7 and the reaction mixture is stirred for at least 30 minutes. After heating to 80 ° C, 90 g of the vacuum salt (25 wt% NaCL / V) of the suspension are added to the resulting solution of ca. 360 ml. The suspension is stirred at room temperature and the solid is filtered off with suction. The monoazo dye of constitution is obtained from the paste by drying at 105 ° C

SO ₃ Na

Example 5

Following the procedure described in Example 1, the synthesis of the diazonium salt of 2-amino-4-nitro-1,3,5-trimethylbenzene-6-sulfonic acid in a batch of 0.03 mol is carried out slowly at a temperature of up to 10 ° C as a slurry. vigorously stirring to 100 ml of a solution prepared by dissolving 7.32 g of 100% 6-amino-1-naphthol-3-sulfonic acid in water with about 15 ml of sodium hydroxide solution with a concentration of c (NaOH) = 2.5 mol / l and previously externally cooled to a temperature below 10 ° C. After decanting the components, the acidity of about 20 ml of 2.5M NaOH is blunted to a pH = 7 0,5 0.5 and the resulting azo dye of the constitution is obtained from the orange solution obtained in the same manner as in Example 4.

Example 6

Monoazo dye constitution

was obtained in the same manner as Example 5‘z of the diazonium salt of 2-amino-4-nitro-1,3,5-trimethylbenzene-6-sulfonic acid and 3-aminophenol-4-sulfonic acid.

The table below illustrates other examples using the listed passive azo components:

Example 7 passive azo component of dye constitution

Sat ₃ h

Example 9

N-methyl-1-acid

_x 0H

H, C t ch ₃ ho ₃ s nhch ₃

Example 10

N-phenyl-peracid

Sat ₃ h

Example 11

N-phenylsulfamic acid ch ₃ o ₂ nh ₃ c

nhso ₃ h ^CH 3 Sat ₃ h

Example 12

N-tosyl-H-acid

Claims (2)

What is claimed is: 1. Azo dyes having a 2-azo-4-nitro-1,3,5-trimethylbenzene-6-sulfo moiety in a molecule of formula I wherein χ denotes hydrogen or a cation, Z is an azo moiety formed by the aliphatic moiety -CO-CH 2 - CO-, a pyrazolone-type heterocycle or an aromatic group C 8 to C 8, ^A denotes the auxochromes -OH, -ΝΗ 2 -OR, -NHAr, -NHR, -NHSO 2 X, -NHSO 2 Ar, -NHC 2 SO 4 X, where X R is alkyl of 1 or 2 carbon atoms and Ar is aryl of 6 to 10 carbon atoms and y is 1 to 3. 2. A process for the preparation of azo dyes according to claim 1, which comprises reacting the diazonium salts of 2-amino-4-nitro-1,3,5-trimethylbenzene-6-sulfonic acid of the formula IIIa or IIb (IIa). wherein Y is a strong acid anion and X is as defined above, with passive azo components of the general formula HZ- (A) _y , wherein Z, A, y are as defined above, at a temperature of 0 to 40 ° C in a pH of 3 to 13.